Materials Science and Engineering R 63 (2009) 127287

Contents lists available at ScienceDirect

Materials Science and Engineering R

journal homepage: www.elsevier.com/locate/mser

Consolidation/synthesis of materials by electric current activated/assisted

sintering
Roberto Orru` a,b, Roberta Licheri a,b, Antonio Mario Locci a,b, Alberto Cincotti a,b, Giacomo Cao a,b,c,*
a
Dipartimento di Ingegneria Chimica e Materiali, Unita` di Ricerca del Consorzio Interuniversitario per la Scienza e Tecnologia dei Materiali (INSTM),
Universita` degli Studi di Cagliari, Piazza dArmi, 09123 Cagliari, Italy
b
Unita` di Ricerca del Consorzio Nazionale delle Ricerche (CNR) Dipartimento di Energia e Trasporti, Universita` degli Studi di Cagliari, Piazza dArmi,
09123 Cagliari, Italy
c
CRS4, Parco Scientico e Tecnologico, POLARIS, Edicio 1, 09010 Pula (CA), Italy

A R T I C L E I N F O A B S T R A C T

Article history: This review article aims to provide an updated and comprehensive description of the development of the
Accepted 28 September 2008 Electric Current Activated/assisted Sintering technique (ECAS) for the obtainment of dense materials
Available online 8 January 2009 including nanostructured ones. The use of ECAS for pure sintering purposes, when starting from already
synthesized powders promoters, and to obtain the desired material by simultaneously performing
Keywords: synthesis and consolidation in one-step is reviewed. Specically, more than a thousand papers published
Consolidation on this subject during the past decades are taken into account.
Pressure assisted
The experimental procedures, formation mechanisms, characteristics, and functionality of a wide
Sintering
spectrum of dense materials fabricated by ECAS are presented. The inuence of the most important
Synthesis
Electric current operating parameters (i.e. current intensity, temperature, processing time, etc.) on product
characteristics and process dynamics is reviewed for a large family of materials including ceramics,
intermetallics, metalceramic and ceramicceramic composites.
In this review, systems where synthesis and densication stages occur simultaneously, i.e. a fully
dense product is formed immediately after reaction completion, as well as those ones for which a
satisfactory densication degree is reached only by maintaining the application of the electric current
once the full reaction conversion is obtained, are identied.
In addition, emphasis is given to the obtainment of nanostructured dense materials due to their rapid
progress and wide applications. Specically, the effect of mechanical activation by ball milling of starting
powders on ECAS process dynamics and product characteristics (i.e. density and microstructure) is
analysed.
The emerging theme from the large majority of the reviewed investigations is the comparison of ECAS
over conventional methods including pressureless sintering, hot pressing, and others. Theoretical
analysis pertaining to such technique is also proposed following the last results obtained on this topic.
2008 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
1.1. Outline . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
1.2. Process description. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
1.2.1. Electric Discharge Sintering (EDS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 131
1.2.2. Resistance Sintering (RS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 134
1.3. Historical developments of ECAS processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 139
2. State of the art of systems investigated . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
2.1. Metals and alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
2.1.1. Aluminum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 147
2.1.2. Cobalt . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148

* Corresponding author at: Dipartimento di Ingegneria Chimica e Materiali, Piazza dArmi, 09123 Cagliari, Italy. Tel.: +39 070 6755058; fax: +39 070 6755057.
E-mail address: cao@visnu.dicm.unica.it (G. Cao).

0927-796X/$ see front matter 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.mser.2008.09.003
128 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

2.1.3. Copper . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 148

2.1.4. Chromium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.1.5. Iridium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.1.6. Iron. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
2.1.7. Magnesium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 150
2.1.8. Molybdenum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.1.9. Nickel . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 151
2.1.10. Niobium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
2.1.11. Rare-earth metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
2.1.12. Tantalum . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
2.1.13. Titanium. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
2.1.14. Tungsten . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
2.2. Intermetallics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
2.2.1. Nb/Al . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
2.2.2. Ni/Al . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
2.2.3. Fe/Al . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
2.2.4. Ti/Al . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 155
2.2.5. Ti/Ni . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 158
2.2.6. Ir/Nb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
2.2.7. Ti/Al/Nb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
2.3. Carbides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
2.3.1. BxCy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 159
2.3.2. CrxCy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
2.3.3. Fe3C . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
2.3.4. SiC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 161
2.3.5. TiC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
2.3.6. WC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
2.3.7. Al3BC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
2.3.8. AlZrC2 and Zr2Al3C5 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
2.3.9. Cr2AlC. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
2.3.10. Ti3AlC2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 165
2.3.11. Ti2AlC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
2.3.12. Ti3SiC2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
2.4. Borides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
2.4.1. HfB2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
2.4.2. MgB2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 168
2.4.3. SiB6 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
2.5. Nitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
2.5.1. AlN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 169
2.5.2. Si3N4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 170
2.5.3. TiN . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
2.5.4. Other nitrides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
2.6. Silicides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
2.6.1. MoSi2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
2.6.2. FeSi2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
2.6.3. Other silicides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
2.7. Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
2.7.1. Titanates . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
2.7.2. Ferrites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
2.7.3. (Na/K)NbO3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2.7.4. Al2O3-based oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 180
2.7.5. Zirconia-based oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 183
2.7.6. Alumina/zirconia oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
2.7.7. SiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
2.7.8. Mullite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
2.7.9. TiO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 187
2.7.10. Ceria . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.7.11. MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.7.12. ZnO-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.7.13. CaCoO-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 189
2.7.14. CaSiO3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
2.7.15. Oxynitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
2.7.16. SnO2-based oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
2.7.17. La-based oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 190
2.7.18. MxV2O5 (M = Cu, Ag, Zn) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
2.7.19. Other oxides. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 191
2.8. Sialon . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
2.9. Ceramicmetal and ceramicintermetallic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
2.9.1. Cemented carbides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
2.9.2. Other carbides, nitrides and boridesmetal/intermetallic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
2.9.3. Ceramic particles reinforced metal matrix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 129

2.9.4. Metalintermetallics and metalalloys composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

2.9.5. Metalsilicides composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
2.9.6. Oxides/metal or oxides/intermetallic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
2.9.7. Other ceramic-metal and ceramic intermetallic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
2.10. Ceramicceramic composites. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
2.10.1. Al2O3-containing composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
2.10.2. SiC-containing composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 214
2.10.3. Si3N4-containing composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 217
2.10.4. Ti3SiC2-containing composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
2.10.5. Zirconia-containing composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
2.10.6. Borides-containing composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
2.10.7. Other ceramicceramic composites systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2.11. HA-containing materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
2.12. Chalcogenides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
2.13. Polymer-containing materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.14. Functionally graded, coatings and laminated materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
2.15. Systems for joining. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 234
2.16. Graphite/carbon-containing materials. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
2.17. Other systems. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2.17.1. MgSiBi . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2.17.2. SiGe . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
2.17.3. CoSb-based. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
2.17.4. ZnSb . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
2.17.5. ZrNiSn-based materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
2.17.6. Fe-magnetic alloys. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
2.17.7. Ba6C60 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.17.8. Boron icosahedra compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.17.9. Carbonitrides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
2.17.10. LiHf2(PO4)3 and LiTi2(PO4)3-based. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.17.11. Zn-doped CuAlS2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.17.12. ZnS-family phosphors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
2.17.13. Sn24P19.3BrxI8x . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
3. Modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 245
4. Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 276
Acknowledgements. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
Appendix A. List of ECAS processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 278

1. Introduction countries, being Japan characterized by the largest number of ECAS

1.1. Outline
This review article aims to provide an updated and compre-
hensive description of the development of the Electric Current
Activated/assisted Sintering (ECAS). When applying this technique,
loose powders or a cold formed compact to be consolidated are
inserted into a container which is heated to and then held at the
desired temperature, while pressure is applied and maintained for a
given period of time. Heat is provided by passing an electric current
through the powders and/or their container, thus exploiting the
consequent Joule effect.
The increasing importance of the ECAS method as a tool for
consolidation of powders is demonstrated by the large number of
papers published in the recent years. It should be noted that
references written in English language, at least at the abstract level,
since 1922 to 2007 are taking into account. Specically, Fig. 1
shows those ones published on this topic since the rst pioneering
work published during the last century [1]. From Fig. 1 the
seemingly exponential increase in the number of papers since
1999 may be clearly observed.
Since the commercialization of the ECAS method was initiated
in Japan, it is not surprising that the vast majority of published
papers are from Japanese authors, as it can be seen from Fig. 2.
China and Korea reach the second and third position, respectively,
while the contribution of the remaining countries is less numerous.
This distribution reects the equipment availability in these
installations.
As it will be shown subsequently in this review, the use of the
electric current to aid pressure assisted sintering of materials is the
subject of a large number of investigations. The emerging theme is
that this technology seems characterized by technological and
economical advantages over conventional sintering methods such
as faster heating rate, lower sintering temperature, shorter holding
time, consolidation of difcult-to-sinter-powders, elimination of
the need of sintering aids, no need of cold compaction, less
sensitivity to initial powders characteristics, and marked com-
parative improvements in the properties of materials consolidated.
In particular, lower temperatures and shorter processing times
give the possibility to sinter nanometric or metastable powders to
near theoretical density with little grain growth or retention of
metastability and cleaned grain boundaries.
Moreover, due to the shorter processing time, air sintering often
results appropriate with no need of controlled environments. In
addition, the relatively short cycle time can prevent undesirable
phase transformations or reaction in the initial materials. Further-
more, due to its characteristics, fully sintered parts of uniform
density, close or equal to theoretical, or of controlled porosity, can
be produced by ECAS process very rapidly to near nal cong-
uration, with very low reject rates of the produced objects. For
costly materials, this means considerable cost savings from
reduced machining requirements and materials scrap.
In addition, it should be noted that for engineering purposes
shorter processing times usually result in productivity gains. As
130 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 1. Number of publications related to ECAS processes.

a consequence, sintered parts of higher quality may be expected to
be obtained at lower processing costs. ECAS has demonstrated
considerable potential for rapid transfer of laboratory developed
technology to industry with no scale-up necessary for parts up to
5 cm in diameter [2].
1.2. Process description
The ECAS process is schematically shown in Fig. 3. It
simultaneously applies an electric current along with a mechan-
ical pressure in order to consolidate powders or synthesize and
simultaneously densify specic products with desired congura-
tion and density. The applied electric current and mechanical load
may be constant throughout the sintering cycle or may vary
during the selected densication stages. In particular, the current
may be adjusted by an automatic controller so that a prescribed
temperature cycle is followed.
Powders to be consolidated, which can be electrically conduct-
ing or insulating, are placed in a container (die, tube, etc.) and
heated by applying the electric current. In the case of conducting
powders the container can be conducting or insulating. Alter-
natively, instead of an insulating container, a conductive container
with insulating material lining on the inner surface can be used. On
the contrary, when the powders are insulating, the container
should necessary be conducting in order to guarantee the electrical
circuit closure. For the same reason, the electrodes carrying the
current, and all blocks, spacers or plungers inserted if necessary in
the circuit should be made of electrical conducting material
(copper, graphite, stainless steel, etc.). Conducting powders are
heated by Joule effect and by heat transfer from the container and
electrodes, while the non-conductive powders are heated only
through the latter way. Conductive containers can be of graphite,
ceramic, or steel. The use of graphite containers, which are mostly
applied in ECAS processes, limits the mechanical pressure levels to
low values, generally 100 MPa, but provides a reducing component
to the sintering environment. The mechanical load may be
constant throughout the sintering cycle or changed in different
densication stages.
While similar in some aspects to Hot Pressing (HP), the ECAS
process is characterized by the application of the electric current

Fig. 2. Number of publications related to ECAS processes by country.

 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 3. Schematic representation of the Electric Current Assisted Sintering (ECAS)
process.
through a power supply, leading to very rapid and efcient heating.
The heating rate during the ECAS process depends on the geometry
of the container/sample ensemble, its thermal and electrical
properties, and on the electric power supplier. Heating rates as
high as 1000 8C/min are frequently achieved. As a consequence, the
processing time ranges from fraction of seconds to minutes
depending on the material, part size, conguration, and equipment
capacity.
On the contrary, in conventional HP techniques, the powder
container is typically heated by radiation from the enclosing
furnace through external heating elements and convection of inert
gases if applicable. Therefore, the sample is heated as a
consequence of the heat transfer occurring by conduction from
the external surface of the container to the powders. The resulting
heating rate is then typically slow and the process can last hours. In
addition, a lot of heat is wasted as the whole volume of space is
heated and the compact indirectly receives heat from the hot
environment. On the other hand, ECAS processes are characterized
by the efcient use of the heat input, particularly when electrically
insulating container is used and the electric current is applied for
extremely short duration (down to few hundreds of microse-
conds).
It should be however mentioned that in ECAS processes the
problem of adequate electrical conductance of the powders and the
achievement of homogenous temperature distribution is particu-
larly acute. In fact, current and consequent temperature distribu-
tions within the sample are very sensitive to the homogeneity of
density distribution. Moreover, large density spatial variation,
especially at the beginning of current ow, may result in high local
overheating or even melting.
For these reasons, most of the specimens sintered so far have
either cylindrical or rectangular shape leading to the conclusion
that parts may be more successfully sintered by the ECAS process if
they have small sizes and simple shapes. Furthermore, even when
consolidating simple parts which also have uniform thickness in
131
the direction of pressing and of current passage, problems are
encountered in obtaining uniform temperature distribution.
The electric current delivered during ECAS processes can in
general assume different intensity and waveform which depend
upon the power supply characteristics. However, regardless the
waveform of the applied current during the ECAS process, it should
be emphasized that Joule heating, which is in turn responsible of
the temperature reached during the process, is related to the root
mean squared of the instantaneous current intensity, as dened by
the following equation:
v
u tZt
u
u1
IRMS t I2 tdt (1.1)
t
t
where I represents the instantaneous current and t the sampling
time.
The mechanical load during ECAS processes is typically
provided uniaxially. However, specic experimental set-up have
been designed in order to apply isostatic [3] or quasi-isostatic [4]
pressure to the sample to be consolidated. Ultra-high isostatic
pressure up to 8 GPa was also recently available [5].
With respect to the applied current characteristics, several
classications of the ECAS processes have been reported [68].
However, in the authors view, the various consolidation techni-
ques which make use of an electrical current can be divided in two
main categories:
 Resistance Sintering (RS).
 Electric Discharge Sintering (EDS).
This classication is partially adapted from the one recently
reported in the literature by other authors [9].
RS involves the application of a low-voltage (of the order of few
tens of volts)high current (of the order of thousands of amps)
with a suchlike waveform (direct current (DC), alternate current
(AC), rectied current (RC), pulsed, etc.). On the other hand, EDS
made use of the electrical energy stored in a capacitor bank and
suddenly released to the powder compacts. Higher voltages and
higher current with respect to RS are typically involved during EDS,
being the electric energy discharged through few heavy pulses. In
addition, the change of current with time (dI/dt) during the EDS
process has the potential to provide a signicant contribution to
the compaction by exploiting electromagnetic phenomena [10,11].
Another signicant difference between EDS and RS processes is the
characteristic processing time. Specically, the EDS processing
time typically falls in the range 105 to 102 s, while the one of RS
processes is of the order of 100 to 103 s.
In Fig. 4, the relative amount of scientic reports regarding the
two methods are reported. It can be seen that the RS technique is
the more deeply investigated. In what follows a general description
of the two methods will be given.
1.2.1. Electric Discharge Sintering (EDS)
In this process, also named electric discharge compaction
(EDC) [12] or Environmental Electro-Discharge Sintering (EEDS)
[13,14], electrical energy is suddenly discharged from a capacitor
bank through a column of powders contained in an electrically
non-conducting tube. The high transient current passing through
the column causes heating and sintering of individual powder
particles. Simultaneously, this current generates an intense
magnetic eld in the azimuthal direction, which tends to collapse
the powder body radially inward. Hence, after discharge, the
compacted preform is free to slide within the container and can be
removed easily for subsequently processing [10,11]. The ease with
132 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 4. Relative amount of scientic reports regarding the two main ECAS processes.

which the preform can be removed from its container, cheapness

of containers and the fact that the latter one may be reused several
times before replacement are claimed to be particular advantages
of this method of compaction [15,16].
The rst electrical discharge unit for compacting the preforms
was originally built as a magnetic forming machine [17]. The
capacitor bank typically consists of several capacitors of a total
capacitance up to 25 mF [18] while a charging voltage up to 30 kV
[19] may be reached. The capacitor bank is charged using a variable
transformer and rectication and smoothing unit [10,11,17,20].
The scheme of the discharge circuit, and the equivalent electrical
circuit are shown in Fig. 5 where the column of metal powder
works as a short circuit resistance across the capacitor bank
[10,11,21]. The applied discharge current density and intensity can
reach up to 2800 MA/m2 [9] and 90 kA [19,22], respectively. In
particular, the current was found to decrease monotonically with
increasing length of the specimen, whereas it increased when
specimen diameter is augmented [10]. A typical waveform of the
current owing through the powder column during this process
is reported in Fig. 6, where critical, over- and under-damped
situations are shown [1012].
Other investigations [23] however, reported that the process
may be constituted of two stages. During the rst one, the powder
are formed by means of a high-voltage pulse, while during the
second phase the proper sintering operation is carried out at
Fig. 5. (a) Scheme of EDS process; (b) equivalent electric circuit. Adapted from
Clyens et al. [10].
a current density in the sample of the order of 102 to 103 A/cm2.
The need for such a two-stage sintering was reported to be caused
by the fact that during EDS processes the electrical resistance of
samples may decrease by about six orders of magnitude.
The process can be in general performed with or without
pressure application [24]. In the former case, static as well as
dynamic pressure can be applied. Static mechanical pressures up to
710 MPa have been applied [18]. The effects of simultaneously
applying dynamic axial load and electrical discharge were studied
by varying the duration between the onset of discharge and that of
maximum axial force in order to obtain a more dense compact [24].
In another work, it was indicated that in order to have a reasonably
high-achieved density (>95%), the green density should be more
than 80%, thus creating the need of a cold pressing stage [25]. In
addition, it was observed that a minimum amount of pressure
is necessary for effective discharge to occour [18]. In fact, when

Fig. 6. Typical waveforms of the current owing through a powder column during EDS process. Critical, over- and under-damped situations are shown. Adapted form
Alp et al. [12].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 7. Typical shapes of metal powder preforms obtained by EDS. Adapted from Al-
Hassani [15].
discharge was passed through loose powder not only densication
does not take place, but also intense sparking occurred between
particles resulting in the rupture of the container [18]. This was
attributed to the lack of sufcient energy input to overcome the air
gaps [18].
Several metallic powders have been processed by EDS,
although not always effectively [15,16,18,25], being the process
most successful with ferrous materials [20]. It was reported that
bars and strips have been produced by means of this process
[15,16], in addition to samples generally characterized by a high
aspect ratio [20]. As shown in Fig. 7, complicated shapes such as
angled bars, and strips with sharp corners have been also
compacted by using suitable powder particle size arrangement
[12,21]. The careful choice and positioning of particles according
to their mesh sizes was reported to be essential in order to guide
the current in desired directions and to achieve a fairly homo-
geneous product in density and mechanical properties [12,24]. It
was also claimed that long powder metallurgy bars of hard facing
materials as those obtained by this method are normally difcult
to produce without prolonged sintering and high costs [12].
Variables such as electrical circuit parameters, powder proper-
ties, as well as column dimensions and geometry, inuence the
success of compaction for a given energy input [12,16]. However,
Fig. 8. Typical surface appearance at different magnications of a porous titanium implant compact after EDS. Adapted from An et al. [13].
133
the relative density obtained was typically low when mechanical
load is not applied [12,24], and therefore, a swaging and a sintering
step were reported to be necessary in order to obtain dense
sample [10].
In addition, it was claimed that the porous product of this high-
voltage powder-forming process has a number of possible
applications, such as debris ltration, uid ow control, capacitor
and catalyst bodies, and pressure surge protection units [20]. It was
indeed found that the tensile strengths of the various preforms
were much greater than those ones of preforms of the same density
obtained using an isostatic press being not possible to handle and
measure the tensile strengths of isostatically formed preforms of
such density [11]. The great increase in strengths was attributed
to the formation of interparticle welds due to heating during
the passage of the electrical discharge through metal powder
which developed good metalmetal bonds between the base
metals [11,24]. Therefore, this process was also judged useful as a
preforming stage for certain metal working processes because it
uses simple and inexpensive tools [20]. Moreover, it was claimed
that this process had potential for development due to its
simplicity and rapidity [11,12].
It is interesting to note that in powder compacts with usual
particle size distribution from few to about 150 mm, the diffusion
taking place during the very short sintering time of EDS is insu-
fcient to accomplish homogenization or reactions even at
temperature just below the appearance of a liquid phase. There-
fore, in order to achieve a considerable degree of alloying or
reaction between the metal powders in the mixture, the compact
has to be heated high enough so that a liquid phase is formed [26].
It was also found that in EDS processes interparticle welding into
continuous axial wires or brous structures aligned in the
direction of current ow can arise [10,21], specically when
the current ows through the body characterized by low aspect
ratio (large diameter) [20].
Higher degree of densication in the center of the samples is
very often obtained as a direct consequence of the higher
temperature generated in the core of the powder column [16].
In addition, the samples tended to have a higher density at both
ends of the compact than elsewhere [10]. Typical surface
appearance of a porous titanium implant compact after the
discharge is shown in Fig. 8 which illustrates the porous-surfaced
feature. Fig. 9 is an optical micrograph that illustrates a typical
compact cross-section. It is seen that a solid core can be formed by
the discharge in the center of the compact which is gradually
surrounded by a porous layer. The solid core was composed of
powder particles which were deformed and partially melt and
consequently welded together. The porous layer consisted of
powder particles that were connected by necks in three dimen-
sions [13,14].
A schematic production route of bars through EDS technique is
shown in Fig. 10 [10,11]. After the container is lled with the
134 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 9. Typical solid titanium core appearing in EDS sample. Adapted from An
et al. [13].
powders to be consolidated, it is plugged between two copper
electrodes pushed into contact with the powders column [10,11].
During discharge powders must be conned in some electrically
insulating container [10]. Pyrex glass tubes have been found to be
the most suitable for the production, since they could be used
repeatedly without pitting of the inner surface and cracks or
deformation [10,11]. Then, this method consists of charging
electric energy into capacitors and discharging it via a high-
voltage switch directly to the loose powder column [10,11]. Also
Perspex and PVC tubes have been used [15]. In addition, for strips
and complicated cross-section bars, containers made from card-
board are found to give excellent results [15]. If the density of the
obtained object is lower than the one required by the nal
application swaging and sintering steps can follow the EDS one.
The energy associated with the discharge through the powder
column is proportional to the current owing [11]. The current
Fig. 10. The production route of bars by EDS. Partially adapted from Clyens and
Johnson [10].
level, distribution and period are governed mainly by the
capacitance, resistance and inductance of the circuit (cf. Fig. 5)
[16]. While the change in inductance during the process is typically
small, the variation of the electric resistance of the circuit, due to
heating and progressive welding of particles, is appreciable [16]. It
was also noted that the higher the current owing in the circuit, the
larger are the magnetic body forces which may contribute to
increase green density and strength [16]. Therefore, the instanta-
neous current density in the specimen is the most important factor
which determines the success of the compaction process [16].
Thus it would be expected that, as the current is increased, there
would be an increase in the degree of compaction [11]. It should be
noted, however, that welding and compaction occur only for a
certain range of discharge energy [10,11]. The corresponding
acceptable range depends upon the dimension of the powders
column and the type of material being compacted [10,11]. Too
large discharge energy causes melting of the core or the sample to
completely melt or to disintegrate like an exploding wire, then
bursting its container [10,11,15,16]. It was mentioned that the
latter event can also happen as a consequence of fulgurite-type
phenomenon [16] which is normally found during geological
excavations and it is believed to be due to large current discharges
from lightning [16].
Conversely, there is a minimum voltage below which preforms
were not sufciently strong [21]. In addition, too small energy
discharge would give rise to a magnetic eld which would not be
intense enough to reduce the diameter of the powder body and
consequently it would be difcult to remove it from the Pyrex tube
without damage [10,11]. This condition can be explained on the
basis of the role played by the compact electrical resistance. If the
resistance is too high, current for sintering will not be sufcient
[26]. If the resistance is too low, sintering will not be satisfactory
because the current will not pass uniformly through the cross-
section of the compact [26]. In fact, in this latter case, a very small
current will rst follows the least resistance path in the compact
[26]. This path will be heated sufciently to cause break down of
resistance and more current will then ow through. The path will
be soon greatly overheated and expelled, while the rest of the
compact through which current hardly passes remains relatively
cold [26]. A criterion for estimating the energy input required to
obtain a satisfactory densication of the sample was also proposed
[23,25,27] while additional details about the EDS technique can be
found in dedicated reviews previously published [28].
Another EDS method named High-Energy High-Rate (HEHR)
consolidation takes advantage of a 10 MJ Homo-Polar Generator
(HPG), which converts stored rotational kinetic energy into
electrical one using the Faraday effect [29]. The HPG is a low-
voltage (525 V), high current device that is most advantageously
operated in a pulsed mode [29,30]. The bonding which occurs
during consolidation by this technique stems from the pulse
resistive heating which is produced at the interparticle interfaces
[29]. The applied current pulse is very high and can reach a
maximum up to 250 kA after few hundreds ms, while the current
density ranges in the interval 100500 MA/m2 [30,31]. The process
lasts typically less than 3 s, with most of the energy delivered
during the rst 0.5 s [30]. At the onset of the pulse, sufcient
pressure is applied and held constant for an additional time in the
range 35 min [29]. The specic energy input varies in the range
40014250 J/g [29,32]. Schematic processing outputs of this
technique are reported in Fig. 11 [29].
1.2.2. Resistance Sintering (RS)
During more than 80 years of scientic investigation performed
on the RS process, several custom-built or commercial apparatuses
have been used. In addition, different electric current waveforms
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 135

Fig. 11. Typical consolidation pulse shape applied during the HEHR process. Adapted from Elkabir et al. [29].

have been applied and a number of names and acronyms have been
introduced to designate the RS process. Fig. 12 shows the relative
distribution of the different designation adopted so far. It should be
mentioned that a distinction has to be made when the word
plasma has been used to designate one of the several RS
processes. In fact, in these cases, the specimen is not bathed in an
external plasma environment as in the real plasma sintering or
microwave sintering [8].
However, it is not an exception that different names and
acronyms have been used to indicate processes which involved
the application of the same electric current waveform or the
utilization of the same apparatus. On the other hand, in some
cases identical names have been used to designate RS processes
where different electric current waveforms have been applied or
different apparatuses have been employed. These considera-
tions, in addition to the fact that quite frequently details of the
adopted apparatus or applied current values have not been
reported or properly specied, may generate uncertainty in the
identication of the main electric features of the process under
investigation.
Therefore, since the application of an electric current is the
main feature of RS techniques, in authors view a clear classica-
tion of them may be obtained by considering the electric current
waveform that is applied during the process. In fact, on the base of
the literature review, it is possible to note that, despite the various
possible forms (square, sinusoidal, seesaw, etc.), the scientic
community has most of the time adopted the current waveforms
shown in Fig. 13, where the parameters needed for their
characterization are also indicated.
The simpler current waveform is the constant DC (cf. Fig. 13a),
which is completely characterized by the current intensity I, while
the AC, shown in Fig. 13b, is determined by maximum current
intensity Imax, along with its frequency v. The third waveform
(cf. Fig. 13c) is the pulsed DC, where the parameters needed for its
complete denition are the maximum current Imax, the pulse
duration tpulse, and the on- and the off-time, tON and tOFF,

Fig. 12. RS processes designation.

136 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 13. Typical electric current waveforms applied in the RS processes: (a) constant DC; (b) AC; (c) pulsed DC and (d) pulsed DC + DC.

respectively. In Fig. 13d, a peculiar RS process where the electric
current is applied in two stages, is shown. During the rst one, a
pulsed electric current is imposed while a constant DC followed in
the second stage. The parameters that dene the rst stage are the
maximum current Imax, the on-time tON and the off-time tOFF,
while the current intensity I is sufcient to describe the second
stage. However, in addition to the parameters that characterize
each stage, their relative duration, tI and tII, should be given.
The train of squared pulses, schematically shown in Fig. 13d,
may be compared to the corresponding experimental ones
reported in Fig. 14, which are taken from one of the sole two
papers where this information is available [7,33].
It is important to mention that a precise description of the
applied current, as well as the complete set of parameters needed
for its characterization, is rarely reported in the literature.
Therefore, the current waveforms shown in Fig. 13 should not

Fig. 14. Experimental measurements of the electric current having the waveform of the type shown in Fig. 13. Adapted from Matsugi et al. [7].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 137

Fig. 15. Relative distribution of the current waveforms applied in the RS processes as reported in the reviewed literature.

be considered exhaustive since different combinations of wave- waveforms shown in Fig. 13c or 13d have been commercialized. An
forms or pulses having different shape may have been applied apparatus similar to the Sumitomo machine is commercialized by
without explicitly reporting the corresponding details. This Izumi Technology Co. Ltd. It appears from the literature [36] that
relatively scarce attention paid to the electric features of the RS this apparatus has the possibility to vary the pulse shape and the
process is conrmed by the fact that experimental measurements pulse frequency, i.e. the pulse duration tpulse (cf. Fig. 13c) of the
of the applied electric current have been reported only in few
papers [7,3346], despite the quite relevant number of investiga-
tions related to RS processes (cf. Figs. 1 and 2).
The analysis of the scientic literature reveals that the relative
distribution of the use of the current waveforms reported in Fig. 13
is the one shown in Fig. 15. The relative amount of papers where
the waveform of the applied current was not specied is also
reported. It can be clearly seen that in the vast majority of the
scientic investigations dealing with RS processes, the application
of a DC pulsed current is involved. Such a distribution is due to the
widespread utilization of a commercial RS apparatus developed by
the Sumitomo Coal Mining Co. Ltd. (Japan), which is indeed based
on the application of an electric current having the waveform
reported in Fig. 13c. It was reported that this apparatus was based
on patents led in 1960s and marked in the late 1980s by
Sumitomo itself and another Japanese Company (Sodick Co. Ltd.)
[47]. Details about the electric current applied during the so called
Spark Plasma Sintering (SPS) process were rstly reported therein.
In particular, the electric source was indicated to be similar to that
one of an electric discharge machine [47]. It was also therein
specied that a low-voltage high current power was supplied.
Moreover, a pulse interval (tpulse) of 1 ms was specied, while by
using a different model of the same vendor (Sumitomo Coal Mining
Co. Ltd.), a pulse duration of 2.7 ms was reported by others
investigators [48]. On the other hand the duration of the pulses
applied by the Sumitomo apparatus is typically indicated to be
3.3 ms, while the on-time and the off-time can be set in the ranges
3300 ms and 330 ms, respectively. Experimental measurements
of the electric current applied by Sumitomo apparatus was rstly
reported by Song et al. [35], while a more detailed analysis was
lately carried out by Munir and co-workers [37,38]. Fig. 16 shows
the applied current pattern as a function of the on-time tON/off-
time tOFF ratio. Presently, different scales of Sumitomo machines
are available with the possibility to produce dense bodies whose
dimension are of the order of 101 m, by applying electric currents
up to 20 kA at few tens of volts.
RS processes involving the application of constant DC or AC
typically take advantage of custom-built apparatuses. On the other Fig. 16. Pulse patterns for various on-time/off-time ratios applied by the Sumitomo
hand, other apparatuses which apply electric current having the Coal Mining Co. Ltd. apparatus. Adapted from Chen et al. [38].
138 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 17. Schematic representation of the PAS process. Adapted from Groza et al. [50].

applied current. Very versatile RS machines able to apply such
electric current pattern are nowadays commercialized also by FCT
Systeme GmBH (Germany). An electric current of up 60 kA can be
applied by means of this apparatus with the possibility to vary all
the pulses sequence parameters, i.e. shape, frequency, on-time,
and off-time, and also to apply a constant DC. In particular, a pulsed
DC with on/off cycles of 0225 ms (on-time)/0255 ms (off-time)
can be generated using this apparatus [39,49].
A commercial apparatus which allows one to impose the
current waveform shown in Fig. 13d was developed in Japan by
Sodick Co. Ltd. [50]. Some authors reported that this apparatus
started to be commercialized in the 1960s [51], while others dated
its development in 1988 [52]. A prototype-version of a semi-
automated system was designed and developed in 1996 [53].
The method which takes advantage of the Sodick apparatus is
schematically depicted in Fig. 17, while typical processing
parameters are reported in Table 1. In the rst stage of this
process, the pulsed electric current is applied under a relatively
low pressure, while the imposition of DC followed in the second
stage [50]. The option to apply the two stages simultaneously was
also mentioned [8]. It was later specied that in this process, an AC
current rectier was used to achieve a controlled DC pulsing [8]. It
was therein also reported that the duration of each pulse may be
varied between 1 and 300 ms and that on and off pulses may have
different durations.
Commercial apparatuses which involve the application of
electric current having the waveform reported in Fig. 13d were
developed also by Materials Modication Inc., USA [54] and by
Eltek Co., Korea [55]. In the former case, a pulsed DC voltage (5 V
maximum and 500 A average current) is rstly applied through the
powder compacts [54]. Subsequently, a relatively high DC voltage
of about 10 V is applied to achieve rapid densication by resistance
sintering. As can be deduced by the description reported above,
this apparatus seems identical to the Sodick one. On the other
hand, the apparatus made by Eltek Co. includes a 18 V, 2800 A DC
power supply, and similarly to the Sodick one, the electric current
is applied in two stages. During the rst one, a pulsed current with
20 ms on-time and 10 ms off-time is provided while, during the
second stage, a DC is supplied.
A RS apparatus is commercialized also by the Superior Graphite
Co. Ltd. (USA) and named Electroconsolidation1. This apparatus is
quite different from other ECAS ones in the sense that pre-
compacted powders to be densied are immersed within a bed of
free owing particles that are placed inside a die [56]. The
electrically conducting granular medium acts as pressure trans-
mitter and resistive heat source while a low voltages and high DC
currents (up to 10 kA) DC are supplied. Despite the fact that a
uniaxial pressure is applied, the specimen is actually exposed to
pseudo-isostatic pressure conditions [51].
A peculiar non-commercial apparatus was developed at the
Warsaw University of Technology, Warsaw (Poland) [34]. By
means this apparatus, high current electric impulses are applied to
the material to be consolidated [34]. The high current discharges
pulses are delivered periodically from a battery of capacitors,
charged at a maximum of 10 kV [34]. The duration time of each
impulse was about 500 ms [34] or 50 ms [57], while the pulse
frequency was about 20 kHz [34]. The electric current intensity
was of the order of tens of kA (up to 80 kA). Fig. 18 shows examples
of the pulse current and voltage waveforms during the capacitor
discharge [34].
Moreover, thanks to the very short time during which the
current heats the powder, compared with the interval between
successive impulses (in the range 0.52 s [46]), the sintering
process has a quasi-adiabatic character, which means that the

Table 1
Typical PAS processing parameters.
Applied pressure 10100 MPa
Pulse voltage 25 V
Pulse current 750 A
Pulse on-state duration 22000 ms
Pulse off-state duration 22000 ms
First stage duration 3090 s
Resistance heating voltage Up to 70 V
Resistance heating current 6004000 A
Fig. 18. Examples of the electric current (a) and voltage (b) waveforms during the
Total processing time 10900 s
PPS. Adapted from Michalski et al. [34].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 19. Schematic representation of the temperature change during the PPS.
Adapted from Michalski et al. [34].
average temperature of the particles being sintered is manifold
lower than the instantaneous temperature that is achieved during
the current ow periods [34]. Fig. 19 shows schematically the
temperature variation during process [34].
The delivered energy for each pulse is typically of the order of
few kJ (up to 8.1 kJ) [41] and the pulse repetition frequency in the
range 0.52 Hz [42]. In this process, the temperature and the
heating rate during the sintering are governed by controlling the
pulse discharge energy (E = CV2/2 where V is the charge voltage and
C the capacitance of the capacitor battery [46]). It should be
mentioned that, thanks to the high energy delivered during a pulse,
this technique was claimed to be much more intensive than other
similar ones [46].
The distribution of the vendors of the various commercial
apparatuses which take advantage of the characteristics of the RS
processes considered so far is reported in Fig. 20. The relative
amount of scientic articles where the adoption of custom-built
apparatuses is specied or details about the apparatus are not
reported, is also shown.
In order to summarize some of the relevant information
reported so far, the various RS process are historically listed in
Table 2 along with the corresponding reported applied current
characteristics and the apparatus adopted. It can be clearly seen
that, as already mentioned, diverse current waveforms and/or
apparatus are adopted for the same process. In the last column of
Fig. 20. Relative distribution of apparatuses adopted in the RS processes as reported
in the reviewed literature.
139
Table 2 the references indicate where, at our best knowledge, the
process name/acronym, and for each process name/acronym, the
different applied current waveforms or adopted apparatus were
reported for the rst time. It should be noted that the names ECAS
[127], and eld activated sintering technique (FAST) [102] were
introduced to designate the consolidation methods based on the
application of a electric eld/current regardless their waveforms,
while pulse electric current sintering (PECS) was used by some
authors as a generalization of RS methods which involve the
application of a pulsed electric current [133]. It should be pointed
out once more that the applied characteristics and/or the appa-
ratus adopted were in some cases not specied. Therefore, Table 2
should not be considered as comprehensive of all possible com-
binations of process name, applied current and apparatus adopted
in this research eld.
1.3. Historical developments of ECAS processes
Although the recent widespread use of ECAS to consolidate
powder materials has been generated by the increasing availability
of commercial- and custom-built devices (cf. Section 1.2), its origin
is much older [43]. In fact, several processes which apply an
electric current or an electric eld to assist powder consolidation
have been developed in the past. In what follows, the historical
development of ECAS process is presented along with a thorough
discussion of the root reports and patents related to it. Particular
attention is paid on the applied electric current/voltage character-
istics and the most important claimed effects of the electric
current/voltage imposition are highlighted.
The rst example to our best knowledge is a U.S. Patent of 1922
[1]. It was reported about an invention related to the production of
dense articles starting from oxides powders where the electric
current ows directly through the sample to bring it at the
appropriate sintering temperature. On the other hand, the idea of
simultaneously applying a uniaxial mechanical load and an electric
current to sinter metal powders is due to Hoyt in 1927 [134]. In
Fig. 21 the drawing accompanying the Hoyts patent is shown. In
particular, a mechanical pressure was applied through the
electrodes to the conned WC/Co powder mixture and a direct
or alternate electric current was simultaneously supplied through
the electrodes connected to an external electric circuit, thereby
heating the powdered material to a temperature sufciently high
to sinter the sample thoroughly. The reported processing time was
of the order of minutes, while no information were given about the
characteristics (amperage, frequency, etc.) of the applied electric
current. Following this idea and using the same technique, in 1927
Gilson [135] performed the reactive sintering of WC/Co starting
from elemental powders W, C, and Co. Although, also in this patent,
information about the applied electric current was not reported,
this method can be considered one of the older examples of
reactive sintering assisted by electric current.
While the process patented by Hoyt needed some minutes of
current application to obtain fully dense bodies, Taylor in 1933
[136] achieved the complete densication of the WC/Co cemented
carbide in about one second or fraction thereof by modifying the
original Hoyts design. In particular, the shorter processing time
needed by the Taylors apparatus is due to the ability of discharging
a pulse of direct current to the samples followed by the imposition
of alternate current. The electric discharge was obtained by having,
in parallel with the sample to be sintered, a condenser connected to
a 2500 V source of direct current. Taylor motivated the necessity of
the electric discharge on the basis of the difculties that sometime
may be experienced in initiating a ow of electric current
through certain powders when connecting the system directly
to a low-voltage source of alternating current due to the high initial
140 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Table 2
Overview of RS processes.

Process name Reported applied current characteristics Apparatus vendor Reference

Electric sintering [58]

Spark sintering AC Japax Scientic Corp. [59]

Combination of AC and DC [60,61]
Pulsed DC + DC [7]
Pulsed DC Sumitomo Coal Mining Co. Ltd. [62]

Electric discharge sintering Combination of low-frequency AC, [63]

high frequency AC and/or DC
Pulsed [64]

Spark discharge sintering [65]

Electrically activated pressure sintering Combination of low-frequency [66]

AC and/or DC + high frequency AC

Electrical discharge-type activated pressure sintering Combination of low-frequency [67]

AC and/or DC + high frequency AC

Spark isostatic pressing (SIP) Superimposed AC+DC [3]

Electric pulse sintering Pulsed [68]

Direct resistance sintering AC [69]

Resistance sintering [70]

AC [71]
Combination of AC and DC [6]

(Direct) Electric resistance sintering AC [72]

Plasma activated sintering (PAS) Pulsed DC + DC [73]

Pulsed DC + DC Sodick Co. Ltd. [50]
Pulsed + DC Materials Modication Inc. [74]
DC Sodick Co. Ltd. [75]
Pulsed DC Sumitomo Coal Mining Co Ltd. [76]

Electric current sintering [77]

Plasma assisted sintering (PAS) Pulsed DC + DC Sodick Co. Ltd. [78]

Spark plasma sintering (SPS) Pulsed DC Sumitomo Coal Mining Co. Ltd. [79]
Pulsed + DC Sodick Co. Ltd. [80]
Pulsed Izumi Technology Co. Ltd. [81]
Pulsed DC Izumi Technology Co. Ltd. [82]
DC Izumi Technology Co. Ltd. [83]
AC [84]
FCT Systeme GmBH [85]
Pulsed DC Eltek Co. Ltd. [86]
Pulsed DC FCT Systeme GmBH [87]

Field activated pressure assisted (FAPA) combustion synthesis Pulsed DC + DC Sodick Co. Ltd. [88]
DC Sodick Co. Ltd. [89]
AC [90]
Pulsed DC Sumitomo Coal Mining Co. Ltd. [90]

Instrumented electric discharge consolidation Combination of pulsed, AC and DC [91]

Spark plasma activated sintering Pulsed DC [92]

Electric discharge consolidation Combination of pulsed, AC and DC [33]

Electric pulse current sintering [93]

Electric pulse discharge Pulsed DC + DC [94]

Field assisted densication Pulsed DC + DC [95]

2
Plasma pressure compaction (PPC) or P C Pulsed DC + DC Materials Modication Inc. [54]
DC Materials Modication Inc. [96]
Pulsed DC Materials Modication Inc. [97]

Pulse electric current sintering (PECS) Pulsed DC Sumitomo Coal Minino Co. Ltd. [98]
Pulsed DC Izumi Technology Co. Ltd. [99]
Pulsed Izumi Technology Co. Ltd. [100]
Pulsed DC FCT Systeme GmBH [101]

Field activated sintering technique (FAST) Pulsed DC + DC [102]

Pulsed DC + DC Sodick Co. Ltd. [103]
Pulsed DC Sumitomo Coal Mining Co. Ltd. [104]
Pulsed DC FCT Systeme GmBH [49]
Pulsed [105]

Pulse discharge sintering (PDS) Pulsed + superimposed DC and pulsed [106]

 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 141

Table 2 (Continued )
Process name Reported applied current characteristics Apparatus vendor Reference

Pulsed + DC [107]
Pulsed DC Sumitomo Coal Mining Co. Ltd [108]
Sodick Co. Ltd. [109]

Electric pulse assisted (EPA) consolidation Pulse DC + DC [110]

Field activated pressure assisted synthesis AC [111]

Pulsed DC Sumitomo Coal Mining Co. Ltd [112]

Pulse current sintering (PCS) Pulsed [113]

Pulsed DC Sumitomo Coal Mining Co. Ltd [114]
Pulsed S.S. Alloy [115]

Electroconsolidation DC Superior Graphite Co. Ltd. [56]

Electric eld assisted sintering (EFAS) Pulsed DC Sumitomo Coal Mining Co. Ltd. [116]
DC [117]

Pulse current hot pressing (PCHP) Pulsed DC Sumitomo Coal Mining Co. Ltd. [35]

Pulse current pressure sintering (PCPS) Pulsed DC Sumitomo Coal Mining Co. Ltd. [118]
Pulsed [119]

Pulse high current (PHC) heating sintering Pulsed DC Sumitomo Coal Mining Co. Ltd. [120]

Pulse plasma sintering (PPS) Pulsed [34]

Impulse plasma sintering Pulsed [121]

Plasma sintering Pulsed S.S. Alloy [122]

Pulse current hot quasi-isostatic pressing (PCHIP) Pulsed DC Sumitomo Coal Mining Co. Ltd. [4]

Resistance heated hot pressing Pulsed DC Sumitomo Coal Mining Co. Ltd. [123]

Electric pressure sintering (EPS) [124]

Pulsed electric current pressure sintering (PECPS) Pulsed DC [125]

Pulsed DC Sumitomo Coal Mining Co. Ltd [126]

Resistance sintering under ultra-high pressure AC [5]

Electric current assisted sintering (ECAS) [127]

DC [128]

Pulsed current activated sintering (PCAS) Pulsed DC + DC Eltek Co. Ltd. [55]

Pulse electric discharge consolidation Combination of pulsed, AC and DC [129]

Resistive sintering DC [130]

Spark pressure sintering Combination of pulsed, AC and DC [129]

Electroplastic compression (EC) [131]

Electric conduction sintering AC [132]

resistance of the powdered materials. Taylor claimed in his patent
that the electric discharge reduces the resistance of the powder to
be consolidated, permits the current to ow through the sample
when the system is connected to the low-voltage generator, thus
heating it to the desired sintering temperature. However, although
the principle of resistance and electro-discharge sintering under
pressure is clearly shown in this patent, few details are given. A
very short sintering period is mentioned, but no values of current
intensity was reported.
Direct passage of electric current through a powder compact to
be consolidated as a method to provide heating during the hot
pressing of objects having simple shapes was mentioned by Jones
in 1940 [58]. In 1944, Cramer [137] patented an apparatus able to
sinter metallic powders in a very short time (1/60 to 1/15 of a
second) by simultaneously applying a mechanical pressure and an
alternate or direct electric current of about 20 kA, corresponding to
a current density of the order of 620 MA/m2, depending on the
nature of the powders to sinter, the degree of porosity of the
compact and the thickness of the latter one. It was reported that
such high current density allows the points or areas within the
compact at which the particles are in contact with each other to be
brought almost instantaneously to the temperature at which
bonding occurs, that is close to the melting point, while the bulk of
the powders in the compact remains in a solid and relatively cold
state. Consequently, the entire mass of the compact is not highly
heated, although it becomes sufciently plastic to permit the
elimination of the sample porosity with the exertion of only
moderate pressure. In addition, Cramer [137] claimed that the
amount of heat employed to bond together the compacts in
accordance with his invention was so small that the temperature of
the entire compact does not rise greatly, so that it can be handled
with the bare hands almost immediately at the end of the process
and the ejection from the die. Cremer [137] built up his apparatus
by adapting a spot welding machine of the press type having
ratings of 40125 kVA and obtained satisfactory results with small
compacts whose a cross-sections were less than about 3 cm
transverse to the direction of current passage.
Ross [138] led a patent in which the method earlier developed
to apply an electric current for sintering under pressure was
modied by including the possibility to apply it intermittently
using pulses of different duration, by varying the current intensity
thus delivered, and regulating the number, intensity, and duration
142 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 21. Design accompanying the S.L. Hoyts patent. Adapted from Hoyt [134].

of current pulses according to the character of the material Fig. 22 shows the current traces of a brush magnetic oscil-
undergoing the consolidating process. It is interesting to note that, lograph during the sintering of iron compacts. In particular, it was
in his patent, Ross conrmed the Cremers idea about possible reported that sintering can be better controlled by using two
advantages of applying pulsating current over continuously current pulses rather than one. In fact, it was explained that the
passing current through the material. In particular, due to the
short duration of current ow during each pulse, the powder
particle can be heated to the sintering temperature at their
contacts point, while the die remains essentially cold.
A method for the production of resin bonded abrasive article
wherein the abrasive mix is made electrically conductive by the
addition of carbon particles was patented by Rushmer and
Goepfert [139,140]. Following these patents, electrically insulating
materials can be heated by the passage of current through them
while a mechanical load is also applied.
In 1950s, a process named resistance sintering under pres-
sure was studied intensively at Rensselaer Polytechnic Institute
(USA) on the basis of several contracts with the Navy Bureau of
Ships [26]. The apparatuses used were similar to spot welding
machines and followed the ideas patented by Taylor in 1933
and Cremer in 1944. The low-voltage high current (of the
order of 38200 MA/m2) power was supplied by a welding
transformer connected to a 600 V single-phase current motor- Fig. 22. Brush oscillograph current traces recorded during the resistance sintering
generator set. under pressure. Adapted from Lenel [26].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
surface oxide lm typically present on several powder particles
greatly inuence the resistance sintering of the sample. Particu-
larly, in powders which are difcult to deform plastically, it was
judged important to remove these surface lm during resistance
sintering. In this regard, the voltage and the current for the rst
pulse were reported to be adjusted in order to break down the
resistance (oxide surface layer) of the compact, with an application
time long just enough to accomplished this purpose without
overheating the compact, while the second pulse did the actual
sintering.
It was also mentioned that attempts to gain an understanding
of the basic characteristics of this process and to learn in what
respect it differs from other powder metallurgy processes were
along the way. At the same time, the application of resistance
sintering to a number of different electrically conductive mate-
rials was investigated. However, the size of parts sintered by this
method was mentioned to be limited. Most of the (1/2) in.
diameter specimens required currents of 525 kA to be sintered in
1030 cycles at Rensselaer Polytechnic Institute. It had been
shown that larger parts up to 3 in. diameter can be resistance
sintered under pressure as well when the sintering times are
lengthened to several seconds and a sufciently large power
source is available. Nevertheless, it was pointed out that the size
limitation must always be considered.
Other applications of the ECAS process were lately patented
[141144]. In particular, Balaguer [142] patented a method for
producing carbon dense article starting from different carbonac-
eous raw materials by using the ECAS technique. As shown in
Fig. 23, a peculiar feature of this apparatus consists in the different
orientation of pressure application and current ows. A low-
voltage (15 V) high-amperage alternate or direct current (1
10 kA) was typically applied for 152 min depending upon the
oven dimensions and the desired heating rate and temperature.
Progress in the commercial utilization of the electric current
activated/assisted sintering was achieved in the 1960s. It was
reported that in 1965 a new brand technique was taken out of the
laboratory and put into production at Japax Scientic Corp., Menlo
Fig. 23. Schematic representation of the process patented by Balaguer. Adapted
from Balaguer [142].
143
Park, CA (USA) in association with the Japax Inc. of Kanegawa
(Japan) [59,145]. In addition, U.S. patents have been issued on the
process with additional patents scheduled for later submission
[145]. The proposed ECAS method, was claimed to combine
pressing and sintering of powder metal parts in one shot by the
impulsive force of an unspecied spark energy, and therefore
called spark sintering.
Although scientic investigations about the claimed effects of
the electric current were not available, it was stated that, by that
time, this process had progressed well beyond the economic
feasibility phase [145]. As an example, the production by Japax of a
semi-automatic spark sintering machine for one of the worlds
largest manufacturers of precision micrometer was mentioned
[145]. In particular, the machine directly sinters WC powders to
the leading edge of a steel micrometer spindle. In another
application, Japax Inc. licensed a large bearing manufacturer to
fabricate aluminum motor bearings. It also licensed an electrical
contact manufacturer to spark sinter silvercadmium oxide disks
directly to a matching copper substrate disk [145].
Generally speaking, it was claimed that this process had been
capable of achieving results not possible with conventional
sintering methods, along with versatility and almost unlimited
capabilities [145]. However, it was also reported that large-scale
applications were not straightforward.
Speculations about the fundamental mechanisms of the spark
sintering method were addressed in the same articles [59,145]. It is
interesting to note that the development of the spark sintering
technique was reported to be based on the nding that metal
particles exposed to the vacuum of space readily weld to each
other without heat supply. It was claimed that heat is not critical in
welding metal particles together, but what is of critical importance
is the stripping of oxides and other contaminants from the
contacting surfaces of the particles in an induced atmosphere that
is substantially free of atmospheric gases [59]. In ordinary
sintering this is accomplished with heat and the introduction of
inert gases into the sintering furnaces. In space, this occurs as a
result of natural vacuum, while in cold welding, it is accomplished
by massive surface crystal deformation. In each case, however, the
stripping of surface contaminants exposed a virgin metal surface
that has a higher energy level than the internal energy of the
particle. Then, physically, the surface crystals of the particle tend to
combine with those of contacting particle and thereby reduce the
surface energy level to the that one of its internal energy [59].
Therefore, when two or more such surfaces are in contact, a weld is
produced by the instantaneous bridging over of intersurface
crystals as in diffusion bonding.
Application of this principle was reported to be the heart of
spark sintering [59]. In particular, the presence of an oxide layer
on the metal particle surface is advantageously utilized since a
dielectric gap between adjacent particles is formed. In fact, when
a high energy electrical discharge is supplied by a capacitor bank
to the powders compact, a spark is generated. Then, it was
reported that ionization through the particle gaps occurs causing
current ow there through. In addition, although it was reported
that this is not a critical part of the process, use is made of the
6000 8C temperature of the interparticle spark columns [59]. The
resulting heat, together with the impulsive pressure generated
within the mold by a spark having an energy density in the order
of the 106 J/cm2, disintegrated the surface contaminants of the
powders particles and stripped any atmospheric gases, thereby
creating the momentary condition wherein particle to particle
crystal bridging could occur [59,145]. As a consequence, a
coherent mass, taking the shape of the mold and electrode is
formed when the bridged particles are pressed while still in a
plastically deformable state [59].
144 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Spark discharges between the particles end within a second or
two (depending upon the material being worked). It was reported
[145] that the above phenomena occur within microseconds
reaction-time, the rest of the discharging time being utilized
entirely by the particles crystal structures to link up through
bridging and fusion. After the 1 or 2 s spark discharge, the applied
current is adjusted to heat the resulting mass at a temperature well
below the melting point of the material in order to achieve
additional crystal bonding between the particles and further
densication of the mass. At the end of the curing period, the
current is switched off and a mechanical pressure is applied for the
nal densication. Thus in matter of seconds (just 1215 s) powder
particles are transformed into metal parts with a nal density from
65% to 98% of the theoretical one which can be obtained by
controlling the operating parameters of the process (spark energy
density, duration and frequency of spark discharges, particle size of
the powders, resistive heating current or temperature, and the
external static pressure) [59,145]. In addition, since this process is
so fast, it was claimed that no controlled atmosphere or vacuum
was needed [59].
Although details of the applied electric current were not
mentioned, from the description of the spark sintering process
reported, it is quite clear that from the physical point of view the
Japax technique is similar to the ones developed in the earlier
decades [26,136138]. Perhaps the novelty in DeGroats reports
lays in the speculations about the role played by the applied
electric current. However, experimental evidences of spark
formation as well as of the other phenomena mentioned above
were not reported, and the question if the main current effect is the
spark generation or Joule heating of particle contacts, in addition to
the real mechanism of oxide removal, remained unsolved.
In 1966, Inoue [63] patented an apparatus for electric current
activated/assisted sintering, which is based on the simultaneous
application of an electric current and a mechanical pressure lower
than about 10 MPa. In particular, the applied electric current
resulted from the superimposition of a periodic current upon a
direct current. It was reported that the light contact between the
particles deriving from the low applied pressure along with the
imposition of a periodic/alternate current leads to the formation of
spark discharges within the initial voids present in the sample to
sinter. It was asserted that these electric sparks possess a power of
the order of hundreds and even thousands of joules and therefore
force the particles into bonding contact with a pressure even
greater than that attainable heretofore by mechanical means. It
should be noted that Inoue claimed the innovative features of his
apparatus on the basis of the fact that earlier ECAS technique
required elevated pressure in order to reduce the contact
resistance to a level substantially equal to the internal resistance
of the particles so that a high current could be passed through the
sample to develop the necessary bonding heat. In contrast, Inoue
[63] afrmed that in his method the contact resistance must be
greater than the internal resistance and, preferably, several times
as great so that, at least during the initial stages of the sintering
operation, most of the applied energy is in the form of the spark
discharge with relatively little being dissipated in resistive heating
of the particles. He also claimed that, since the sintering action
occurs immediately upon the spark discharges, the dense body can
be formed in a matter of seconds as compared with earlier methods
requiring tens of minutes and even hours to effect complete
sintering.
From the analysis of Inoues patent several issues arise. First of
all, the application of lower pressures in order to favor sparks
occurrence seems not really innovative. In fact, Hoyt [134] and
Gilson [135] obtained dense bodies applying only 6.9 MPa, that is
even lower than the upper limit reported by Inoue, without
mentioning possible formation of spark discharges. This is also true
when considering the Taylors apparatus, where the applied
mechanical load can be merely the weight of the upper electrode.
Also the claimed shorter processing times are of same order of
magnitude of those reported in the patents mentioned above.
Maybe the most innovative aspect of Inoues patent is the
combination of a direct electric current with a periodic one.
However, the values of the applied current were not provided and
therefore cannot be compared with the ones used in the
apparatuses patented before. It is also only right to mention that
no experimental evidences of the claimed sparks formation were
reported by Inoue. Comparison between results obtained by
applying the direct current only and those ones achieved when a
periodic current was superimposed to the direct one were neither
shown.
In a subsequent patent [146], Inoue explained that the results
obtainable with his invention, which was named electric discharge
sintering, are believed to derive from the fact that the spark
discharge is capable of effecting a partial ionization of the
particulate material at the mutually contacting surfaces of
adjacent particles while simultaneously applying to these ones
sufcient impulsive pressure, in addition to the static or
mechanically applied one to effect rm fusion of the particles.
By clinching what reported in the previous patent, it is also said
[146] that even if a true ionization of the material constituting the
particles does not take place, the development of the spark
discharge appears to result in the concentration of a sufciently
high temperature at the region of discharge so that an interdiffu-
sion of the material constituting the contacting particles takes
place under the impulsive pressure mentioned above. After an
initial fusion resulting from the spark discharge, the bond is
presumably further secured by the passage of electric current
through the body without substantial development of sparking to
provide a resistive or joule heating of the particles, the heat being
concentrated at the limited zone of fusion previously produced so
that a rm welding of each particle to those proximal consequently
results.
However, by contradicting previous process explanation, Inoue
also reported [146] that his electric discharge sintering method
was only satisfactory for producing relatively porous or low-
density bodies, while still claiming that it has the capability to
reduce the sintering time manifold, to increase the variety of
shapes which can be produced by sintering, and to decrease the
basic costs of a sintering installation. It was also reported that
sintered bodies of high-density were precluded in this method as a
consequence of initial spark discharge welding which takes place
at unusually low static pressure. In this patent, Inoue prescribed
that the initial low mechanical pressure (0.010.5 MPa) applied
during the spark discharge should be strongly augmented (up to
100 MPa) concurrently or subsequently to the application of the
electric current, but in any case subsequently to the formation of
conductive bridges between the particles and while the particles,
at least at their interfacial regions, are at temperature at which
they are plastically deformable under the elevated pressure.
According to the Inoues invention [146], the electric current
employed to effect the sintering of the particles comprises at least
two components having specic functions improving the particle-
to-particle bond. In particular, a high-frequency periodic or
alternating (0.1100 MHz) component generating the spark
discharge, a low-frequency (0.110 kHz) and/or a direct current
adapted to generate efciently the joule or resistive heat to
consolidate the particles upon the formation of the conductive
bridge there between should be superimposed during the process.
It was also reported that the high-frequency electric current can
induce a resonance-activation with a subsequent re-orientation
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
and the strain of the crystal lattice of the particles thus providing a
rapid ionization of the substance at the interface between them
and a rapid diffusion of the ions into the crystal lattice, thereby
ensuring a monolithic bond and greatly improving the density of
the sintered body.
Inoue [146] claimed also to have found that advantageous
results, with respect to the density of the sintered body, can be
obtained when the electric current supplied to the electrodes is
reduced to a relatively low level or cut off one or more times prior
to terminating the sintering. Moreover, it was reported that the
proper timing for the current reduction is a function of the nature
of the powdered sample to be sintered and can be determined by
the change in the voltagecurrent characteristic of the sintered
body.
Regarding the results obtained by Inoue [146,147], it should be
mentioned that, although several examples where the electric
current seems to have some effects were reported, a systematic
investigation with the aim to separate the possible effects of
temperature (merely due to the resistive heat dissipated during the
process), mechanical pressure, and electric current characteristics
(amperage, frequency) or the cut-off timing, was not presented.
Nevertheless, lately in 1967, Inoue and co-workers [64] repor-
ted of the sintering and graphitization of amorphous carbon
powders by using an electric pulse current which is considered to
cause an electrical discharge at the contact surfaces of adjacent
carbon particles. The synthesis time was 60300 s but no infor-
mation about the applied electric current, as well as no experi-
mental evidence of the mentioned electrical discharge were given.
In the same year, Inoue patented another invention related to the
electric discharge sintering of particles and, more particularly, to a
method of and an apparatus for controlling the porosity of the nal
samples [148].
In another patent [65], it has been pointed out that one of the
principal barriers to mutual bonding of metallic particles is the
presence of microscopic or submicroscopic lms or skins upon
these particles which impede mutual intercrystalline diffusion of
the particulate materials. Thus, it has been hypothesized that the
high temperature required for prior sintering techniques and the
reducing atmospheres commonly employed, at least partially
destroy these lms and permit the elevated static pressures to
bond the particles together. In the spark discharge technique,
however, it appears that a spark discharge is generated among the
particles, at least predominately conductive, between the electro-
des in contact with the particulate mass and in such light-
contacting relationship that a discharge is generated across the
electrodes and through this mass when an electric current pulse is
applied across the electrodes. This discharge appears to pass
through the mass from one electrode to the other and to be a
composite of numerous discharges between the individual
conductive elements and nearby elements of the mass. It may
be then assumed that the discharge initially erodes or destroys
impulsively any oxide coating which may be present on the
particles and also urges the particles together with a dynamic
pressure or shock wave. These discharges strip the oxide lms from
the particles and break down any diffusion resistant skins at the
boundary surface of most metallic particles. The impulsive energy
associated with these discharges impels the particles into contact
at the resulting virgin surfaces so that diffusion takes place with
the formation of the aforementioned conductive bridges. Further-
more, material is carried by the individual discharges from one
particle to another to form, in effect, conductive bridges between
the particles. Further current ow is concentrated at these bridges
so that the latter ones are almost heated to a state of coalescence
and the bridged particles grow together into a practically mono-
crystalline structure. This patent was based on the idea that the
145
sparks formation during this process can be facilitated by modi-
fying the electric potential across the sample at a relatively high
frequency by vibrating one or both electrodes at sonic or ultrasonic
frequencies and/or by applying a high-frequency periodic or
alternating current across the electrodes and in superimposition
upon the discharge current. Quite puzzlingly, in this patent, it was
reported that even a purely direct current or, with somewhat lower
efciency, a low-frequency alternate current can be effectively
employed for spark sintering if a servo-control system is used to
maintain the electrodes in light contact with the powders. This in
spite of the fact that DC power has degenerated into continuous
current ow almost instantaneously. It was also reported that it is
however advantageous to promote the formation of fusion zones
between the particles by the application of current surges or pulses
superimposed on the DC component which induces electro-
transportation of material within the sinterable mass. When the
load current is periodic or chargeable in the course of sintering, a
dispersion of the sparks is produced, with a more widespread
distribution of the sinter points along the particle surfaces.
According to another aspect of this invention, it should be
mentioned that tools for varying the pulse frequency, width,
waveform, and interval in accordance with the material to sinter,
were provided. The corresponding values of the applied voltage
and current reported in the patent examples were of the order or
magnitude of 10 V and 1000 A, respectively. Even in this patent
[65] experimental evidence of the intrinsic effect of the electric
current as well as of the inuence of the various combinations of
current waveform, were not reported.
Nevertheless, looking for ways to cut costs of beryllium parts for
missiles and spacecraft, Lockheed Missiles & Space Co. (LMSC), a
division of Lockheed Aircraft Corp., was intrigued by the reported
speed of the process patented by K. Inoue [61]. Then, Lockheed
Aircraft Corp. obtained a license from the inventor, becoming the
owner of the world rights (Japan excluded) of the Inoues process.
In 1967 Lockheed Missiles & Space Co. received the rst apparatus,
and in 1969 an extensive use of the Inoues patented technique by
the Lockheed division and Anocut Engineering Co. was reported
[61,66,67,149151].
The process, named as spark sintering instead of electric
discharge sintering, was presented as the latest method for
producing powder metal (P/M) parts due its capability to combine
pressing and sintering in a single operation. In addition, it was
already advanced to industrial scale since a semi-automatic
system was developed. After an active R&D program, it was
reported that Lockheed had began to produce several beryllium
parts for one of its missile programs and aerospace applications. In
particular, the fabrication of beryllium component used in the U.S.
Navy Poseidon missile was mentioned [61]. For instance, beryllium
rings were machined into guidance gimbals for Minuteman
missiles [149].
Stimulated by the successful and economical production of fully
consolidated beryllium parts, extensive experimental investiga-
tions on the processing of a wide range of materials were men-
tioned. In particular, attention to the materials difcult to produce
by conventional P/M techniques was paid [61,66,67,149151]. It
was also reported that spark sintering appeared to be a very
effective process for consolidating alloy powders that have high
creep resistance at elevated temperature because process para-
meters can be readily adjusted to produce a temperature that lies
within the very narrow band between onset of plasticity and
melting [150].
Considerable success had also been achieved in forming and
simultaneously bonding powders to solids by this technique.
Complex congurations with minimized machining and materials
cost were produced [149]. Essentially full density had been
146 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
achieved in the powder portion of the built-up part, along with a
good bond between it and the solid component. A potential
application was then identied in the simultaneous forming and
bonding of bosses or ttings to jet engine cases.
It was also reported that the encouraging results motivated
Lockheed to acquire rights and patents of the spark sintering
process in July 1968. Then, Lockheed actively pursued other
product applications for the process both in house and for
industry in general. Lockheed tried to establish a broadened
industrial usage of the spark sintering method also for other
materials mentioned above [149]. In particular, license agreements
with several US companies were reported to be in various stage of
negotiation. However, it was also specied that Lockheed did not
claim the spark sintering is a superior way of making all possible
powder metallurgy products [149]. In particular, spark sintering
was not expected to compete with conventional pressing and
sintering processes for high volume production of small parts
[149]. Instead, it is useful for production of parts or preforms which
must have densities higher than those attainable by conventional
powder metallurgy methods, or are too large to be produced
economically by such methods.
Regarding the electric current application, it was reported that
the spark sintering process consists essentially in two phases [66].
An initial activation under relatively low pressure through the
application of pulsed or moderately high frequency AC current
combined with a DC that tends to produce electric (spark)
discharges in the powders in order to create the initial bonds
between the particle powders. A capacitor bank is used merely to
tune the pulsed or AC superimposed on DC, and not for instan-
taneous powder discharge. Then once the previous stage has
progressed sufciently, resistance heating of the compact under
increased pressure is provided by adjusting the electrical energy
until the desired densication is obtained.
Typical spark sintering cycle is reported in Fig. 24, where the
rst time phase produces incipient sintering while the powders are
heated to sintering temperature. The apparatuses typically used in
these investigations had a maximum power output up to 1050 kVA
and a maximum AC/DC current of 70 kA [61,67,151]. Voltage
typically varies in the range 510 V during the few minutes to
produce an item part. Typical current of the total current density
(AC and DC) were of about 2300 kA/m2. However, the operating
conditions were reported to be varied depending on part size and
complexity, material composition and desired density [66,149]. It
was also specied that both alternating and direct current were
used to speed up the process and produce better bonds between
powder particles, which in turn was reported to promote more
uniform part density [61]. In addition, a combination of high-
Fig. 24. Spark sintering process cycle. Adapted from Bangs [60].
frequency AC plus DC, and/or low frequency AC power was claimed
to result in the highest densities and greatest rates of densication,
permitting relatively short cycles [67,151]. However, no experi-
mental evidences or data were reported neither in this article.
Indeed, it should be noted that some of the characteristics of the
applied electric current (frequency, AC/DC combinations, etc.) as
well as a systematic investigation of their effects on the process
and product were not reported. Therefore, the real effect on
combining AC and DC still remains unclear in the mentioned
reports. In this regard, kind of qualitative explanation where a mix
of direct and alternating current was used, was reported during an
interview to Lockhead Missiles & Space Company researchers [60].
In particular, R.W. Boesel literally said: . . . It yields better results
than AC or DC alone. AC tends to agitate the powder metal particles
and produces a more homogenous current path through the material.
With DC alone there is the tendency for the energy to ow to become
channeled and thereby create hot spots in the materials. . . .. This
explanation was in addition to the fact that the occurrence of
sparks during the sintering process had not experimentally
demonstrated yet.
Some additional explanations were given from the Tokyo
Institute of Technology, Tokyo [3]. The process investigated was
the same developed at Lockheed, and the apparatus consists in an
AC generator working at 2 kHz and a DC rectier with a current
density up to about 3 kA/m2. The AC and DC are applied
simultaneously, but since the electrical resistance of metal
powders to DC are higher than that to AC, the former acts as
the prime generator of Joule heating. It is interesting to note that, in
addition to the already claimed formation of spark discharges,
Saito and Sawaoka [3] motivated the application of a high
frequency AC power on the basis of the induced skin effect. When
the sintering of the specimen does not take place homogeneously
during the process, the AC acts effectively on the poorly peripheral
sintered parts of the specimen. Again, however, experimental
evidences of these claimed effects were absent.
As already mentioned above, it was reported that in the 1970s,
the spark sintering has been established as a practical and
economical process in Japan and USA. However, a fundamental
comprehension of the real role played by the electric current/
voltage was still lacking. In addition, some problems related to the
ECAS processes were highlighted by Weissler [6,70]. In particular,
it was reported that the area of application of this process may be
limited by the typical use of graphite dies which are characterized
by low wear resistance with a consequent increase of the pro-
cessing costs. Therefore, to increase the economy of the process,
the use of wear resistance alumina dies was proposed instead of
graphite ones. It was also reported that the use of short time high
current pulses like the Taylors or EDS apparatuses to produce
dense parts of conducting powders in non conducting dies failed
mainly because of inhomogeneous current distribution within the
powder compact. To overcome this problem, the arrangement
developed at Lockheed Missiles and Space Co. which involves the
application of alternating and direct current simultaneously, was
mentioned. It was also specied that the frequency of the
alternating current and the AC/DC ratio were selected in such a
way that, due to the skin effect, heating of margin zones of the
sample occurs [3]. This rather expensive technique was judged
practical only if the current concentration within low-ohmic
compacts can be suppressed, which typically takes place when
metallic materials are used. Weissler also mentioned about a
report entitled Spark sintering of powder metals of the Naval
Ordnance Station of Louisville (USA) which provides processing
details and fabrication costs. The equipment described therein
was reported to be rather inefcient with respect to plunger
movement and temperature control and high in labor cost.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Besides the latter ones, the wear of graphite dies was reported to
be a serious problem.
Nowadays, more than 1800 scientic articles have been
published (cf. Fig. 1), with an exponential growth starting in the
earlier 90 as a consequence of the availability of commercial ECAS
devices (cf. paragraph 1.2). Hundreds of elemental, compounds or
alloys powders have been consolidated by the ECAS process (cf.
chapter 2). However, only few percent of the total number of
published articles deal with the intrinsic effect of the applied
current/voltage, and therefore a complete understanding of the
fundamental mechanisms taking place during this process has not
been achieved yet. In addition, although it is claimed [152154]
that several Japanese companies have adopted this process as
advanced powder metallurgy technique and intensive work has
been performed on its automation, ECAS industrial applications
seem rather limited in the rest of the world.
2. State of the art of systems investigated
The historical background presented so far, where the
characteristics of the various consolidation methods based on
the application of the electric eld or current are reported, gives
now the possibility to illustrate the large number of materials
synthesized/sintered by these techniques. Specically, the follow-
ing classes of materials, which are well known to be attractive for
several science and engineering applications, will be taken into
account to provide excellent examples of ECAS features: metals
and alloys, intermetallics, carbides, borides, nitrides, silicides,
oxides, sialon, ceramicmetal and ceramicintermetallic compo-
sites, ceramicceramic composites, hydroxyapatite-based materi-
als, chalcogenides, polymer-based materials, functional graded
materials, systems for joining, graphite/carbon-based materials
including composites containing carbon-nanotubes, and other
systems.
2.1. Metals and alloys
2.1.1. Aluminum
The rst investigation related to the use of electric current to
activate sintering of alloys based on aluminum was performed by
EDS in Soviet Union [155]. Specically, Al alloys containing Cu in
the range 5.730 wt.% were considered and a possible explanation
of the intensication of the alloy formation by EDS was given.
The densication of the X7091 alloy (Al6.5Zn, 2.5Mg, 1.5Cu,
0.4Co, 0.04Fe, 0.05Si) was carried out by HEHR [29]. It was found
that densication is improved as the energy input is increased
Fig. 25. TEM results of the SPS-consolidated cryomilled 5083 Al: (a) representative bright-eld image, and (b) distribution histogram of the Al grain size as determined from
the TEM images. Adapted from Ye et al. [164].
147
(4002500 kJ/kg) and compact density greater than 95% of the
theoretical value was achieved. It was stated that this processing
method is able to break the oxide layer covering initial powders
thus improving bonding among particles.
The consolidation by EDC of atomized Al-based alloy powders
was also investigated [156,157]. In particular, for the case of the
Al8Cr2Ti alloy, the density reached 96% of the theoretical value
when the applied input energy was 4 kJ/g under a mechanical
pressure of 103 MPa. In addition, transmission electron micro-
scopy (TEM) observations conrmed the removal of oxide layer
during the EDC process [157].
Pure Al powder compacts were prepared by SPS under different
temperature, loading and frequencies conditions [36,158,159]. It
was found that similar compact densities were obtained at 873 K,
9.4 MPa and 40 kHz or 623 K, 23.5 MPa, and 40 kHz, but the
corresponding electrical resistivity and tensile properties were
not the same, being in the rst case similar to that of base Al metal.
This fact is due to the presence of the oxide lm at the interface
between particles [158,159]. Specically, at the SPS process
conditions above (873 K), the oxide lm at the Al particles surface
breakdown and a metalmetal bonding takes place. Regarding
the effect of pulse frequency on densication, deformation and
microstructure of the sintered compacts, it was found not
signicant at least within the frequency range investigated, i.e.
040 kHz [36]. The inuence of sintering temperature, pressure,
temperature at which the load is applied and current ow was
recently investigated when relatively coarse pure Al powders
were processed by SPS [160]. Better results in terms of mechanical
properties are obtained when the mechanical load is applied at
high temperature. In addition, using the optimized SPS operating
conditions, i.e. heating rate of 100 K/min, 525 8C, dwell time of
1 min, applying 60 MPa at 475 8C, the mechanical properties and
fracture morphology of the obtained product are similar to those
of pure annealed wrought Al.
High-grade compacts of 7075 aluminum alloy obtained by
rapidly solidied powders were produced by SPS after optimiza-
tion of the most important processing parameters (pulse discharge
time, maximum temperature, holding time, cooling conditions
after sintering) [161]. Specically, when the SPS samples were
rapidly cooled, they maintained the same supersaturated state of
the initial rapidly solidied powders. High wear-resistant bulk Al-
based alloys, i.e. Al8Mn2Ce [162] and Al10La5Ni [163], have
been also recently prepared by the SPS method.
Several nanocrystalline or quasi-crystalline Al-based alloys
powders have been consolidated taking advantage of the various
current activated sintering methods were the powders to be
148 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 26. Microstructure of the cell edge solid of aluminum foams obtained by electric furnace sintering (a) and by SPS (b). Adapted from Wen et al. [175].
processed have been produced by mechanical milling [49,164
166]. Specically, mechanically milled nanostructured Al17Si
5Fe3.5Cu1.1Mg0.6Zr (wt.%) powders were consolidated by
FAST to produce bulk nanostructured compacts [49]. Fully dense
nanocrystalline 5083 Al alloy was obtained by combining the
cryomilling technique and SPS [164]. Specically, the cryomilled
powders, which exhibit an average grain size of about 25 nm, were
consolidated by SPS (350 8C, 80 MPa, 300 s) thus obtaining a
product with approximately 50 nm grain size (cf. Fig. 25).
After milling in liquid nitrogen, nanocrystalline Al2.3Cu
1.47Mg0.19Si1.08Fe1.0Ni0.16Sc (wt.%) alloy powders were
densied by SPS (400 8C, 104 MPa, 6 min) and the microstructure
and aging behavior of the obtained product was studied [165]. A
bulk nanocrystalline Al5 at.%Fe alloy with high-strength and large
plastic strain was fabricated by mechanical alloying and SPS [166].
AlCuFe alloy powders (crystallite size of about 10 nm) obtained
by ball milling in presence of a liquid medium were FAST sintered
(700 8C, 55 MPa, 20 min) to obtain a homogeneous bulk solid with
uniform ultra-ne microstructure [167]. Al10La4Ni4Fe bulk
metallic glasses (96% relative density) were successfully obtained
starting from ball milled powders and spark plasma sintering
(613 K, 600 MPa, about 65 min) [168].
The consolidation behavior by SPS of nanocrystalline
(Al + 12.5 at.%M)3Zr (M = Cu, Mn) alloy powders prepared by ball
milling was investigated [169171]. A SPS-515S apparatus (12:2
onoff pulse ratio) was employed under the conditions of sintering
temperature in the 560800 8C, 100 8C/min heating rate, 50 MPa
pressure. It was found that the (Al + 12.5 at.%Cu)3Zr ball milled
powders prepared could be successfully consolidated to full density
at 580 8C that is 300400 8C lower than the conventional con-
solidation temperature of Al3Zr. Analogously, the (Al + 12.5 at.%
Mn)3Zr powders were nearly fully densied at 620 8C without taking
holding time by SPS. Their average grain size were less than 10 nm,
which is reported to be the smallest grain sizes obtained for the
nanocrystalline bulk specimens prepared by various alternative
consolidation methods.
The SPS process was recently applied to produce bulk
nanostructured pure Al after air-atomized pure Al powders were
mechanically ground with stearic acid, as a process control agent,
in a vibratory ball mill [172]. Regarding the characteristics of the
SPS products it was found that materials obtained from no
mechanically treated and 64 h milled powders exhibited a Vickers
hardness of HV 39 and HV 159, respectively.
A mixture of micro and nano-sized Al7Cr1Fe powders were
processed by means of the P2C technique by initially pulsing the
powders at 150 8C for 10 min and subsequently consolidating
them at 550 8C and 40 MPa for 10 min [173]. The effect of sintering
temperature and time during the densication of AlSiCuFe
quasi-crystalline powder by SPS was investigated and the optimal
conditions (650 8C, 30 min) to obtain dense cylindrical samples
were obtained [174].
Aluminum foams were prepared by SPS (773 K, 20 MPa, 5 min)
in the framework of a process which consisted of four steps:
mixing of Al and NaCl, pressing, sintering and leaching, in order to
eliminate the imbedded NaCl particles [175]. For the sake of
comparison, sintering was also carried out using an electric furnace
(923 K, 3 h). Besides the relatively lower sintering time and
temperature required by SPS, the characteristics of the obtained
foams were different. In particular, the microstructure of the
product obtained by SPS was microvoid free and ne-grained
(4 mm) (cf. Fig. 26) and the plateau stress is relatively higher than
that obtained using electric furnace sintering.
An approach consisting of SPS followed by space-holding NaCl
dissolution was also adopted by Hakamada et al. [176,177] to
obtain porous Al with a porosity of 78% and pore size of 850
1000 mm. The effect of the processing conditions on compressive
properties was investigated and the optimal conditions to produce
robust porous Al were 843 K, 20 MPa, 10 min sintering time and
3 mm Al powder size [177].
2.1.2. Cobalt
The SPS technology was utilized for the synthesis of a new Co-
based glassy bulk alloy (Co65Ti20W15) starting from mechanically
alloyed powders [178]. The consolidation by SPS was performed
under Ar atmosphere at 843 K, using a heating rate of 4.95 K/s and
a mechanical pressure of 19.638.2 MPa. The sample was
consolidated within 180 s thus reaching a relative density above
99.6%. In addition, the chemically homogeneous glassy structure is
maintained and the product exhibits high Vickers microhardness
values (8.698.83 GPa).
Porous Co29Cr6Mo compacts for biomedical use were
obtained by SPS starting from powders processed by plasma
rotating electrode and characterized by a diameter range (610
700 mm) [179]. The inuence of SPS temperature on porosity of
obtained products was investigated. It was found that by varying
the sintering temperature in the range 10231273 K the specimen
porosity could be changed between 10.8% and 39.4%. The Youngs
modulus of the compact after annealing was found still relatively
higher than that of human cortical bone but approximately one-
fourth of that characteristic of cast CoCrMo alloy.
2.1.3. Copper
Copper powders were sintered by PAS and the inuence of PAS
parameters (pulse current, direct current, pressure) on the
densication process was investigated [180]. Sintering experi-
ments were carried out in a PAS-V-K apparatus (Sodick Ltd.) and
consisted of two stages. In the rst one, a pulse current of 400 A
was applied for 030 s while during the second one a DC current
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
was varied from 300 to 800 A for 300330 s and a mechanical
pressure of 12.625.2 MPa was applied. A larger DC caused a
higher heating rate and, correspondingly, a higher densication
rate. In contrast, when the current was maintained constant,
higher mechanical pressures led to lower heating and densication
rates. Moreover, it was found that the application of the pulse
electric current before application of the DC promoted the
densication process of Cu powders.
The consolidation of pure Cu powders by P2C was investigated
using different processing conditions, i.e. electric pulse and non-
electric pulse, temperature, and time [96]. It was found that
pulsing the sample prior to densication produced a nal P2C
product with higher microhardness. The comparison of product
properties (microstructure and hardness) obtained when starting
from nano- or microsized powders and using identical P2C
processing conditions was also investigated by the same authors
[97].
CuNi composite samples were investigated by EDS [181]. It
was found that while isothermal sintering requires 4 h at 1050 8C
to attain the homogenization of a Cu50Ni mixture, only 45 s are
needed when using EDS. Cu15.0Zn8.1Al shape memory alloys
were manufactured by SPS under different gaseous atmospheres
and powder size [182]. Resistance sintering was used under
mechanical pressure of 68 GPa and input power of 1823 kW for
50 s to prepare dense CuW composite product containing 580%
of Cu [5]. Higher input energy was found benet for the
preparation of higher density W5Cu composite while not
signicant effects were obtained when the Cu20%W was taken
into account.
SPS was used to consolidate Cu-based amorphous powders
obtained by gas atomization [183185]. In particular, a Cu6Ni
22Zr18Ti metallic glass bulk product with a relative density
higher than 98% was successfully fabricated [183]. Fig. 27 shows an
optical micrograph of the obtained bulk metallic glass after a
chemical etching. It is observed that the ner particles were
distributed between the coarser ones to give a well-consolidated
product without forming any pore.
The previous alloy was also combined with another Ni-based
alloy to produce metallic glass matrix composites [184,186].
The fabrication by SPS of amorphous bulk Cu33Ti11Zr6-
Ni2Sn1Si (at.%) alloy was investigated when starting from gas-
atomized powders [187189]. In particular, products without
crystalline particles and retained pores were obtained by SPS
when applying 300 and 700 MPa and rapid heating and cooling
conditions [188].
Fig. 27. Optical micrograph of the SPSed Cu6Ni22Zr18Ti metallic glass. Adapted
from Kim et al. [183].
149
2.1.4. Chromium
The sintering of chromium by an electrical current activation
technique was investigated by Andrushchik et al. [190]. The
minimum sample porosity and material structure defectiveness
were obtained under the optimal operation conditions correspond-
ing to a sintering temperature of 1673 K and a holding time at this
temperature of 300 s.
2.1.5. Iridium
Various binary and quaternary Ir-based alloys have been
prepared by the PECS process [191193]. In particular, ve Ir-
based alloys were prepared either starting from elemental [191] of
pre-alloyed [192] powders. PECS process was performed in both
cases at 1800 K for 4 h and the relative density of all the obtained
compact exceeded 90%. However, some improvement were
obtained using pre-alloyed powders. Three quaternary IrNb
NiAl alloys, i.e. (Ir13.5Nb8.1Ni1.9Al, Ir10Nb41.6Ni8.4Al,
and Ir2.21Nb76.9Ni9.96Al), were also fabricated by PECS
process using elemental powders [193]. It was found that the
phase formation and microstructure of the obtained sintered alloys
were quite different from that of the samples fabricated by
conventional arc melting method.
2.1.6. Iron
The inuence of sintering conditions during resistance sintering
on iron and steel parts of ve sorts of complex contour was
examined by Sakai and Hara [69]. In particular, the effect of the
presence of a suitable insulator to be inserted between metal
powders and die wall was also studied. The compaction of iron
powders over 95% relative density was obtained by resistance
sintering at 800 8C in less than 6 min and at a heating rate of 600 K/
s [194]. It was found that the heating step was the most important
stage during which the sintering densication was almost
completed.
Fully dense nanostructured Fe0.8 wt.%C products with grain
size of about 150 nm containing a few nanometer Fe3C dispersoids
were obtained by SPS at 600 8C (70 MPa) for 10 min starting from
mechanically milled Fe and graphite nanocrystalline powders
[195].
FeCo-based nanocrystalline materials were prepared by SPS
[196] or FAST [197] using powders produced by mechanically
alloying. FeCo bulk products with over 95% of the theoretical
density and grain size of about 30 nm were attained by SPS at 900 8C
(60 MPa) for 5 min (cf. Fig. 28) while the starting alloy powder
possessed an average grain size in the range 1015 nm [196].
Fig. 28. Field emission-SEM morphology of the FeCo specimen processed by SPS at
900 8C. Adapted from Kim et al. [196].
150 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 29. Apparent porosity of stainless steel samples obtained using HP and SPS
under different sintering conditions. Adapted from Wang et al. [204].
The FAST technique (900 8C, 125 MPa) was also found to
preserve the ne microstructure of the initial ball milled powders
when investigating the preparation of bulk nanostructured FeCo
CrV magnets [197].
New bulk FePt-based alloys (Fe50Pt, Fe35Pt30P and Fe
44Pt3C) were developed by a process involving the SPS of
mechanically treated powders [198]. When in contact with
articial saliva, the obtained alloys resulted highly stable also
during long-term exposure.
Nanostructured steel powders prepared by mechanical alloying
were consolidated by current activated sintering processes [199
201]. In particular, high-nitrogen stainless steel (FeCrNiN and
FeCrMoN) powders produced by mechanical alloying were
compacted by SPS at 900 8C (10 min heating time to the
compaction temperature and 5 min holding time) and the obtained
product retained the original powder nanostructure [199]. Fe
18Cr11Mn nanostructured stainless steel powders with high
nitrogen content were rst produced by mechanical alloying
(attritor or Spex mill) and subsequently densied by SPS at 800 8C
for 7 min thus obtaining an almost fully dense product with
nanograin sizes in the range 14.548.8 nm [200]. Ball milled 316L
steel (Fe17Cr13Ni2.2Mo0.8Si0.02C) powders consisting of
austenite and martensite with crystallite size in the range of 10
20 nm were compacted by pulse current sintering technique,
which allowed to obtain fully dense samples with austenitic
structure characterized by grain size in the range of 150200 nm
[201]. The SPS technique was also used to rapidly (6 min) sinter the
Fig. 30. Current ows through the randomly hollow sphere (RHS) sample during SPS: (a) current ows through the RHS ball wall; (b) extra Joule heating helps the elimination
of micro-pores and (c) spark plasma generates at ssure or mass gap in the RHS ball wall, resulting in the evaporation/condensation mass transferring. Adapted from Khor
et al. [205].
Fe2Cu2Ni1Mo0.8C alloy mixed or milled powders [202,203].
Specically, the effects of milling time and sintering parameters on
the densication degree, microstructure, mechanical properties
and fractured characteristics of SPS products were investigated.
The fabrication of porous stainless steel by SPS was investigated
by analyzing the effect of the parameters during sintering pro-
cesses on properties, such as porosity and compressive strength
[204]. A comparison with the corresponding results obtained by HP
was performed. It was found that, to obtain similar porosity, the
sintering temperature of SPS process is lower than in the HP
process, and the holding time relatively shorter (cf. Fig. 29). In
addition, compressive properties of the SPS samples were superior
to those of the HP samples.
The densication of stainless steel 316L randomly hollow
sphere (RHS) structures was studied by SPS in the temperature
range 10001200 8C and adopting a soaking time of 3 min [205].
The mechanism of SPS densication of RHS cell wall was proposed
as schematically represented in Fig. 30. It was also found that
microhardness and the Youngs modulus of the RHS cell wall
increases as the SPS temperature was increased.
2.1.7. Magnesium
A rapidly solidied Mg alloy (AZ91) prepared by a roll technique
was processed, after being crushed into ne powders, by pulse
current sintering at 673 K [206]. The obtained pre-formed
compacts were extruded into a bar using semi-solid consolidation
process at 723 K at a pressure 40% lower than that needed for as-
cast alloys. In addition, the obtained consolidated specimen after
heat treatment showed high tensile strength 350 MPa. Thus, the
proposed process, which takes advantage of the pulse current
sintering machine, is able to lead to an improvement of formability
and tensile strength of AZ91 alloys.
Porous magnesium-based materials of various plateau stresses
were fabricated by PECS method using chips of magnesium alloys
(AZ91D, AM60B, AZ31) as raw materials [207]. During PECS
experiments the samples were heated for 10 min from ambient
temperature to the sintering temperature (500, 530, 550, 575, and
600 8C), and held at that temperature for 10 more minutes. The
effect of pore ratio on the properties of the porous material was
investigated. It was found that the condition for preparing the
well-joined porous materials using PECS process is to use alloys
that have large amount of low melting compounds and large semi-
solid temperature range. The plateau stresses of the porous
materials investigated in this study are in the range from 1.3 to
37.3 MPa and pore ratio is the most important factor that affects
plateau stress.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 151

2.1.8. Molybdenum
The preparation of bulk molybdenum samples was investigated
starting from either micro- [208], or nanopowders [209] using the
P2C technique. When staring from microsized (47 mm) powders,
samples were consolidated at 1650 8C, 48 MPa, for 12 min, up to
theoretical density of 98%. In addition, it was found that pulsing the
powders prior to consolidation had in this case little effect on
microhardness of the obtained compact as compared to the case
when the process was conducted under no-pulse conditions [208].
When nanocrystalline (100 nm) powders were used as starting
material, the sample consolidation (97% theoretical density) was
attained at 1400 8C, 48 MPa for 3 min [209]. It was found that the
compact obtained when staring from nanocrystalline powders is
characterized by higher microhardness (2.95 GPa) as compared to
the case of microsized powders (2.16 GPa).
Powders of the Mo-based alloy TZM (0.47 wt.%Ti, 0.109 wt.%Zr,
0.018 wt.%C, 0.0016 wt.% O, 0.0004 wt.% N, <0.01 wt.% Fe, Si, and
Ni, <0.0001 wt.% H) were densied in 23 s at pressures up to Fig. 31. XRD patterns of consolidated Ni15Zr13Ti3Si2Sn7Nb1Al samples. Adapted
690 MPa taking advantage of the HEHR resistance sintering from Lee et al. [186].
technique [30]. The effects of specic energy density (up to
9000 J/g) and applied pressure (up to 690 MPa) on product at a sintering temperature of 773 K with a loading pressure of
densication were investigated. Sample densities over 96% were 600 MPa [212]. The consolidation of Ni20Zr16Ti2Si3Sn amorphous
obtained at specic energies greater than 3200 J/g. In addition, powders produced by the gas atomization process, and coated by
product density was found not affected by the applied pressure in ductile Cu, was also investigated by SPS [188]. Densication was
the range 280690 MPa. performed at 500 8C for 10 min and by applying a mechanical
pressure in the range of 300350 MPa. The SPS compact exhibited
2.1.9. Nickel a relative density of over 98% and high hardness (>800 Hv).
EDC experiments were carried out using oxidized Ni powders to A closed cellular NiP alloy was recently fabricated by SPS using
investigate the compaction evolution during EDC process, in order phenol resin spherical particles coated with a Ni6%P alloy as
to understand the mechanism of the oxide breakdown and neck starting material [35,213]. A SPS-515 apparatus (7 MPa, 700 8C,
formation during passage of a high-voltage and high-density 15 min) was used. A metallic cellular material with ne, equiaxed
current [210]. On the basis of the experimental results, a four steps and controllable cellular structure was obtained. An example of the
mechanism, which includes the electronic and physical breakdown structure of the cellular NiP alloy obtained by SPS is reported in
of the oxide layer, and neck formation and growth, was postulated. Fig. 32. In particular, it was found that the compressive strength of
Ni powders were rapidly densied by SPS in 360 s of heating the alloy with smaller cell size was higher than that with a larger
time from ambient temperature to 900 8C and by applying a cell size. Moreover, it was observed that when ne cells were
mechanical pressure of 40 MPa [82]. It was reported that Ni added to a coarse cellular structure the resulting compressive
densication takes place rapidly because of the promotion of neck strength was improved.
growth and plastic deformation of powder particles during the The preparation by SPS of Ni5W/Ni12W/Ni5W (at.%) alloy
initial stage of SPS. composite substrates to be used for coating conductors was
Ni43 at.%Mo catalysts were fabricated by SPS starting from investigated starting from Ni and W commercial powders [214].
ball milled powders consisting of an agglomerated amorphous The latter ones were rst mixed according to the alloys compositions
matrix in which nanocrystalline Mo was dispersed [211]. SPS was and packed in the graphite die in the due sequence. SPS was
performed at different temperatures (from 400 to 1300 8C) and performed in vacuum at 900 8C for 30 min, 112 8C/min heating rate,
processing times (35 min) and by applying a mechanical under an applied pressure of 30 MPa. It was found that the outer
pressure of 120 MPa. The obtained products represents electro- Ni5W layer in the composite substrates had a sharp and pure cube
active Raney electrodes of different densities and reactivity. In
particular, samples characterized by relatively ne-grained
nonequilibrium phases which behave as electro-active sites,
were able to effectively catalyze the hydrogen evolution reaction
in KOH 30% solution at 70 8C.
Ni-based bulk metallic glass were obtained by SPS starting from
Ni15Zr13Ti3Si2Sn7Nb1Al [186] or Ni10Nb15Zr15Ti7.5Pt [212]
amorphous powders prepared by gas atomization. Full consolida-
tion of Ni15Zr13Ti3Si2Sn7Nb1Al was obtained at 843 K for 60 s
with an external pressure in the range 100300 MPa and the
resulting metallic glass displayed similar superplastic behavior to
the as-cast material [186]. From the XRD patterns taken from the
Ni59Zr15Ti13Si3Sn2Nb7Al1 bulk metallic glasses consolidated
with different pressures, a broad halo peak in the 2u range of 36
488 was observed (cf. Fig. 31). The latter one is a characteristic of
the amorphous structure, thus indicating that the amorphous
structure was remained during SPS process. Fig. 32. SEM image of a cellular NiP alloy specimen 3035 mm cell size and 55%
The sintered glassy Ni10Nb15Zr15Ti7.5Pt specimens with porosity obtained by SPS under 7 MPa pressure, 700 8C temperature, and 15 min
nearly 100% relative density were obtained by the SPS process sintering time. Adapted from Song and Kishimoto [213].
152 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 33. SPSed Sm bulk with amorphous structure: (a) TEM analysis of the amorphous structure; the inset shows the selected area electron diffraction (SAED) pattern and (b)
HRTEM image of locally enlarged area of the amorphous structure. Adapted from Song et al. [220].

texture, while the use of the Ni12W alloy in the core of the composite
substrates not only enhances the mechanical property, but also
degrades the ferromagnetism of the whole substrates. The average
yield strength of the obtained composite substrate was above
250 MPa, being 100 MPa higher than that of Ni5W substrate.
condensation and using SPS at 573 K and 1 GPa and subsequent
annealing at 623 K [221]. The relative density of the obtained Gd
products was over 99%. In addition, the SPS specimen had an
average grain size of about 10 nm while it increased to about
100 nm after annealing.

2.1.10. Niobium 2.1.12. Tantalum

By means of the SPS technique, mechanically alloyed and
blended niobium alloy (NbAl, NbAlW, NbAlMo, and NbAl
N) powders have been consolidated [215,216]. In particular, fully-
dense NbAl compacts (NbxAl, x from 10 to 25 at.%) were
obtained when sintering temperature was 1773 K and with a
mechanical pressure of 49 MPa while higher temperature were
needed to improve compact microstructure for the two ternary
systems NbAlW and NbAlMo [215]. Regarding the NbAlN
compacts, they consisted of phases in the NbAl system in which
the Nb2N phase was dispersed.
Various potential oxidation resistant Nb alloys in the NbxSi
yAlzCr system (x = 2066.7, y = 020, z = 050 at.%) have been
prepared by SPS [217,218]. In order to improve the homogeneity of
product microstructure, Nb, Si, Al, and Cr powder mixtures were
rst pre-sintered in vacuum by SPS at temperatures in the range
11731973 K, under relatively low pressures (1018 MPa) for 0.3
1.8 ks, and the obtained compact was milled. The resulting
powders were then re-sintered in vacuum by SPS in the tem-
perature range of 11731973 K for 0.31.8 ks, under an applied
pressure of 50 MPa. Regarding the characteristics of the obtained
products, it was found for instance that Nb56Si11Al3Cr (at.%)
samples displayed extremely good oxidation resistance in the
temperature range of 7731673 K.
Coarse (15 mm) and nanocrystalline (63 nm) Ta powders were
rapidly consolidated by means of the P2C technique [222]. DC
pulses of 60 ms duration at maximum current amplitude of 1300 A
and a voltage varying between 0 and 5 V were applied for 3 min.
Afterwards, a constant DC voltage was applied to increase the
temperature at a rate of 500 8C/min up to the maximum sintering
value (17502000 8C) which was held for less than 1 min. A
uniaxial pressure of 50 MPa was applied to the powder compact. Ta
powders were consolidated at 2000 and 1750 8C for the case of
micro- and nanocrystalline powders, respectively, thus reaching in
both cases a relative density of 95%.
Sintering by SPS of tantalum powders was also recently
investigated [223]. For the sake of comparison, conventional hot
pressing experiments were also performed. Specically, SPS was
conducted in the sintering temperature range of 15001900 8C,
being the heating rate 100 C/min, the dwell time 1 min and the

2.1.11. Rare-earth metals

Nanocrystalline bulk materials of pure rare-earth metals, in
particular Sm, have been prepared by SPS starting from powders
obtained by inert gas condensation [219,220]. When Sm powders
with an average diameter of about 40 nm were consolidated under
the optimal SPS conditions (240 8C as a nal sintering temperature,
a heating rate of 50 8C/min and a pressure of 50 MPa) a 99% dense
consolidated bulk with crystallite size of about 90 nm was
obtained (cf. Fig. 33). Compared with the conventional polycrystal-
line bulk, Sm nanostructured bulks exhibited substantially
improved physical and mechanical properties, such as microhard-
Fig. 34. Vickers hardness (HV1) of the compacted tantalum samples plotted as a
ness and specic heat capacity. function of the relative sintering density: a slight increase of the hardness of the
Single-phase bulk nanocrystalline Gd samples were obtained samples obtained by the SPS process can be recognized. Adapted from Angerer et al.
starting from nanometer-sized Gd powders prepared by inert gas [223].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
applied pressure in the range 2030 MPa. The obtained compacted
products were characterized in respect to texture, density, Vickers
hardness and phase composition. The relative density of SPS
compacts reached 8495% of the theoretical value depending upon
the sintering temperature. It was found that the SPS compacted
sample have a little higher hardness at a given density as compared
to the HP products (cf. Fig. 34). This result was possibly explained
by the different microstructure of the two products as a con-
sequence of the different mechanisms involved in the two
processes due to the signicant reduction of the holding time
(SPS process takes 1 min instead of 60 min by HP). The inuence of
the SPS method on the texture rearranging process was also
investigated and the differences from the conditions encountered
during conventional HP process were highlighted.
2.1.13. Titanium
The inuence of processing conditions on mechanical and
corrosion properties of nal products obtained during consolida-
tion of titanium and titanium alloy (Ti6Al4V and Ti6Al2Sn
4Zr6Mo) powders by resistance sintering was widely investigated
by Zenshiro and Kiyoaki [224227]. It was found that the variation
of electric resistance during sintering is related to the current level,
applied pressure, particles size, pre-treatment of powders and the
presence of other alloying metal powders. Specically, regarding
the latter aspect, while Mo and Cr to Ti led to a decrease of compact
electric resistance, the addition of Al gave rise to the opposite
effect.
Ti compacts 96% dense were produced by resistance sintering
within 2 s and the corresponding microstructural and mechanical
properties were investigated [228]. It was found that the obtained
sintered Ti samples exhibit relatively higher yield stress and
ultimate tensile strength as compared to analogous products
obtained by other P/M techniques.
More recently, the densication of coarse titanium powder by
SPS was investigated [229]. In addition, the SPS samples were
deformed in compression either in the same SPS apparatus or in a
HP furnace to evaluate the eventual contribution to densication of
spark discharging or anisotropic heating. The obtained results
showed that none of them played a role in densication.
SPS was also used for preparing a TiPt alloy starting from Ti
and Pt powders [230]. The resulting SPS product consisted of a Ti
matrix with dispersed Pt and some TiPt intermetallics (in
particular Ti3Pt), which are responsible of the high corrosion
resistance exhibited by the material.
Due to their importance for potential clinical use because of
their mechanical properties and good biocompatibility, porous Ti
and Ti alloys have been studied using different current activated
sintering techniques [13,14,231234]. Sintered porous Ti and Ti
6Al4V compacts with continuous pores were fabricated by SPS
[231,235]. The obtained specimens (about 30% porosity) were
characterized in terms of compressive stressstrain and biocom-
patibility. It was found that compressive strength was increased
after annealing the SPS compact in vacuum at 1000 8C for 24 h.
Regarding biocompatibility, the sintered compacts displayed their
ability to be covered with hydroxyapatite (HA) when immersed in
simulated body uid (SBF). More recently, this aspect was deeper
investigated by the same authors [234]. It was found that the
amount of HA precipitated in SPS porous compact was more than
100 times higher than that obtained on Ti plate substrates
subjected to the same immersion in SBF. This fact was related to
the increase of specic surface area obtained using a porous
structure which stimulates HA precipitation.
Ti porous compacts were also efciently produced through the
EEDS technique in less than 400 ms [13,14,232,233]. Starting
materials consisted of Ti atomized powders were subjected to
153
discharges of 7502000 J per 0.7 g powder. The obtained porous
compact displayed much higher compressive strengths as
compared to the human teeth and sintered Ti implants fabricated
with conventional sintering methods.
Starting from atomized powders, titanium and Ti6Al4V
porous-surfaced implants were also prepared by the EDC
technique and the obtained product rst characterized in terms
of mechanical properties and biological response [236240]. It was
found that electrodischarge technique did not alter the physical
characteristic of the material during compaction. Regarding the
biological aspect, the evaluation of the bone response in rabbit
tibia was evaluated. It was found that the EDC implants are
biocompatible and support rapid osteointegration. On the basis of
the obtained results, the authors stated that the proposed method
may be suitable, after additional investigations, for the develop-
ment of an easily fabricated, cost-effective dental implant.
More recently, still starting from atomized spherical Ti6Al4V
powder, porous and porous-surfaced implant compacts were also
obtained by EDS [241243]. It was found that by properly
manipulating the discharge condition such as input energy and
capacitance, it was possible to obtain Ti6Al4V implants with
various porosities in short times (<155 ms).
Due to demonstrated ability of current activated method to
fabricate non-equilibrium materials, some Ti-based amorphous
bulk materials have been obtained. In particular, Ti(37.5  X)
at.%SiX at.%Fe (X = 010) amorphous powders prepared by
mechanically alloying were successfully consolidated using a pulse
current sintering process at 813 K under 1.5 GPa [244]. Following
the same approach, more recently the same authors successfully
produced Ti45 at.%Zr38 at.%Ni bulk quasi-crystal at 813 K under
an applied pressure of 500 MPa [245]. Along these lines, a dense
quasi-crystalline Ti45Zr35Ni17Cu3 alloy was prepared by combin-
ing the mechanical alloying powder treatment with subsequent
pulse discharge sintering [246,247].
Powders with a nanocrystalline structure of a-Ti(X) (X = Ta or
Nb) solid solution prepared by milling of Ti10Ta and Ti10Nb
(at.%) were pulse plasma sintered and a nal compact with 99.5
and 92% relative density, respectively, was obtained [248]. TEM
investigations of compacted samples showed that the pulse
plasma sintering process caused in both alloys the formation of
a two-phase a + b structure, with a mean grain size of 220 nm.
2.1.14. Tungsten
HEHR technique was used to consolidate selected unalloyed
tungsten and tungsten-based alloys (WNb, WNi, and tungsten
heavy alloys with boron carbide) [32]. The inuence of process
parameters such as pressure and specic energy input on the
consolidation of different alloy systems was described in terms of
microstructure and property relationships.
The densication of untreated tungsten powder was performed
by PAS at temperatures between 2050 and 2685 K for 28 min in
air or vacuum [2]. The density values ranged between 80.2 and
91.5% and the initial micron grain size was retained after
consolidation at temperatures of 2350 and 2400 K.
Compacts of W powders were consolidated by P2C using a
commercially available powders ranging in average particle size
from submicron to 12 mm [249].
Either pulsing or non-pulsing experiments were conducted. For
samples in which pulsing cycle was performed, the pulsed current
was increased at a rate of 100 A/min to the desired pulsing current
(10002500 A) which was held for a selected time interval and a
pressure of 1215 MPa was applied. Afterwards, the pulsed current
was rst turned off and then switched to the constant current
mode. Current was increased to give a heating rate in the range 25
20 8C/min up to the holding temperature (6001750 8C) was
154 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
reached and maintained for 015 min. Pressures ranging from 32
to 190 MPa were applied to the dies throughout the consolidation
experiments. Higher applied pressures resulted in denser com-
pacts. A maximum relative density of 96.7% was obtained. Pulsed
current treatment of W powders prior to consolidation had
neither positive nor negative effects on densication. All samples
consolidated above 1200 8C display grain growth although the
short cycle time of the P2C process.
2.2. Intermetallics
2.2.1. Nb/Al
The synthesis/consolidation of Nb3Al intermetallic was inves-
tigated by PAS using nanocrystalline Nb15.4 at.% Al powders
obtained by mechanical alloying [250252]. The PAS process was
conducted at temperatures ranging from 750 to 1250 8C for 3
14 min under a constant pressure of 30 MPa. An electrical
discharge step of 80 ms cycles on and off was initially performed
with a total duration of 30 s. When starting from 4 h milled
powders, a fully dense Nb3Al product was obtained in 3 min at
1250 8C or 6 min at 1140 8C.
Dense Nb3Al intermetallic was also fabricated by SPS from
powders prepared by hydriding and dehydriding [253]. The
consolidation was conducted at 1773 and 1873 K for 5 min under
a pressure of 49 MPa and with heating rate of 10 K/min. When
T = 1773 K, the obtained product consisted of Nb3Al as a major
phase along with a small amount of Nb2Al, while at T = 1873 K a
single Nb3Al phase product resulted. In addition, nal samples
presented a microstructure ner as compared to that obtained by
diffusion annealing of ne Nb/Al layers. The sintered samples also
presented a high temperature strength and superconductivity
superior to those obtained with other techniques.
The EDC process was used for the densication of a Nb23 at.%
Al multiphase system prepared by mechanical alloying [254].
Green bodies with relative density between 75 and 85% were rst
produced by cold compaction under a pressure up to 450 MPa and
subsequently discharged with high-voltage, high-density current
pulse (discharge time <500 ms and input energy of 0.51.0 kJ g1).
A solid bulk with a relative density of 9899% and consisting of a
mixture of two intermetallic phases of Nb2Al and Nb3Al, with grain
sizes lower than 32 nm, was obtained.
The simultaneous synthesis and densication of nanocrystal-
line NbAl3 material was produced by FAPAS when using Nb + 3Al
mechanically activated powders [255]. To avoid the possible
extrusion of molten Al from the die, a two steps process was
adopted during sintering. In the rst one, during which no
mechanical load was applied, the current was increased to 1000 A
and this value was held for 90120 s to form the NbAl3 phase. To
consolidate the reaction product, in the second stage, the current
was increased to 15001650 A and a uniaxial pressure of 56
84 MPa was simultaneously applied for 30210 min. The relative
density of the end-product ranged from 85 to 96% and the
crystallite size, determined by XRD line-broadening analysis, was
in the range of 57150 nm.
The preparation of fully dense NbAl3 intermetallic was also
carried out taking advantage of the SPS machine (515S model) and
using ball co-milled Nb and Al powders [256]. As for the reasons
mentioned above, a two steps temperature and pressure programs
were adopted. Basically, the rst step was conducted at 20 MPa
and consisted of increasing the temperature from the ambient
value to 600 8C in 10 min and maintaining this value for additional
5 min. This step was followed by a second thermal stage, where the
pressure was increased to 40 MPa and the temperature was
changed from 600 to 1000 8C in 5 min. The sample was then
maintained at 1000 8C for 5 more minutes. A nal product
consisting of a near fully dense (97.5  2.5% of the theoretical
density) single-phase NbAl3 with crystallite size less than 100 nm
was obtained.
2.2.2. Ni/Al
The consolidation behavior of atomized NiAl powders with
average particle size of 6 mm was investigated using the PAS
technique in the temperature range of 11001343 8C, sintering
time 0.53 min, and by maintaining the mechanical pressure
constant at 30 MPa [257]. The sintering process was performed
using a DC current (10004000 A) and was preceded by a step
consisting of 30 s of pulsed electrical discharge (25 V and
750 MPa). Compact densities higher than 95% were obtained at
temperature above 1175 8C and the nearly theoretical density was
achieved at 1330 8C. No signicant grain growth (26 mm) was
observed during the process because of the short time exposure of
the specimen to high temperatures.
The PPS method was applied to a mixture made of Ni and Al
powders to produce dense NiAl [34]. The synthesis/consolidation
process was performed by rst heating for 300 s the sample to a
temperature of 910 K at a rate of about 10 K/s, by using a high
current pulses where the discharge energy and voltage were equal
to 1.6 kJ and 4 kV, respectively. Subsequently, the sample was
further heated to 1420 K at a rate of about 10 K/s with a discharge
energy and voltage of 4.9 kJ and 7 kV, respectively. The specimen
was then maintained at this temperature for 10 min. The entire
sintering process was carried out under a mechanical pressure of
30 MPa. The study of the formation mechanism of NiAl by this
process revealed that the sintering process is accompanied by an
self-propagating high-temperature synthesis (SHS) reaction. In
particular, molten Al rst reacts at 910 K with solid Ni to form NiAl3
and Ni2Al3, and then, at a temperature of about 1420 K, the latter
intermetallics interact with unreacted Ni to form the equilibrium
phase NiAl.
2.2.3. Fe/Al
The synthesis and simultaneous consolidation of nanostruc-
tured FeAl was performed by FAPAS starting from mechanically
activated Fe and Al powders (in the stoichiometric Fe:Al ratio of
53:47) [111,258260]. Ball milled powders with crystallite size in
the range 7090 nm were exposed to high AC currents (60 Hz,
12501500 A) and pressures (70106 MPa). Under these condi-
tions, a reaction was initiated and completed in a very short period
of time (2.53.5 min). The relative density of the obtained product
Fig. 35. Representative secondary electron SEM micrograph showing the
morphology of the FeAl synthesized material obtained by FAPAS from
mechanically alloyed podwer. Adapted from Ji et al. [260].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 155

Fig. 36. TEM bright-eld micrographs showing: (a) a ne-grained zone and (b) a coarse-grained zone present in the SPS Y2O3 reinforced Fe40Al (at.%) sintered sample.
Adapted from Ji et al. [263].

was in the range 9899% and the crystallite size of the synthesized properties of sintered samples were improved as compared to
FeAl, as determined by XRD peak prole analysis, ranged from 32 those obtained with the coarser powder.
to 89 nm. However, the latter values were in large disagreement
with the results obtained subsequently by SEM and TEM 2.2.4. Ti/Al
investigations, where grains size was found in the range 0.8 The EDC method was applied for the synthesis of fully dense
4 mm (cf. Fig. 35) [260]. nano-Ti50Al50 starting from amorphous powders obtained by
The same authors followed a similar approach for the synthesis mechanical alloying of Ti and Al [33,91]. In particular, a constant
and simultaneous consolidation of nanostructured iron aluminides
(Fe47 at.%Al and Fe60 at.%Al) while using the SPS machine (1050
model) instead of the FAPAS apparatus [261]. Experiments were
performed under a pressure of 70 MPa, using a DC current which
was increased from 0 to 1750 in 20 s and then held at the
maximum value for 220 s. The obtained products revealed the
presence of the FeAl phase only for both compositions. The
synthesized FeAl displayed a relative density of 93.5% and 98.5% for
the case of Fe47 at.%Al and Fe60 at.%Al, respectively, and a
crystallite size ranging from 30 to 50 nm.
Recently, the SPS technique was further tested to obtain bulk
nanostructured materials from Y2O3 reinforced Fe40Al(at.%)Zr
B milled powders [262,263]. In the rst paper [262] the SPS
machine (1050 model) was used and powders were processed
either at low or high temperature levels, although the correspond-
ing values were not reported. In the rst case, a signicant amount
of porosity was still present in the nal sample and a thin oxide
layer was formed at the surface of powder particle. On the other
hand, high temperature processing causes the breakage of this
layer and a good densication was obtained as a consequence of
plastic ow and local liquid sintering. In another publication [263],
while using the same powders of the previous paper, sintering
experiments were carried out employing the SPS apparatus (515S
model) and more details were given. Specically, a uniaxial load of
70 MPa was applied, the sintering temperature was 1050 8C and
the heating rate was 250 8C/min. The microstructure of the
obtained samples was heterogeneous with ne grains, having size
in the range of 100400 nm, together with larger grains in the
micrometric range (cf. Fig. 36).
The effect of iron particle size on the properties of Fe3Al-based
intermetallics obtained by SPS from mechanical alloyed powders
was recently studied [264]. The synthesis/consolidation process
was performed using an SPS-1050 machine at 1050 8C for 5 min
under the applied pressure of 50 MPa. Homogeneous and ne
microstructure was obtained by using 23 mm iron powder (cf.
Fig. 37). However, Fe3AlC0.5 was also found in the product as a
consequence of the graphite diffusion from the die/plungers. The Fig. 37. Microstructure of the Fe3Al samples by SPS process: (a) coarse powder and
relative densities of samples were nearly 100%. The mechanical (b) ne powder. Adapted from He et al. [264].
156 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 38. TEM images showing the microstructure of TiAl alloys fabricated with PDS process using mechanically allowed powders: (a) TiAl and (b) TiAl(Cr). Adapted from Sun
and Hashimoto [270].

DC + AC of 1000 A under 87 MPa was applied for 70 s. It was found
that the temperature to obtain full densication after discharging
rectangular pulses was 1286 K while it increases to 1350 K when
superimposing AC, characterized by not rectangular pulses. In
addition, better ductility properties were reached when operating
with rectangular pulses.
The microstructural characteristics and impact properties of
titaniumaluminide (Ti53 mol%Al) compacts produced by spark
sintering when using powders prepared by combustion synthesis
were investigated [7,265]. The combustion synthesized powders
consisting of Ti3Al, TiAl and a-Ti were subjected to the application of
a pulsed electrical discharge followed by resistance heating at four
temperatures, i.e. 1573, 1623, 1648, and 1673 K, for 0.9 and 1.8 ks
under an applied pressure of 18.9 and 33 MPa. Depending upon
temperature levels reached during sintering, different microstruc-
tures and impact properties were obtained. In any case, specimens
with high densities and approaching the equilibrium state can be
obtained in a shorter time by spark sintering with respect to
conventional sintering. Such shorter high temperature exposure
was found important to prevent grain growth.
Elemental Ti and Al as well as commercial TiAl powders were
reacted/consolidated by SPS (1050 model) to obtain dense Ti-
aluminides [266]. After mixing Ti and Al in the stoichiometry
Ti48 at.%Al, the resulting powders were sintered at different
temperatures up to about 1500 K, at a pressure of 13 MPa and with
a holding time of 6 min. Relative densities higher than 98% were
reached above 1373 K for the case of elemental powders, while TiAl
powders required at least 100 K more. The obtained products
consisted of TiAl and Ti3Al, being the amount of latter phase
reduced after heat treatment. It was found that fracture toughness
of TiAl fabricated by SPS (KIC = 26.6 MPa m1/2) was superior to the
analogous prepared via hot pressing (KIC = 1924 MPa m1/2) when
tested under the same conditions.
The densication of Ti50Al50 powders prepared via mechanical
alloying was also recently conducted by SPS [267]. Sintering of the
compacts was carried out at temperatures of 11001200 8C with a
compaction pressure of 30 MPa and a heating rate of 30 8C/min. In
particular, sintering performed at 1150 8C led to the obtainment of
low-porosity samples.
The pulse discharge sintering (PDS) was used in combination
with mechanical alloying (MA) for the synthesis of different TiAl
alloys [106,268271]. Along these lines, the manufacturing of rod
shape TiAl was carried out, and unmilled powder element mixture
was also used for the sake of comparison [268]. The sintered TiAl
rods were found to be homogeneous both in density and in
microstructure along the axial direction. This work indicated that
rod shape TiAl alloys with thin cross-section could be successfully
sintered with this process. The same process (MAPDS) was also
used for the fabrication of TiAl exhaust valves starting from chip Al
and sponge Ti [269,271]. The obtained sintered specimens had a
relative density of 99% and exhibited the same composition and
level of fracture strength as those sintered from the powdered Ti/Al
system, while less expensive materials have been used.
Mechanically alloyed powders of Ti50Al and Ti48Al2Cr
were also sintered and concurrently consolidated by the PDS
process [270]. The optimal operating conditions consisted of the
application of a maximum pressure of 38 MPa, a pulse current of
800A for the initial 30 s and a direct current with superimposed
pulse wave for a programmed thermal cycle. The latter one
involved the achievement of the maximum temperature of 1323 K
which was maintained for 900 s. Fig. 38 shows the TEM obser-
vation results of the TiAl (a) and TiAl(Cr) (b) specimen fabricated by
PDS. Equiaxed gamma grains with a large number of twins were
found in both specimens. The alloy with chromium addition
showed coarser microstructure and superior mechanical proper-
ties to that without additives, both at the ambient and elevated
temperatures (cf. Fig. 39).
Titanium aluminides with different Mg contents of 0, 0.37, 1.84,
3.61 and 15.8 mol% were also PD sintered in 900 s, thus leading to
complete transformation from the supersaturated a-Ti structure to
TiAl with small amount of Ti3Al phase [106]. It was found that the
content of Ti3Al phase in the sintered material decreased with an
increase in the magnesium content. While the TiAl alloy without
Fig. 39. Fracture strength and fracture strain of the TiAl and TiAl(Cr) alloys as
functions of testing temperature. Adapted from Sun and Hashimoto [270].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
magnesium addition showed a submicron structure with equiaxed
gamma grains, the microstructure was coarsened by the addition
of Mg. With an increase in the magnesium content the density of
the material decreased monotonically. This nding is attributed to
the dissolution of light magnesium atoms to the TiAl structure and
the decrease in the Ti3Al phase content. Small amount of
magnesium addition (0.37 mol%) increased the Youngs modulus
of TiAl alloy, but further increases in the magnesium content
decreased the Youngs modulus.
The fabrication of dense Ti50Al, Ti(50  x)Al  xCr (x = 2, 6)
and (50  x)TiAlxCr (x = 2, 6) intermetallics by SPS was inves-
tigated starting from Ti, Al and Cr powders [272]. Sintering was
performed at 1273 K (0.17 K/s heating rate and 5 min of holding
time) and 49 MPa. The sample displacement changed very rapidly
at 823 K as an indication of the occurrence of a combustion
reaction. Most of the fabricated samples resulted well densied.
Regarding product composition, the formed phases of Ti:Al = 1:1
composition samples were TiAl and Ti3Al, and TiAl added Cr
samples consisted of TiAl, Ti3Al, Cr2Al, and Cr9Al17 phases.
Nanocrystalline TiAlX and Al3TiX (X = Cr, Mn or Fe) alloys
have been produced by SPS using mechanical alloyed powders
[273]. Sintering was performed with an applied pressure of 50 MPa
and dwell temperature of 1073 K (Al3TiX) or 1373 K (TiAlX) with
a holding time of 900 s. The SPS technique allowed the obtainment
of dense products (porosity less than 4.3%) and the retention of
nanosized grains as well as the formation of equilibrium phases.
Fig. 40. TEM images of nanocrystalline (Al + x at.%Mn)3Ti fabricated by SPS: (a) 0 at.%Mn; (b) 6 at.%Mn; (c) 8 at.%Mn and (d) 12 at.%Mn. Adapted from Jang et al. [275].
157
Specically, sintered TiAlX alloys consisted of the g-TiAl phase
and the a2 phase. Their average grain size varied between 100 and
150 nm. The Al3TiX alloys were constituted by a single-phase
with an L12 structure and an average grain size of about 30 nm.
The pulse plasma sintering method was employed for the
consolidation of ball milled TiAlCr intermetallics with powder
size of about 20 nm [57]. For the sake of comparison, powder
densication was also performed by hot pressing. It was found that
average density of density of samples obtained by PPS and HP were
98 and 95%, respectively. In addition, TEM investigation revealed
that while PPS samples exhibited grains size in the range of tens of
nanometers, the grains of HP specimens were relatively larger,
although less than 1 mm. In addition, the corresponding strength
and elongation during compression was higher in the rst case.
Ti50Al and Ti48Al2Cr2Nb (at.%) powders were recently
consolidated by P2C to produce near net shape parts in the form of
disks or tiles [274]. The temperature and pressure levels were
10001200 8C, 54 MPa and 12001400 8C, 3037 MPa, for the
cases of Ti50Al and Ti48Al2Cr2Nb, respectively. The obtained
samples were fully dense and a minimal grain growth was
observed to occur during consolidation.
The fabrication of dense (Al + xMn)3Ti intermetallic compounds
(x = 012 at.%) by SPS using mechanical alloyed powders was
studied [275]. Sintering was carried out in vacuum at various
temperatures up to about 900 8C, 100 8C/min heating rate, and
50 MPa pressure. It was observed that the shrinkage of Al3Ti
158 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

and (Al + xMn)3Ti (x = 12 at.%) samples stopped to increase at
about 865 and 660 8C, respectively. Consequently, products grain
size decreased as the amount of Mn was augmented. Fig. 40 shows
TEM micrographs on nanocrystalline (Al + xMn)3Ti prepared by
SPS. All samples had relative densities over 9899% of the
theoretical values. In addition, the (Al + 0.08Mn)3Ti specimen
exhibited the best thermal stability with average grain sizes of less
than 60 and 100 nm after heat treatments at 900 and 1100 8C,
respectively.
2.2.5. Ti/Ni
Bulk NiTi materials with rened microstructure was obtained
by SPS (1030 model) starting from amorphous mechanically
alloyed NiTi powders [48]. A multiphases dense product consisting
of Ni3Ti, NiTi2, as major phases, and NiTi, in less quantity, and
characterized by grain size lower than 500 nm was produced in
10 min at the sintering temperature of 900 8C and with a pressure
of 50 MPa.
The synthesis of dense NiTi was also obtained directly starting
from Ti and Ni elemental powders and taking advantage of the
FAPAS technique [276]. It was found that increasing the current
intensity in the range 8001500 A (45855290 kA/m2) and the
synthesis time in the range 040 min resulted in a decrease of the
amounts of the secondary phases (unreacted Ti, Ni3Ti, NiTi2,
Ni4Ti3). Fig. 41 shows the inuence of the current level on product
microstructure when the synthesis time was 20 min. Under the

Fig. 41. Product microstructure obtained under different current levels during the synthesis of NiTi by FAPAS (20 min, Ti particle size <45 mm, Ni particle size 37 mm): (a)
800 A; (b) 900 A; (c) 1000 A; (d) 1100 A; (e) 1200 A; (f) 1300 A; (g) 1400 A and (h) 1500 A. Adapted from Locci et al. [276].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
optimal conditions identied (1500 A, 110 MPa) it was demon-
strated that, in comparison with others conventional powder
metallurgy methods, the FAPAS technique made possible the
synthesis of relatively homogeneous (only 5.77.8 mol% of NiTi2)
and dense (99% relative density) products in a shorter synthesis
time (20 min).
A pulse current pressure sintering equipment was used for the
consolidation at various sintering temperatures of TiNi alloy
powder prepared by mechanical alloying [277]. The obtained
compact displayed a tensile strength and elongation of approxi-
mately 780 MPa and 7.5%, respectively. This was reported to be the
superior tensile properties of shape memory alloys fabricated by
powder metallurgy techniques.
Powders of Ti50Ni50 with a mean particle size of about 50 nm
were spark plasma sintered at different temperatures in the range
7001000 8C with a heating rate of 50 8C/min and an applied
pressure of 30 MPa [278,279]. The application of the high DC
current was preceded by a pulse electric discharge (25 V, 750 A) for
30 s. It was found that below 800 8C, sintered products have high
porosity but with apparent shape memory effect. On the other
hand, samples sintered at temperatures higher than 900 8C are
denser, but the occurrence of oxidation phenomena resulted in loss
of the shape memory effect [278]. The product obtained under the
optimal sintering conditions (800 8C) was also characterized for
biological applications [279]. After being in contact at 60 8C for
40 min with a solution containing H2O2 and HCl, and post thermal
treated at 400 8C for 1 h, the surface of SPS sample was covered by
an optimal TiO2 coating of anatase thus enhancing its bioactivity.
Moreover, the in vitro cell culture conducted using osteoblast cells
and a biomimetic test in simulated body uid, demonstrated the
biocompatibility of the spark plasma sintered NiTi product.
The SPS process was also utilized for the fabrication of NiTi alloy
samples with different porosities (0, 13%, 25%) starting from NiTi
commercial powders [280,281]. Depending upon the nal density
to be achieved, the SPS operating condition were properly chosen,
i.e. 750 8C, 5 MPa, 5 min, to obtain a relative density of 75%, 800 8C,
25 MPa, 5 min, for samples 87% dense, and 850 8C, 50 MPa, 5 min,
for zero porosity compacts. The 13% porosity sample exhibited a
round microstructure with high ductility, while the 25% porous
product displayed much lower stress ow as compared to that of
the 13% porosity [280]. With the aim of possibly using the SPS
Fig. 42. Cross-section of the 13% porous NiTi product obtained by SPS. Adapted from
Zhao et al. [281].
159
products as a high energy absorbing material, their corresponding
compression behavior was analyzed by investigating an energy
absorbing composite structure made of a concentric NiTi spring
and the 13% porosity SPS NiTi [281]. A cross-section of the 13%
porous NiTi sample SPS sample is shown in Fig. 42.
The composite structure displayed not only high reversible
forcedisplacement relation for small to intermediate loading but
also high energy absorbing property when subjected to large
compressive load. Along this direction, a Ni50.9 at.%Ti shape
memory alloy (SMA) sample with 12% porosity was also fabricated
by SPS at 800 8C, 25 MPa, 5 min and the corresponding superelastic
response was analyzed at various temperatures [282]. It was found
that the porous NiTi produced by SPS displayed a strain rate
sensitivity similar to that of any solid ductile NiTi SMA.
2.2.6. Ir/Nb
The fabrication of single-phase Ir3Nb by PECS was investigated
starting either from a powdered alloy ingot of Ir25 at.%Nb
prepared by arc melting or from pure Ir and Nb elemental powders
in 3:1 atomic ratio [283]. Samples were sintered in vacuum in the
temperature range 17002000 8C, 0.0162.5 8C/s heating rate, 0
4 h holding times, and 40 MPa pressure. For the case of ingot
powder, the relative densities of the obtained products were
between 70 and 90%. At the same sintering temperature (1900 8C),
densication was improved when increasing holding time but this
effect was not signicant for holding times higher than 1 h. When
using elemental powders as raw material, the obtained samples
went to nearly full densication. However, the alloying process
was not completed during sintering and pure Nb was still present
at the end of the process.
2.2.7. Ti/Al/Nb
Several compositions based on Ti75xAl25Nbx alloys (x = 0, 3, 7,
11, 13 at.%) were prepared using Ti, Al, and Nb powders and taking
advantage of the PDS process technique [284]. Sintering was
performed at 1473 K for 10 min under a uniaxial pressure of
56 MPa. In all these cases, specimen with full density were
obtained. Although from XRD analysis a single-phase was revealed,
samples contained also Nb-rich areas. The oxidation rates were
measured from 10731273 K in air for 50 h. It was revealed that Nb
added Ti3Al tended to form ner oxide grain and denser oxide layer
and the oxidation rate could be clearly reduced by increasing Nb
content.
2.3. Carbides
2.3.1. BxCy
B12+xC3x bulk targets (x = 01.0) used for the preparation of
thin lms of B12+xC3x by pulsed ion-beam evaporation were
synthesized by SPS [285]. No detailed information related to the
SPS conditions adopted during the synthesis process were reported
in the paper.
Another investigation involves the preparation of natural nB4nC
and isotopically enriched samples of 10B412C, (10B0.7511B0.25)4 12C,
(10B0.2011B0.80)412C, 10B413C, 10B4(12C0.5013C0.50), 11B4(12C0.5013C0.50)
11
B412C, 11B413C by the SPS method starting from 10B, 11B, 12C, 13C
[286]. Sintering was performed in Ar atmosphere at 2000 8C for
20 min, under an applied pressure of 37 MPa. Products with relative
density higher than 96% were obtained and characterized in terms of
thermal diffusivity by the laser ash method over the temperature
range from 290 to 1450 K. It was found that thermal conductivity
decreased only with increasing the mean mass of boron.
The FAPAS method was used to obtain dense ne-grained B4C
materials starting from mechanically activated B and C (amor-
phous or graphite) powders [84]. Sintering experiments were
160 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 43. TEM micrographs of boron carbide samples: (a) synthesized at 1300 8C showing small particle size; (b) synthesized at 1300 8C showing twins and (c) synthesized at
2100 8C. Adapted from Anselmi-Tamburini et al. [288].
conducted in Ar atmosphere with a maximum applied pressure of
79 MPa. To eliminate adsorbed impurities, the sample was rst
preheated with a constant current of 1000 A for 5 min with a
maximum temperature of about 950 8C. The subsequent sintering
stage was performed at 1750 A and the measured maximum
temperature was approximately 1450 8C. Relative densities of up
to 95% were obtained. TEM observations showed that the product
consisted of grains with size ranging from 100 nm to some
micrometers.
The densication of B4C powder was also investigated by P2C
[287]. Consolidation was performed starting either from pure
boron carbide or in presence of small amounts of sintering aids,
i.e. Al2O3, graphite or TiB2. The process was conducted under an
applied pressure of 32 MPa, an heating rate of 2550 8C/min, and
the powders were maintained at a temperature of 1650 8C for
5 min. It was found that the maximum relative density achieved in
absence of sintering aids was 82.6% and additions of graphite and
TiB2 resulted in no signicant increase in density. Conversely, with
the addition of a small amount (3 wt.%) of Al2O3, densities as high
as 97% theoretical were attained.
The effect of the synthesis temperature on the defect
concentration in B4C prepared from elements by SPS was recently
investigated [288]. SPS experiments (SPS-1050 model machine)
were carried out in vacuum in the temperatures range 1300
2100 8C, heating rate 200 8C/min, 10 min holding time, under a
uniaxial pressure of 70 MPa. Dense samples with up to about 95%
relative density were obtained. It was observed that while the
synthesis of B4C started to occur at about 1000 8C and was
completed in the range 12001300 8C, signicant densication
commenced at 15001600 8C. XRD analysis revealed that the
obtained products exhibited extensive crystallographic disorder.
However, a decrease in the defect structure of B4C took place as the
synthesis temperature was increased (cf. Fig. 43).
Additional results were reported by the same authors [289],
where it was shown the possibility to synthesize less-crystallized
boron carbide with several defects (mainly twins) just after the
completion of B4C formation in the SPS machine. At this point, the
still porous boron carbide with the twins was pulverized and
subjected to densication in the SPS. It was found that in this case
the consolidation was successfully initiated at the lower sintering
temperature of 1600 8C as compared with commercial powders.
2.3.2. CrxCy
Three different chromium carbides, i.e. Cr3C2, Cr7 C3 and Cr23C6,
have been synthesized and consolidated in a single step by pulsed
electric current pressure sintering starting from Cr and carbon
(amorphous) powders mixed in appropriate proportions, i.e. 3:2,
7:3, and 23:6, respectively [125]. Sintering was performed in
vacuum under a uniaxial pressure of 30 MPa and using an electric
pulsed current (on/off pulse interval 12:2). The heating rate up to
the maximum temperature, which was varied in the range 1150
1350 8C, was 100 8C/min and the holding time was about 10 min.
Fig. 44 shows four representative fracture surfaces of Cr3C2
products fabricated by pulsed electric current pressure sintering at
various temperatures. Average grains size increased monotonically
from 1.6 to 5.0 mm with increased temperature. Final products
consisted of chromium carbides with small amounts of Cr2O3, as a
consequence of the presence of oxygen traces adsorbed on the
initial Cr powder. Dense Cr3C2 ceramics (98.9% relative density)
with 3.6 mm average grain were obtained at 1300 8C. Moreover,
the obtained products displayed good mechanical properties such
as bending strength, Vickers hardness, and fracture toughness of
670690 MPa, 1719 GPa, and 7.1 MPa m1/2, respectively.
2.3.3. Fe3C
The synthesis and simultaneous consolidation of cementite by
SPS and the inuence of various elements addition (Cr, Mo, Mn, Ti,
Ni, and Si) on the fabrication and properties of the resulting
products have been widely investigated in Japan [290293]. Ball
milled iron and graphite powders mixed at compositions of 75 at.%
Fe and 25 at.% C were spark plasma sintered in vacuum at 1173 K
for 300 s under a pressure of 50 MPa [290]. A 98% dense product
consisting of cementite with minor amounts of other phases was
obtained and the microhardness value of the cementite bulk was
measured to be 1000 HV.
In order to examine the effect of alloying additions on the
surface structure and properties of cementite bulk material,
elemental powders were rst mixed at various compositions
corresponding to (Fe1xMx)75C25 (when M = Cr, Mn, V, Mo, Ti, Ni
and Si) and the resulting mixtures were subjected to SPS at 1173 K
for 900 s under 50 MPa [291]. The formation of alloyed cementite
was observed with additions up to 5% of Cr, Mo, V and Mn while the
presence of the same content of Si, Ni, and Ti was found to enhance
cementite decomposition during aging. The hardness and Youngs
modulus of the obtained material were increased by the addition of
both Cr and Mn. Correspondingly a slight decrease of heat capacity
was observed.
Using the bulk cementite samples produced as described
previously, high temperature deformation behavior of cementite
were investigated [292]. Specically, in order to avoid decom-
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 161

Fig. 44. SEM photographs for fracture surfaces of Cr3C2 ceramics sintered for 10 min at (a) 1200 8C; (b) 1250 8C; (c) 1300 8C and (d) 1350 8C by pulsed electric current pressure
sintering. Adapted from Hirota et al. [125].

position at high temperature, the (Fe0.95Mn0.05)3C was considered.
Bulk cementite displayed brittle fracture when deformed at a high
strain rate at elevated temperatures. However, it could be defor-
med in a large extent by superplastic deformation at stresses in the
range of 100150 MPa at about 1000 K.
The same type of bulk cementite {(Fe0.95Mn0.05)75C25} was also
characterized by analyzing its deformation behavior by compres-
sion, bending and tension tests at various temperatures and
strain rates [294]. It was found that the strength is signicantly
dependent on temperature and the maximum value of compres-
sive strength measured was 3.2 GPa at 573 K, while at room
temperature, specimens broke with brittle fracture.
Single-phase cementite and cementiteiron composite obtai-
ned by mechanical alloying and SPS as described above were
further characterized to determine their abrasive wear property
[293]. It was found that they had both good wear resistances when
the applied pressures were lower than 0.15 MPa. Conversely, if the
pressure level was higher than 0.31 MPa, the abrasive wear
resistance of steels having a cementite volume fraction higher than
75% became signicantly lower.
2.3.4. SiC
SiC powders (a- and b-type) doped with a low content of Al2O3
(2.64 wt.%) and Y2O3 (1.76 wt.%) oxide or Al4C3 (2.04 wt.%), B4C
(0.39 wt.%) and C (1.77 wt.%) non-oxide additives were rapidly
consolidated by SPS [295]. Powders mixtures were processed
under Ar atmosphere in a SPS-1050 machine at 1700 8C for 10 min,
100 8C/min heating rate and 47 MPa applied pressure. The relative
density of the obtained products was in the range 95.299.7%.
Different products microstructures were obtained when using the
oxide or non-oxide additives. Moreover, compared with the Al2O3
Y2O3-doped SiC ceramics, the Al4C3B4CC-doped SiC ceramics
displayed higher densities, lower fracture toughness, and higher
hardness.
The consolidation by SPS of the Al4C3 (2.04 wt.%)B4C
(0.4 wt.%)-doped ceramic was investigated starting from b-SiC
nanopowders (30 nm) [296]. In all SPS experiments (SPS-1050),
the sintering temperature and applied pressure were maintained
at 1600 8C and 47 MPa, respectively, while heating rates were
varied in the range 100400 8C/min and the holding time was set to
2 or 5 min. A near to full consolidation (relative density higher than
99.5%) was achieved. A signicant grain growth was observed to
occur during the sintering process and grain size increased with
the increase of heating rate (cf. Fig. 45).
An intense research activity on densication by SPS of nano-
structured b-SiC powders (520 nm crystallite sized) prepared by
reactive ball milling was conducted by a joint collaboration
between Japan and US groups [297302]. Consolidation was

Fig. 45. SEM micrographs of the plasma etched surfaces of the SPSed SiC ceramics when varying the heating rate (1600 8C sintering temperature, 5 min holding time): (a)
100 8C/min; (b) 200 8C/min and (c) 400 8C/min. Adapted from Zhou et al. [296].
162 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 46. TEM micrograph of the SiC dense product fabricated using ball milled
powders by SPS at 1700 8C and 10 min holding time. Adapted from Yamamoto et al.
[297].
carried out under vacuum using a SPS-1050 apparatus under
40 MPa pressure, sintering temperature in the range 1000
1900 8C, heating rate 180 8C/min, holding time ranging from 0
to 30 min. High-density (>98%) nanostructured SiC products (30
50 nm) were obtained by sintering at 1700 8C for 10 min without
the use of additives (cf. Fig. 46). It was evidenced that the
densication process was enhanced by a disorderorder transfor-
mation.
The effect of grain size and relative density on the mechanical
properties of the obtained products was also studied and
corresponding values were compared with those ones of the
reference samples fabricated using commercial b-SiC powder with
BC sintering additive [300]. It was found that Vickers hardness,
bending strength, and Youngs modulus of SPS products without
additives and using ball milled powders increased with relative
density. However, these properties were lower than those
corresponding to reference samples with sintering additives,
although the relative density was about the same. This behavior
was reported to be likely caused by the difference of grain bonding
strength due to the presence of sintering additives.
Further studies of the effect of sintering temperature on the
characteristics (grain size, density, thermal and electric properties)
of the obtained nanostructured SiC dense materials have been
conducted [302]. By maintaining constant the applied pressure
(100 MPa), heating rate (180 K/min), and holding time (10 min), it
was found that crystallite size increased from 26 to 61 nm when
increasing the temperature in the range 20732173 K while
relative density remained about the same (99.4%). Correspond-
ingly, both thermal and electrical conductivity of SiC were
observed to increase as a consequence of grain growth.
More recently, the inuence of sintering temperature, holding
time and applied pressure on the consolidation and grain growth
kinetics during the SPS of a pure commercially available ne SiC
powder (mean grain size 0.5 mm) was investigated [303]. Two SPS
machines, i.e. the SPS-2050 and SPS-2080 models, were used.
The temperature was raised automatically at 600 8C, then rst
increased to 1600 8C at 100 8C/min and, subsequently, from
1600 8C to the nal temperature (17501850 8C) with a rate of
50 8C/min. Initial pressure was set to 50 MPa. Afterwards, two
pressure conditions were used: 75 MPa were applied when the
nal temperature was achieved, while in the other case the same
pressure level was maintained since 1000 8C were reached.
Moreover, holding time was examined in the range 110 min.
Sample density was found to increase with temperature and
holding time while SiC was consolidated up to 92% at 1850 8C for
5 min under 75 MPa. It was also observed that diffusion and
migration mechanisms that promote grain growth were strongly
dependent on temperature, which is strictly related to pulsed
current intensity. In addition, to let grain morphology and size
remaining unchanged, it was evidenced that the temperature of
the ultimate pressure must be close to the maximum temperature
of the process.
2.3.5. TiC
A plasma activated sintering method was employed for the
densication of Ti44C56 nanostructured powders (3 nm grain sized
and average particle diameter less than 0.4 mm) synthesized by
ball milling of elemental Ti and graphite powders [304]. Sintering
was performed in vacuum at 1963 K under an applied pressure in
the range of 19.638.2 MPa for 300 s. A fully dense (99.98% of the
theoretical density) products with TiC average grain size of
approximately 70 nm were obtained. Moreover, the obtained
compacts were characterized by 32 GPa hardness, 272.6 GPa bulk
modulus, 181 GPa shear modulus and a Poissons ratio of 0.261.
TiC samples to be used as substrate for hot lament diamond
deposition were recently fabricated by PDS using TiC and TiH2 (less
than 18 wt.%) as raw materials [305]. Porous products were needed
to create more nucleation sites thus improving the adhesion of
diamond lms to the substrate. PDS was performed in vacuum at
5060 8C/min heating rate, 10001200 8C holding temperature,
5 min holding time and 50 MPa. It was found that the porous
substrate obtained at 1050 8C was accompanied by a gain in
nucleation density as compared to the non porous samples.
The optimal temperature of the resulting substrate in terms of
highest growth rate was found to be in the range 9001000 8C.
2.3.6. WC
The fabrication of dense binderless tungsten carbide was widely
investigated using several electric current activated sintering
techniques. For example, WC nanopowders (grain size of about
7 nm), prepared by a solid-state reaction process of WO3, Mg and C
followed by MgO leaching, were consolidated in vacuum using a
plasma activated sintering method [306]. Densication was
carried out at 1963 K for 300 s under applied pressures in the
range 19.638.2 MPa. A near to fully dense WC material was
obtained. The consolidation process led to a slight grain growth
with an average size of approximately 40 nm.
The plasma pressure compaction was also utilized for the
obtainment of bulk WC starting from three different powder
particle sizes (0.2, 0.8 and 12 mm) [307]. Consolidation experi-
ments were performed in vacuum at 1500 8C for 1 min with an
applied pressure of 45 MPa and under conditions of pulse and no-
pulse current. It was found that the application of a DC pulse
current resulted in samples with higher density and microhard-
ness as compared to those obtained without pulsing the powders
before consolidation (cf. Fig. 47). The maximum density value
achieved was 96%.
Dense WC was obtained by the SPS process using different WC
powders sizes, i.e. 0.57, 1.33 and 4.06 mm [308]. Powders were
sintered in vacuum at a temperature range of 15501800 8C,
100 8C/min heating rate, without holding time and under 50 MPa
mechanical pressure. The full density was reached when the
sintering temperature was equal or higher than 1700 8C. The
density of the sintered compact was observed to decrease as
particle sized was decreased. This fact was due to the decarbur-
ization occurring during the sintering process which is enhanced
by the higher amount of surface oxide in the ner WC. In addition,
an abnormal grain growth was observed when the sintering time
was over 1 min and the sintering temperature was higher than
1700 8C. The latter phenomenon corresponded to an increase in
fracture toughness.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 163

Fig. 47. Bar graphs depicting the comparison of pulse with no-pulse conditions at different powder particle size on (a) microhardness and (b) density of bulk tungsten carbide
samples obtained by plasma pressure compaction. Adapted from Srivatsan et al. [307].

Tungsten carbides materials were also produced by the FAPACS

process using tungsten and carbon powders with different W:C
mole ratio, i.e., 1:1, 1:1.1, 1:1.2, 1:1.3, and 1:1.4 [309]. Sintering
was performed in vacuum under 60 MPa mechanical pressure,
3000 A current, 3 min processing time. The corresponding max-
imum temperature and heating rate were 1250 and 1200 8C,
respectively. When considering the mixtures beside that with
molar ratio 1:1, a combustion synthesis reaction was observed to
occur at about 850 8C. Conversely, when the stoichiometric W + C
mixture was processed, the starting powders reacted at higher
temperature (about 1200 8C). In all cases, XRD analysis revealed
the presence of WC and W2C in nal samples. Their relative
densities ranged from 81.1 to 89.9% and Vickers microhardness
values at 1 kg force were from 423 to 731 kg mm2.
Ultra-ne WC powders (200 nm) were sintered without the
addition of any binder phase in a SPS-2040 apparatus under
vacuum using a maximum uniaxial pressure of 60 MPa, 3 K/s
average heating rate, 15731873 K sintering temperature, 08 min Fig. 48. Relative density of WC SPSed samples plotted vs. the sintering temperature
holding time at the sintering temperature [310]. The density of the at different holding time. Adapted from Huang et al. [310].
164 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
nal samples increased when increasing either the temperature or
the holding time (cf. Fig. 48).
In particular, samples with density over 98% resulted above
1673 K and almost fully dense products (99.6%) were obtained
when sintering at 1773 K for 4 min. Only a slight grain growth was
observed during the SPS process. Regarding mechanical properties,
Vickers hardness and fracture toughness were over 2600 HV and in
the range 915 MPa m1/2, respectively.
The consolidation of binderless WC samples by using the P2C
method was investigated using three different WC powder size
particles (0.2, 0.8, and 1.2 mm) and in the sintering temperatures
range of 16001700 8C [311]. During the process a uniaxial pressure
of 10 MPa was rst applied for 3 min (rst stage) and, subsequently,
it was augmented to 35 MPa for 1 min (second stage). A pulsed
current of 1000 A, 60 Hz and 50 cycles were used. The obtained
products were characterized in terms of grain size, and mechanical
properties, i.e. hardness, fracture toughness, and wear resistance. It
was seen that samples obtained from ner powders displayed a
larger nal grain size thus indicating that the experimental
conditions adopted are accompanied by a signicant grain growth.
The highest Vickers hardness value (HV100 = 19.2 GPa) was found
using 1.2 mm sized powders sintered at 1600 8C. Fracture toughness,
Fig. 49. SEM micrographs of the polished and fractured WC (a and c) and WC1VC (b and d) grades, PECS for 1.5 min at 1900 8C, and the polished WC4VC (e) and WC12VC (f)
grades, PECS for 1.5 min at 1800 8C. Adapted from Huang et al. [312].
KIC, values with a maximum load of 30 kg between 6.6  0.7 and
8.7  0.8 MPa m1/2 were obtained for the specimens investigated.
Regarding wear resistance characteristics, very low wear constant
values of approximately 108 mm3/Nm were obtained in all cases,
indicating an excellent tribological performance.
WC and WCxVC materials (x = 116 wt.%) were consolidated
using a Type HP D 25/1 (FCT Systeme) apparatus starting from WC
and VC commercial powders without metallic binder additives
[312]. Densication process was conducted under vacuum in the
temperature range 16001900 8C for 1.54 min, 200300 8C/min
heating rate, and under an applied pressure which was varied
during the process from 16 to 30 MPa at 1050 8C and from 30 to
60 MPa during the heating stage from 1050 to the sintering
temperature. Fully dense WC and WC1 wt.%VC products were
obtained at 1900 8C for 1.5 min (cf. Fig. 49).
The increasing of VC content was found to favor the compact
densication. Specically, when x = 16 wt.%, full consolidation was
obtained at 1600 8C. This fact was related to the formation of a
(V,W)C solid solution during the process. It was also observed that
as VC content was augmented grains size grew rapidly.
Regarding the mechanical properties of the sintered samples, a
maximum Vickers hardness (HV10) of 27.39  0.13 GPa and fracture
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
toughness of 4.38  0.18 MPa m1/2 were obtained for pure WC and
WC1 wt.% VC materials, respectively. By increasing the VC content,
hardness was found to decrease linearly down to 21.41  0.20 GPa
when x = 16 wt.% and also fracture toughness slightly decreases. This
feature was attributed to both the presence of the VC phase as well as
to grain growth.
2.3.7. Al3BC
The fabrication of dense Al3BC materials was successfully
achieved by SPS using powders obtained after heat treating of
mechanically milled Al15 at.% MgB2 powders in presence of
stearic acid as a process control agent [313]. The obtained product,
consisting of Al3BC, AlB2, g-Al2O3 and spinel MgAl2O4, was
consolidated via SPS in vacuum at 873 K, 49 MPa/1 h holding
time thus giving rise to a fully dense bulk nanocomposite materials
was obtained.
2.3.8. AlZrC2 and Zr2Al3C5
The pulse electric current sintering of AlZrC2 and Zr2Al3C5
powders prepared by a solid-state reaction using Al, ZrC and
carbon, was studied [314316]. For instance, the PECS of AlZrC2
powders was investigated in the temperature range 17002000 8C,
40 MPa mechanical pressure, 5 min holding time [314,315]. Both
densities and mechanical properties of the obtained products were
improved as the sintering temperature was increased. Specically,
the AlZrC2 material sintered at 2000 8C displayed a bulk density of
5.12 g/cm3, fracture strength and Vickers hardness of 380 MPa and
11.1 GPa, respectively.
2.3.9. Cr2AlC
The fabrication of the ternary compound Cr2AlC by a pulsed
electric current activation method was performed using either
coarse or ne Cr/Al/C powders [317]. Experiments were carried out
taking advantage of a FCT-Systeme apparatus under an applied
pressure of 50 MPa, in a temperature range of 11001400 8C for
5 min, 200 8C/min heating rate, 50 MPa. Regardless of the reactants
particle size, the product consisted of Cr2AlC, as major phase, with
minor amounts of Cr7C3 and Cr2Al, whose presence was decreased
Fig. 50. BSE images of Cr2AlC samples obtained by PECS and HP: (a) coarser powders PECSed at 1400 8C, (b) ner powders PECSed at 1400 8C, (c) coarser powders HPed at
1400 8C and (d) ner powders HPed at 1400 8C. Adapted from Tian et al. [317].
165
as temperature was increased. Thus, under the optimal conditions
of 1400 8C/5 min/50 MPa, only traces of Cr7C3 were present as
undesired phase in the nal bulk product. When comparing with
HP samples obtained starting from the same powders, it was found
that the pulse activated method was able to fabricate almost pure
Cr2AlC materials in a much shorter time, i.e. 5 min, instead of 1 h.
Moreover, PECS samples exhibited higher hardness than speci-
mens fabricated by HP, i.e. 5.6 and 4.5 GPa for the cases of PECS and
HP, respectively, when starting from ner Cr and Al powders. This
fact was attributed to the relatively slightly smaller grain size as
well as fewer and smaller pores observed in products obtained by
PECS as compared to those prepared by HP (cf. Fig. 50).
2.3.10. Ti3AlC2
The mechanism of formation of the ternary compound Ti3AlC2,
was investigated by SPS using Ti, Al4C3 and C (activated carbon) as
reactants [318]. SPS experiments were performed in vacuum using
a Dr. Sinter 1020 SPS machine under a mechanical pressure of
22 MPa, 1300 8C sintering temperature, 600 8C/min heating rate,
and holding time in the range 17 min. It was found that as the
temperature was increased, Ti6C octahedra are formed. Then two
different intermediate products, i.e. Ti2AlC or TiC, are obtained
from the Ti6C octahedra depending on different sintering
temperatures. Finally, the intermediate products transform to
Ti3AlC2 as the soaking time is extended. In particular, the
mechanism involving Ti2AlC was preferred if the temperature
was below 1600 8C.
The same authors [319], successfully prepared bulk polycrystal-
line samples of Ti3AlC2 by SPS at a pressure of 22 MPa and
temperature of 1250 8C. Two different processing routes were
followed. One was analogous to that adopted above for the
mechanistic study, while in the second one Ti, Al and activated
carbon were rst reacted by SHS and the resulting porous products
consolidated by SPS. The resulting polycrystalline Ti3AlC2 ceramics
had a density of 4.24  0.02 g/cm3 and displayed interesting
mechanical properties like 552  30 MPa exural strength and
9.1  0.3 MPa m1/2 fracture toughness (KIC), the latter being much
higher than the most common structural ceramics.
166 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 51. SEM micrographs showing the microstructure of the Ti3AlC2 samples sintered at different temperatures for 15 min: (a) 1250 8C, (b) 1300 8C, (c) 1350 8C and (d)
1400 8C. Adapted from Zou et al. [109].

A similar approach to synthesize and consolidate in one-step 2.3.11. Ti2AlC

the Ti3AlC2 compound was proposed in the literature and consisted The fabrication of the dense polycrystalline Ti2AlC material by
in involving the pulse plasma sintering method while starting from the SPS equipment was investigated using elemental Ti, Al and C
Ti, Al4C3 and TiC [109], TiH2, Al, and TiC [320], or Ti, Al, and TiC powders with molar ratios of 2:1:1, 2:1.1:1, and 2:1.2:1 [322,323].
[321]. The starting mixtures were sintered in vacuum employing a SPS-
During the rst investigation a Ti/Al4C3/TiC powder mixture 1050 apparatus. A heating rate of 80 8C/min, 30 MPa applied
(molar ratio: 7:1:3) was processed by PDS (PAS-V, Sodick Co. Ltd.) pressure, sintering temperature in the range 9001300 8C, 12:2
in the sintering temperature range 8001500 8C, 50 8C/min heating onoff time ratio, and 8 min holding time were the other main
rate, 50 MPa applied pressure, and 015 min sintering time [109]. processing conditions. A high purity Ti2AlC dense product (99.8%
It was found that the formation of the nal desired compound relative density) with 520 mm grain sized was obtained with a
during the synthesis/consolidation process involved also the molar ratio of Ti:Al:C = 2:1.2:1 under the optimal synthesis
intermediate AlTi3, Ti3AlC and Ti2AlC phases. A fully dense product temperature of 1100 8C. Moreover, the obtained material displayed
almost consisting of a single-phase Ti3AlC2 was fabricated at a Vickers hardness of 4 GPa (at l N and 30 s) and could be machined
1400 8C for 15 min. Product microstructure is made of plate-like using common machining tools.
grains with size of about 510 mm in width and more than 50 mm
in length (cf. Fig. 51). 2.3.12. Ti3SiC2
When the reactive sintering process was carried out starting The fabrication of the ternary Ti3SiC2 compound was carried out
from TiH2, Al, and TiC powders, the powder were rst mixed in in a single step by PAS starting from Ti, Si and graphite powders in a
molar ratio corresponding to Ti:Al:C = 2.8:1:1.8 and then pro-
cessed by PDS using 50 8C/min heating rate, 50 MPa mec-
hanical pressure, being the sintering temperature investigated
in the range 8001400 8C, and 060 min soaking time [320].
Dehydrogenation of TiH2 was observed to occur during the PDS
process below 800 8C. The formation of Ti3AlC2 was found to
involve the AlTi3, Al3Ti, AlTi and Ti2AlC intermediate phases. The
effect of sintering temperature on Ti2AlC and TiC content in the
nal samples is shown in Fig. 52. In particular at temperatures over
1300 8C, a single-phase dense Ti3AlC2 product (> 99.3 relative
density) was obtained.
Finally, the rapid synthesis and consolidation through PDS of
Ti3AlC2 was also investigated using Ti, Al and TiC powders mixed in
two different proportions corresponding to Ti:Al:C molar ratios
equal to 1:1:2 (stoichiometric) and 2:2:3 (slightly off stoichio-
metric) [321]. The sintering temperature was varied in the range
8001450 8C, the heating rate was set to 50 8C/min, the applied
pressure was 50 MPa and the holding time was ranging from 0 to
15 min. When the Ti:Al:C molar ratio equal to 2:2:3 was selected, a
single-phase Ti3AlC2 with relative density higher than 99% was Fig. 52. Ti2AlC and TiC contents as functions of sintering temperature during
obtained at 1300 8C for 15 min. synthesis of Ti3AlC2. Adapted from Zou et al. [320].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 53. SEM of thermally etched surface of Ti3SiC2 obtained by PAS. Adapted from
Feng et al. [324].
3:1:2 molar ratio [324]. The synthesis/densication process was
conducted under vacuum and consisted of two stages. During the
rst one an electric pulsed current (10% on) of 100 A was applied
for 99 s under a pressure of 34.5 MPa while in the second stage the
current (non pulsed) was increased up to 18003500 A with an
holding time in the range 02 h and applied pressure in the range
34.468.8 MPa. The maximum temperature values achieved were
ranged from 1525 to 2500 8C. The optimal condition to give a
nearly dense product characterized by density values of
4.53  0.02 g/cm3 very close to the reported theoretical value of
4.531 g/cm3, and containing small amounts (2 mol%) of TiC as a
second phase, was a temperature of 1525 8C maintained for 2 h as
well as an applied pressure of 34.4 MPa. Dense samples synthesized
in this study were examined by optical and electron microscopy.
Fig. 53 shows a SEM of a surface of Ti3SiC2 which was thermally
etched in vacuum at 1200 8C for 20 min. The gure shows densely
packed elongated grains with no evidence of porosity. The maximum
size in the elongated dimension of these grains is about 25 mm, which
is smaller by a factor of four than the average grain size (100 mm)
reported for samples produced by HIPing at 1600 8C for 4 h [324].
Numerous papers on the synthesis and characterization of
Ti3SiC2-based materials by means of the PDS technique were
published by a Japanese research group [325335].
Specically this ternary compound was rst synthesized by
reacting a Ti, SiC, and TiC powder mixture in the 4:2:1 molar
ratio [325]. PDS process was conducted under vacuum at the
temperature range of 12501450 8C for 15120 min with a heating
rate of 5060 8C/min and 50 MPa mechanical pressure. The purity
and density of the obtained Ti3SiC2 product were higher than
92 vol.% and 99%, respectively, when the sintering temperature
was higher than 1350 8C. At this latter value, the TiC content was
about constant in the sintering time interval of 15120 min.
Regarding samples microstructure, it was found to be of three
types, i.e. ne, coarse and duplex grains, depending on the
sintering temperature and time.
Beside the already investigated Ti/SiC/TiC reactants, another
powders mixture, i.e. Ti/TiSi2/TiC with 1:1:4 or 1:1:3 molar ratio
was tested to synthesize the Ti3SiC2 compound by PDS [326]. The
process was carried out in a temperature range of 11001325 8C
for 060 min, 5060 8C/min heating rate and 50 MPa pressure. It
was found that the formation of Ti3SiC2 phase commenced at
temperatures above 1200 8C. The obtained products consisted of
the desired compound along with TiC as a second phase. In
particular, when the sintering was conducted at a temperature
near 1300 8C for 15 min, the maximum product purity for the 1:1:3
and 1:1:4 systems were about 93 and 95 wt.%, respectively. A good
167
densication was achieved by the PDS technique, being the relative
density of 1:1:3 and 1:1:4 samples higher than 99 and 98%,
respectively, at sintering temperatures above 1250 8C. Moreover, a
solidliquid reaction mechanism between TiSi liquid phase and
TiC particles was proposed to interpret the rapid formation of
Ti3SiC2.
To synthesize Ti3SiC2 samples, three further mixtures, i.e. Ti/Si/
C, Ti/SiC/C, and Ti/Si/TiC, were also processed by PDS [328330].
Powder mixtures of Ti/Si/C with stoichiometric (3:1:2) and off-
stoichiometric (3:1.05:2, 3.1.1:2, 3:1.15:2, 5:2:3, and 3:1.5:2)
ratios were pulse discharge sintered in vacuum in a temperature
range of 12001500 8C for 1560 min, 5060 8C/min heating rate
and 50 MPa pressure [328]. It was found that the fabrication of
high purity products was possible only when starting from non-
stoichiometric powders, being the best product obtained with
stoichiometric powders characterized by a Ti3SiC2 content of only
65.2 wt.%. Conversely, when 5Ti/2Si/3C powders were sintered at
1300 8C for 15 min, the TiC content was reduced to about 6.4 wt.%
and the corresponding relative density was approximately 99% of
the theoretical value. When the 3Ti/SiC/C powder mixture was
examined, it was found that the sintered material is characterized
by a secondary TiC phase whose content is higher than 50 wt.%
[330].
Finally, two Ti/Si/TiC powder mixtures with 1:1:2 and 2:2:3
molar ratios were subjected to PDS under the following operating
conditions, i.e. sintering temperature in the range 12001400 8C,
dwell time 8240 min, pressure of 50 MPa, heating rate 5060 8C/
min [329332]. With the aim of minimizing the amount of TiC in
nal products, it was found that the optimum sintering temperature
was in the range of 12501300 8C. Correspondingly, the highest
Ti3SiC2 content was about 9697 wt.% and higher than 99 wt.% for
the cases of the 1:1:2 and 2:2:3 mixtures, respectively. In addition,
when the PDS process was performed at sintering temperatures
above 1275 8C, the relative density of the obtained 2:2:3 samples
was higher than 99%. Moreover, it was also found that the excess of Si
in Ti/Si/TiC samples did not play a specic role in improving the
purity of Ti3SiC2 [332]. Fig. 54 shows the microstructure of the
Ti3SiC2 sample obtained by PDS from 2Ti/2Si/3TiC powders. The
product consists of large plate-shaped grains and small equiaxed
grains and no secondary phases were identied.
Thus, by summarizing the results above, the PDS method seems
to represent a powerful tool for the fabrication of Ti3SiC2-based
materials. Moreover, among the ve different mixtures investi-
gated by PDS, that one corresponding to 2Ti/2Si/3TiC led to the best
Ti3SiC2 product under the optimal sintering conditions of 1300 8C/
15 min/50 MPa.
Fig. 54. SEM micrograph showing the microstructure of the Ti3SiC2 compound
sintered by PDS from 2Ti/2Si/3TiC powder mixtured at 1573 K for 3.6 ks at a
pressure of 50 MPa. Adapted from Sun et al. [330].
168 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Coarse Ti particles (0.15 mm) were also successfully used for
the synthesis of dense Ti3SiC2 by PDS when starting from 2Ti/2Si/
3TiC powder mixtures [334]. In particular, a 99% dense product
with 97.8 wt.% purity was synthesized at 1450 8C for 20 min under
an applied pressure of 50 MPa.
More recently, to investigate the effect of Al addition on the
synthesis of dense Ti3SiC2 by PDS, powder mixtures of 3Ti/SiC/C/
xAl (x = 00.2) were processed by the same group [335]. It was
observed that small amount of Al addition favored both synthesis
and consolidation of Ti3SiC2. In fact, an almost single-phase
product was obtained if x = 0.15 or 0.2, when the sintering
temperature of 1200 8C was held for 15 min.
The various Ti3SiC2 products obtained via PDS by the Japanese
research group as described above have been also extensively
characterized from the mechanical point of view in terms of
deformation, fracture and cyclic fatigue propagation behavior, and
the obtained results are reported elsewhere [333,336338].
The rapid synthesis and consolidation of Ti3SiC2 was performed
by SPS from the starting powders of Ti/Si/TiC mixed in a
stoichiometric ratio of 1:1:2 [339]. The investigation was carried
out in vacuum on a SPS-1050 machine (12/2 onoff time ratio) in
the temperature range 11251400 8C, 100 8C/min heating rate, 20
60 MPa pressure and 010 min holding time. Evidence of the
Ti3SiC2 formation was observed at about 1200 8C, which is several
hundreds degrees lower than the temperature of conventional
reactive hot pressing. The optimal result was obtained at 1250 8C/
60 MPa/10 min and corresponded to an almost fully densied
product consisting of Ti3SiC2 with 2 wt.% TiC.
Another Japanese research group have investigated the synth-
esis/densication of Ti3SiC2 taking advantage of the SPS apparatus
[340342]. Reactant powders used were made of TiC, Ti, carbon
black. The effect of the Al addition on the synthesis process was
investigated by SPS experiments which were performed at 80 8C/
min heating rate, 30 MPa pressure, sintering temperature in the
range 6001400 8C for 030 min holding time. It was found that
the appropriate addition of Al accelerated the formation of Ti3SiC2
and favored its grain growth. Specically a 97.8% dense and pure
Ti3SiC2 product was obtained when the 3Ti/1Si/2C/0.2Al powder
mixture was processed by SPS at 11501250 8C/30 MPa/10 min.
Also, the SPS products displayed a Vickers hardness of 4 GPa (at 1 N
and 30 s). For the sake of comparison, the same powders were
processed by HP and similar products in terms of density and
purity were obtained when sintering at higher temperatures and
longer processing times, i.e. 13001400 8C/30 MPa/2 h.
More recently, the inuence of Al addition to 3Ti/Si/2C powders
on the fabrication of dense Ti3SiC2 by SPS was further examined
[343]. A SPS-2040 model apparatus was used in vacuum under the
Fig. 55. (a) Magnetization and (b) resistivity curves of the SPS-processed MgB2 specimen. Adapted from Lee et al. [345].
condition of 50 MPa mechanical pressure, 100200 8C/min heating
rate, 11001350 8C temperature, and 236 min holding time. It
was found that dense Ti3SiC2 materials (>98%) with TiC content
less than 2 wt.% could be obtained from 3Ti/Si/2C/0.2Al mixtures at
1280 8C when the holding time was higher than 6 min. Product
purity was improved by increasing the holding time but it was
accompanied by an increase in grain size.
2.4. Borides
2.4.1. HfB2
The fabrication of dense HfB2 by SPS (model 1050) was
investigated using either already synthesized HfB2 powders or
reacting hafnium and boron powders in stoichiometric ratio [344].
Specically, sintering of the diboride product was performed in the
temperature range 18001900 8C, heating rate of 100 8C/min,
holding time of 10 min and under a mechanical pressure in the
range of 3095 MPa. However, the maximum relative density
achieved was only 87%. On the other hand, the reaction synthesis
and the simultaneous consolidation performed in the SPS at
1700 8C, 10 min holding time, 95 MPa mechanical pressure, leads
to a HfB2 product with 98% relative density. A similar result was
also obtained when the process was conducted at 1900 8C with
zero holding time.
2.4.2. MgB2
Several investigations have been performed for the fabrication
of the MgB2 superconductor by SPS either starting from already
synthesized powders [345347] or reactants precursors [348
350]. Commercial MgB2 powders were spark plasma sintered
under not well-specied thermal conditions (1060 or 1250 8C for
15 min, electric current sintering of 1200 A) with an applied
pressure of 30 MPa [345,347]. Regarding product microstructure,
faceted MgO particles of about 8% volume fraction were found
dispersed in the predominant MgB2 matrix. The obtained specimen
showed a sharp superconducting transition with an onset TC of
38.5 K, similar to that (39 K) of MgB2 single crystal, and a transition
width (DT) of 0.5 K (cf. Fig. 55).
A similar investigation was performed to obtain highly
densied superconducting materials by processing MgB2 powders
using SPS in the temperature range 9501050 8C, heating rate of
about 200 K/min, dwell time in the range 1030 min, under an
applied pressure of 50 MPa [346]. The XRD analysis revealed that
the product consisted of hexagonal MgB2 as major phase with
small amount of MgO. A density of above 99% was reached in
specimen sintered both at 1000 8C for 30 min or 1050 8C for
10 min. Both samples displayed a critical transition temperature
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
higher than 38.5 K, and a superconducting transition width (DT)
less than 0.5 K. In addition, high critical current densities of
Jc = 7.7  105 A/cm2 in a eld of 0.6 T at 5 K and of 8.3  104 A/cm2
in a eld of 0.09 T at 35 K were obtained. The excellent
superconducting characteristics of the SPS-processed MgB2 were
attributed to the presence of MgO nanoparticles and to the well
uniformly distributed dislocations inside the MgB2 grains.
As mentioned above, the SPS equipment was also used for
synthesizing and simultaneously consolidating the MgB2 mate-
rial [348350]. Specically [348], magnesium was rst distilled
to produce MgH2 which was the precursor to be reacted in the
SPS machine (515 S Model) along with amorphous boron. Powder
mixtures were heated from room temperature to 993 K in 1 h and
then held at this temperature for 1 h. The entire pulse plasma
synthesis process was conducted under an applied pressure of
40 MPa. The microstructure of the obtained specimen displayed a
homogeneous distribution of small pores with size in the range
15 mm. From the compositional point of view, the sample
consisted of magnesium diboride and traces of MgO. The syn-
thesized material exhibited the superconducting transition
with an onset at 37.3 K.
More recently, the simultaneous synthesis and consolidation of
bulk MgB2 superconductors by SPS (515 S model) was obtained
directly starting from Mg and B commercial elemental powders
[349,350]. The inuence of process parameters, i.e. synthesis time
(020 min), dwell temperature (6001000 8C), heating rate (13
400 8C/min) and mechanical pressure conditions (501000 MPa)
on both process dynamics and product characteristics were
systematically investigated. The complete conversion of reactants
into the desired phase was achieved at 800 8C in 10 min and with a
pressure of 50 MPa (cf. Fig. 56).
In addition, it was observed that, within the ranges investi-
gated, while the dwell temperature and sintering time strongly
inuenced reactants conversion and the densication process, not
signicant changes were observed when varying heating rate and
Fig. 56. XRD patterns of SPS products in the MgB system obtained at different
values of dwell temperature TD (P = 50 MPa, tT = 10 min, tD = 5 min): (a) TD = 600 8C;
(b) TD = 700 8C; (c) TD = 800 8C; (d) TD = 900 8C and (e) TD = 1000 8C ((*) MgB2; (~)
MgO; (&) MgB4; (*) Mg). Adapted from Locci et al. [350].
169
pressure. The superconducting properties of the obtained samples,
and particularly the critical current density, resulted comparable
or better than those corresponding to other MgB2 preparation
techniques.
An SPS device was also used for the fabrication of high density
undoped MgB2 ceramic or doped with 5% SiC or 5% B4C [351].
Sintering was carried out in vacuum using a Dr. Sinter machine
(12:2 on:off pulse sequence) in the temperature range of 960
1000 8C, heating rate of about 200 8C/min, 120280 s dwelling
time and under an uniaxial pressure of 63 MPa. All samples
exhibited a relative density higher than 90% and the same onset
Tc = 38.5 K. However, superconducting transition width, impurities
and crystal quality were different depending on the doping.
2.4.3. SiB6
Pure SiB6 (a material which displays excellent thermoelectrical
properties above 700 8C along with other interesting character-
istics), has manifested poor sinterability with conventional
sintering techniques while has been fully densied at the sintering
temperature of 1600 8C by SPS [352]. In addition, it was found that
rare-earth elements like Lanthanum was very effective in evolving
the microstructure of SiB6 phase, thus reducing the sintering
temperature and controlling grain growth.
2.5. Nitrides
2.5.1. AlN
AlN powders (particle size equals to 0.44  0.08 mm) containing
no sintering additives were consolidated by Groza et al. [50] to near
theoretical density (up to 99.3% of theoretical) in 5 min at 1730 8C
under 50 MPa pressure by means of PAS. It was postulated that the in
situ cleaning ability of powder particle during plasma activated
densication leads to enhanced particle sinterability. The initial
particle size of AlN powders was retained in the nal microstructure
that consisted of polycrystalline grains with an average size of
0.77  0.1 mm. The use of PAS process to densify AlN powders to
nearly full theoretical density (9799%) in 510 min was also
investigated by Hensley et al. [353]. The process consists of a pulse
activation step, followed by sintering at 17301800 8C using resis-
tance heating in carbon dies. Submicron size (approx. 0.44 mm) AlN
powders of low oxygen content (<1 wt.%) were consolidated to near
full density in both air and vacuum with no sintering aids or binders.
TEM examination revealed an equiaxed, submicron grain structure
(approx. 0.77 mm) with no apparent pores or intergranular phases. X-
ray powder diffraction revealed no secondary crystalline phases.
When sintering at 1800 8C it was found [354] that grain boundaries
were clean down to atomic-scale resolution and revealed AIN grain-
to-grain contacts throughout the material. EELS (Electron-Energy-
Loss Spectroscopy) data show no evidence for signicant oxygen at
grain boundaries or at grain triple junctions. More recently, AlN
ceramics without sintering aids were fabricated by SPS at 1600 8C,
thus reaching a relative density up to 99.5% [355]. The effect of
microstructure on the thermal conductivity, as analyzed by means of
the phonon scattering mechanism, showed that the very small grains
limit the increase of the thermal conductivity of AlN ceramics
densied by SPS. Sintering aids have been on the other hand
employed by Khor et al. [356]. Specically, pure AlN and calcium
uoride (CaF2)-doped AlN powders are sintered using the SPS
method. Addition of 1 wt.% CaF2 was found to speed up the sintering
process and this yielded thermal conductivity of 110 W/(m K), with
relative density of 95%. SPS of AlN was also carried out with samarium
oxide (Sm2O3) as sintering additive at a sintering temperature as low
as 15001600 8C [357]. There appeared to be a direct correlation
between SPS temperature and number of repeated SPS sintering cycle
per sample with the density of the nal sintered sample. Specically,
170 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
thermal conductivity of AlN samples was improved by increasing the
number of SPS cycle (maximum of 2) and sintering temperature (up to
1600 8C). Thermal conductivity was found to be greatly improved
with the presence of Sm2 O3 as sintering additive. In particular, a
thermal conductivity value of about 118 W/(m K) was found for the
3 wt.% Sm2 O3-doped AlN sample SPSed at 1500 8C for 3 min. Addition
of Sm2O3 greatly improved the densication of AlN sample while
maintaining a ne grain structure. The Sm2O3 dopant modied the
microstructures to decidedly faceted AlN grains, resulting in the
attening of AlNAlN grain contacts. AlN ceramic was also sintered
using SPS by Li et al. [358] with Y2O3, Sm2O3 and Li2O as sintering aids.
Thermal conductivity and strength were found to be greatly improved
with the presence of Sm2O3 as sintering additive, being the thermal
conductivity and bending strength values about 131 W/(m K) and
330 MPa, respectively for the 2 wt.% Sm2O3-doped AlN sample SPS at
1780 C for 5 min. Aluminum nitride/hexagonal boron nitride (h-BN)
composites were prepared by SPS, varying the amount of h-BN from 0
to 30 wt.% [359]. The composites were completely densied when
sintered at 1650 8C for just 4 min under the pressure of 25 MPa with
4 wt.%Y2O3 and 2 wt.%CaF2 as additives, and the Youngs modulus and
bending strength of this material reached values as high as 184.6 GPa
and 394.8 MPa, respectively. Furthermore, the machinability of h-BN/
AlN was greatly improved due to the addition of h-BN. The hardness
of the composites is only 4.98 GPa when the content of h-BN is
15 wt.%. The sintering behavior of AlN/BN composites with 515%
volume fraction of BN was studied by Zhang et al. [360]. Full
densication of AlN/BN composite ceramics could be realized by SPS
technique at temperatures lower than 1800 8C for 3 min. The thermal
conductivity of AlN/BN composites was in the range of 6679 W/mK,
and AlN/BN composites could be cut or drilled by carbides or even
steel tools when BN content is 15% volume fraction. The mechanical
strength of AlN/BN composites was about 330 MPa and was not
remarkably affected by the addition of BN. The improvement of
mechanical properties of AlN/BN composite ceramics was due to the
ne and homogenous microstructure developed during the SPS
process. Transparent AlN ceramics were prepared by SPS technique
with 2.53% (mass fraction) CaF2 or Y2O3 as sintering additive [361
364]. Samples containing 3% CaF2 achieved 99.5% relative density and
52.4% maximum transmittance after 15 min holding time at 1800 8C
and 30 MPa. Sintered bodies were densely compacted and highly pure
with ne grain size and uniform microstructures, and no secondary
phases were observed at the grain boundaries or triple grain
junctions. Yttrium Aluminum Garnet (YAG) in the sample doped
with Y2O3 is found to disrupt the connections of AlN grains and cause
great light diffraction at grain boundaries. The presence of CaF2
induces liquid phase sintering, which promotes the growth of AlN
grains and the densication of the sintered bodies. The sample doped
with 2.5% in mass CaF2 had the best transmittance value of 56.3%.
2.5.2. Si3N4
The densication of b-silicon nitride powders has been
reported by Nishimura et al. [79]. It was found that SPS made
possible the preparation of dense materials (up to 98.5% of
theoretical) more rapidly and at much lower temperatures with
respect to conventional hot pressing, thus minimizing grain
growth during sintering. Using PAS, submicron size, silicon nitride
powders were consolidated by Schneider et al. [78] to >99% of the
theoretical density at 1750 8C in less than 5 min with retention of
the a-phase and the submicron grain size. The silicon nitride
powders were sintered with 5 wt.% Y2O3, and 5 wt.% Y2O3 + 5 wt.%
MgAl2O4 additives. The SPS technique for silicon nitride/additives
mixtures is attractive for retention of ne-grained microstructures
favorable for superplastic deformation. Post superplastic forming
heat treatments to transform the a-Si3N4 to lath-like, creep resis-
tance b-Si3N4 was shown to be another feature of the proposed
processing method. The mechanism of plasma assisted sintering
was also investigated by Schneider et al. [78] using SN-10E silicon
nitride (Ube Industries) with various oxide additives. The
effectiveness of the PAS was thought to be dependent on the
dielectric nature of the oxide additives. As the dielectric storage
capacity of the additive is exceeded, high temperatures are
generated between powder particles as the electrical energy is
released. Samples of Si3N4 mixed powder with oxide sintering
additives, i.e. Y2O3 (5 wt.%) and Al2O3 (3 wt.%), were sintered by
Wada et al. [365] by PECS and hot pressing with the aim of
discussing the characteristic features of the two processing
techniques. The typical low-temperature consolidation and the
plasma effect, which have been reported by several authors to be
classical features of SPS processes, were not conrmed in this
work. On the other hand, when sintering Si3N4 ceramics as
material for electric insulators, the rapid consolidation, which
enabled the nanometer-scale grain size to be maintained in the
dense material, was shown to be the only, albeit important,
advantage of the PECS process with respect to the conventional hot
pressing. It was also shown that a-to b-phase transformation of
Si3N4 was delayed in the surface of the sintered body [366] during
both PECS and hot pressing. The effect of a-/b-phase ratio on Si3N4
properties was investigated by Kawaoka et al. [99]. The b-phase
content of Si3N4 sintered by pulse electric current was varied from
20 to 100 wt.% depending on the sintering condition. It was found
that the fracture toughness increased from 4.6 MPa m1/2 for
20 wt.% b-phase content to 8.2 MPa m1/2 for 95 wt.% b-phase
content, and the fracture strength showed a maximum value of
about 1.6 GPa at 6080 wt.% b-phase content (cf. Fig. 57). Kinetic
aspects of superfast consolidation of silicon nitride-based ceramics
by SPS were also addressed [367]. Specically, the corresponding
phase transformation sequences during the initial stages of the
sintering process, as well as the consolidation mechanisms, were
discussed from the kinetic point of view. a-Si3N4 ceramics were
sintered at a low temperature of 1773 K by using SPS with different
heating rates, and then they were further heat-treated at different
temperatures from 1773 to 2273 K, to study the effect of the
heating rate of SPS on the microstructure and the thermal
conductivity of Si3N4 ceramics after the heat-treatment [368].
Results showed that the heating rate of SPS had great inuence on
the phase transformation and the microstructure of the b-Si3N4
Fig. 57. Variation of fracture strength due to change of b-phase content in silicon
nitride ceramics. Adapted from Kawaoka et al. [99].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
but it did not affect the thermal conductivity of the ceramics. Si3N4
samples prepared by tape casting and lamination were densied
by HP and SPS [369]. A good homogeneity is observed and no single
layers can be distinguished in the fracture surface. Si3N4 ceramics
with V2O5-based glasses as sintering additives were successfully
fabricated by a powder mixing process and rapid sintering by the
PECS method [370]. The fabricated materials exhibited very ne
microstructure with a and b grains. Electric conductivity at room
temperature for the Si3N4/(V2O5B2O3) and at 1000 8C Si3N4/
(V2O5B2O3Al2O3) systems were four and six orders of magnitude
higher at room temperature, and two and three orders of
magnitude higher than the conventional Si3N4, respectively. PECS
has been used by Suganuma et al. [371] to densify a-Si3N4 powder
doped with oxide additives of Y2O3 and Al2O3. A full density (>99%)
was achieved with virtually no transformation to b-phase,
resulting in a microstructure with ne equiaxed grains. With
further holding at the sintering temperature, the a- to b-phase
transformation took place, concurrent with an exaggerated grain
growth of a limited number of elongated b-grains in a ne-grained
matrix, leading to a distinct bimodal grain size distribution. The
average grain size was found to obey a cubic growth law, indicating
that the growth is diffusion-controlled. In contrast, the densica-
tion by hot pressing was accompanied by a signicant degree of the
phase transformation, and the subsequent grain growth gave a
broad normal size distribution. The apparent activation energy for
the phase transformation (cf. Fig. 58) was as high as 1000 kJ/mol
for PECS, almost twice the value for hot pressing (about 500 kJ/
mol), thereby causing the retention of a-phase during the
densication by PECS. SPS was applied by Chen et al. [372] to
prepare a-Si3N4 ceramics of different densities with magnesia,
silicon dioxide, alumina as the sintering aids. The mechanism of
liquid phase sintering was discussed. It was shown that the density
of obtained samples can be controlled from 2.48 to 3.09 g/cm3
while varying the content of the sintering aids. A non-equilibrium
amorphous phase containing a large quantity of well-dispersed
nanocrystalline b-Si3N4 particles obtained by high-energy
mechanical milling of ultrane b-Si3N4 and sintering additives
Fig. 58. Arrhenius plot of the rate constant for the ab phase transformation
during isothermal PECS and hot pressing of silicon nitride. Adapted from Suganuma
et al. [371].
171
of 5-mol% Y2O3 and 2-mol% Al2O3 was consolidated by SPS at a
temperature as low as 1600 8C for 5 min at a heating rate of 300 8C/
min [373]. The fully densied sample consisted of homogeneous
nano-Si3N4 grains with an average diameter of about 70 nm, which
led to noticeable high-temperature ductility and elevated hard-
ness. K, Ca ionic conductive Si3N4 ceramics were fabricated by PECS
[374] with the aim of controlling the composition of grain
boundary phase. The Si3N4 ceramics had glassy phases between
two matrix grains and in multiple grain boundaries, and showed
three orders of magnitude higher conductivity than general silicon
nitride ceramic.
2.5.3. TiN
Nano-sized TiN powders with an average particle size of 19 nm
were rst synthesized by Wang et al. [375] by means of a reduction
nitridation reaction in liquid ammonia starting from titanium
tetrachloride. A consolidation procedure using SPS was subse-
quently applied by maintaining a constant pressure of 60 MPa after
the temperature of 1000 8C was reached. The nal temperature
was held at 1380, 1430, 1480, and 1510 8C for a dwelling time of
1 min, respectively. A dense TiN ceramic (>98% of theoretical) with
mean grain size of 100150 nm was obtained at 1380 8C. TiN/b-
sialon composite particles produced ceramics with TiN networks of
0.10.5 mm wide at 1500 8C, but with TiN grains of 0.12.0 mm
sizes isolated in the sialon matrix at 1600 8C, were SPSed at1500 8C,
thus reaching more than 95% density of the theoretical one,
irrespective of the TiN amount [376]. TiN/sialon ceramics
(25 vol.%) showed a lower electrical resistivity (of about
103 V cm) making these ceramics suitable for electric discharge
machining. Crystalline phases of Al-added TiN, denoted as
(Ti1xAlx)Ny were rst prepared from a mixture of Ti and Al
powders by SHS in a nitrogen atmosphere, and then consolidated
to dense materials (>97% of theoretical) by pulsed electric current
pressure sintering [126]. With increasing Al addition, the optimum
sintering temperatures were lowered, followed by reduction of
grain size. Nano-sized TiN, prepared by controlled hydrolysis of
TiCl4 and Ti(O-i-C3H7)4 solutions followed by nitridation in owing
NH3 gas at 70081000 8C, was densied by SPS at 13001600 8C to
produce TiN ceramics with a relative density of 98% at 1600 8C
[377]. Uniformly sized 12 mm grains in the TiCl4-derived product
and 1020 mm in the Ti(O-i-C3H7)4-derived TiN were revealed.
2.5.4. Other nitrides
Titaniumsiliconnitrogen (TiSiN) composites were pro-
duced from a mixture of Si3N4, titanium nitride (TiN), and titanium
by SPS thus developing wear-resistant materials with good
environmental and biological compatibilities in water and sea
water [378]. The TiSiN composite consisted of Si3N4, TiN, and
titanium metal-rich particles coated with TiSix. Results of sliding
tests in water and in articial sea water showed that the wear
resistance of the TiSiN composite was much better than that of
the titanium metal.
SPS compaction experiments of nanostructured titanium
carbonitride powders, synthesized through rapid condensation
from the gas-phase (high-frequency plasma), have been performed
at 1600 and 1800 8C (sintering time = 1 min) by Angerer et al.
[379]. The sintering results were compared with data obtained by
various conventional sintering techniques such as pressureless
sintering, gas pressure sintering, and hot pressing. The experi-
ments showed that the SPS method is capable of obtaining high
densities (about 94% of theoretical density) combined with small
grain size quotient d/d0 of 5.46.5.
Bulk CrN/Cr2N billet with almost full density was successfully
fabricated using SPS by Aizawa et al. [380]. Ball-on-disk testing was
performed to understand the wear and friction behavior of this
172 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
bulk CrN/Cr2N composite solid. The wear map was constructed as a
function of the sliding velocity and the applied pressure, to
categorize the wear mechanism of this nitride composite.
Two kinds of polycrystalline zirconium nitride (ZrN) pellets
were prepared by SPS [381]. It was found that thermal expansion
was almost independent of porosity. On the other hand, electrical
and thermal conductivities systematically decreased with increas-
ing porosity. Polycrystalline zirconium nitride (ZrN) pellets
displaying three kinds of porosity and the same grain size were
also prepared by the SPS [382]. The room temperature mechanical
properties of the samples were evaluated by ultrasonic pulse echo
measurements.
Nanostructured Cr1xTixN ceramics were prepared by a SPS
technique, using Cr1xTixN powders (3040 nm) synthesized
through a high-temperature nitridation method [383]. It was found
that the nitride powders were highly sintering active, and fully
densied ceramics with a grain size of less than 100 nm could be
obtained at a low sintering temperature of about 1100 8C. In
addition, the high-temperature decomposition of CrN was effec-
tively suppressed under SPS conditions, and the thermal stability of
CrN was improved by forming a Cr1xTixN solid solution. The lattice
constant of Cr1xTixN showed a continuous increase with increasing
TiN concentration, and so did the hardness and grain growth rate;
the electrical resistivity continuously decreased.
2.6. Silicides
2.6.1. MoSi2
MoSi2 from powders of Mo and Si was simultaneously
synthesized and consolidated by means of FAPA [88]. Highly
dense molybdenum silicide up to (99.2%) was produced in one-
step. Minor amounts of Mo5Si3 were present at the boundaries of
MoSi2 grains in the interior of samples made from stoichiometric
reactants. The addition of 2.5 mol% Si excess, however, resulted in
Mo5Si3-free, dense MoSi2 products. Sintered MoSi2 was also
fabricated by a SPS from either MoSi2 powder or mixed powders
of elemental Mo and Si [384]. Dense MoSi2 containing few SiO2
inclusions was obtained by applying in situ synthesis using mixed
powders of Mo and Si. Accelerated oxidation was remarkably
suppressed in the corresponding temperature region of MoSi2.
The effect of mechanical and eld activation on the synthesis of
dense nanometric MoSi2 was investigated by Orru` et al. [385].
Powders of Mo and Si, milled separately or co-milled in a planetary
ball mill, were reacted by SPS under different electric current
conditions. Milled powders reacted faster and required less current
than unmilled powders. Mixtures of powders which were milled
separately (to nanometric size) reacted in the SPS to produce
micrometric a-MoSi2. Similar results were obtained for samples
co-milled to produce nanometric reactants which did not contain
detectable amounts of the product phase. When products form
during milling, they contain both the a and b modications of
MoSi2. The product after the SPS reaction was nanometric MoSi2
with a crystallite size of 140 nm.
Similarly, Mo + 2Si powders were rst co-milled in a specially
designed planetary mill to obtain nanometric reactants but to
avoid formation of any product phases and then subjected to high
AC current (1600 A) and pressure of 106 MPa [386,387]. Under
these conditions, a reaction is initiated and completed within a
short period of time (36 min). The relative density of the product
ranged from 82 to 93%. The crystallite size of the MoSi2 compound
ranged from 58 to 75 nm. In addition, from an isothermal oxidation
at 1273 K for 24 h, only the products synthesized by MAFAPAS
developed a protective layer (the thickness was of about 40 nm) of
SiO2 leading to an improved resistance to pest corrosion. It also
seemed that the hardness of MoSi2 produced from the MA step
Fig. 59. X-ray diffraction patterns of (a) Mo + 2Si milled powders and (b) SPS
product. Adapted from Sannia et al. [388].
(1500 HV), was greater than the hardness of MoSi2 prepared
without the MA step (1000 HV). In addition, the effect of
mechanical activation through high-energy ball milling of reactant
powders on the subsequent synthesis of MoSi2 by SPS was
investigated [388]. Milling (06 h) produced signicant changes in
the dispersion and crystallite size of the reactants initially, and
resulted in the partial formation of the product in both the low-
temperature (a) and high-temperature (b) modications when
longer milling times were employed. Subsequent eld activated
synthesis resulted in the formation of a-MoSi2 only (cf. Fig. 59).
The initiation of the synthesis reaction required a threshold power
level (equivalent to the level of the current), with the threshold
decreasing with increased milling time. However, the initiation
time increased when milling resulted in the formation of a
signicant amount the product phase, with the increase being
markedly signicant at low power levels. Fine MoSi2 powders
containing a small amount of Mo5Si3 have been prepared by SHS,
followed by SPS for 10 min at 12001500 8C and 30 MPa [389].
Dense MoSi2 materials, in which the grain size was about 7.5 mm,
have been fabricated at 1300 8C. They exhibit excellent mechanical
properties: Vickers hardness (10.6 GPa), fracture toughness
(4.5 MPa m1/2), and bending strength (560 MPa).
Pest oxidation and oxidation kinetics of MoSi2 at 773 K were
investigated and compared using as-cast, SPSed poly-crystalline
MoSi2 and MoSi2 single crystal [390]. Specimens (either poly- or
single-crystalline) containing cracks are liable to pest disintegra-
tion after a certain period of exposure. The MoSi2 single crystal
shows a much lower weight gain compared to the dense poly-
crystal during a 300 h exposure. Mechanical alloying and pulse
discharge sintering (MAPDS) process was employed by Shan et al.
[391] and Park et al. [392] to fabricate MoSi2 alloys with additions
of Al, B or Nb alloy elements. A very ne microstructure compared
to that sintered from the commercial MoSi2 alloy powders was
obtained. Signicant hardness increase was found due to the
renement of the binary MoSi2 microstructure. Alloys made from
powders milled in air showed higher hardness compared to those
in Ar gas. This was because of the oxides formed during milling
process. The Al-added alloy sintered from the powders milled in air
gave the best mechanical properties due to the suppression of SiO2
and formation of ne Al2O3 particles. Mo(Si,Al)2 materials with
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
varying Al content were prepared by SHS followed by SPS [393]. It
has been found that the mechanisms responsible for synthesis of
Mo(Si,Al)2 and single-phase MoSi2 are both liquidsolid reaction.
Addition of Al often degraded the mechanical properties of MoSi2,
but biphasic Mo(Si,Al)2 materials exhibited better mechanical
properties, and improved low temperature oxidation resistance
than monolithic MoSi2. The improvement in the reactivity and
mechanical characteristics of Mo(Si,Al)2 was analyzed using PECS
and HIP [394]. It was found that 23% Mo(Si,Al)2 was generated at
a holding time of 10.8 ks or 40% at a holding time of 36.0 ks in
some regions of the sample that were HIP-treated at 180 MPa. The
results show that PECS sintering and HIP treatment of the
pretreated samples densied the sintered bodies leading to an
increase in hardness.
2.6.2. FeSi2
Heavily porous FeSi2 bulky materials for thermoelectric
conversion elements have been developed by Katsuki et al.
[395] via a SPS process. FeSi2 bulky materials with a porosity
ratio of about 45% were molded into U-type thermoelectric
conversion elements in which the p-type and n-type FeSi2 were
separated by insulating glass ber sheets. The doping elements
used were Co and Mn. Ag mesh electrodes were rmly attached,
simultaneously by the sintering process, to the surface of the
sintered products. A thermoelectric power of 0.50.7 mV/K at 300
500 K and an apparent internal resistivity of 3.99  103 Vm at
448479 K have been obtained, which showed a potential for use
in power generation by gas-combustion and heat-exchange type
thermoelectric processes. Mn- (n-type) and Co- (p-type) doped
FeSi2 powders were molded into the cylindrical element via a spark
plasma sintering process, in which Mn- and Co-doped parts were
separated by a thin insulator sheet [396]. Thus, a thermoelectric
power generation system using reciprocating ow combustion in a
porous thermoelectric conversion element has been developed and
examined in its performance. Fully densied and porous b-FeSi2
samples were fabricated by using the PECS method [397]. They
were annealed at 1173 K for 5 days to obtain b-FeSi2 phase.
Oxidation resistance of sintered b-FeSi2 was investigated at
temperatures ranging from 1073 to 1223 K in air. Oxide layer,
which is most likely an amorphous SiO2, was formed on b-FeSi2
samples after oxidation, as revealed by XRD. Granular e-FeSi was
developed below the oxide layer as a result of oxidation of b-FeSi2.
Grain boundary oxidation was not observed. Formation of cracks in
the SiO2 layer and b-FeSi2 was not observed even in on the porous
samples. Fe2Si5-based alloys was fabricated by SPS and subse-
quently heat-treated [398]. A two-phase structure consisting of b-
FeSi2 and Si dispersoids was obtained by the eutectoid decom-
position of a-Fe2Si5 phase during annealing. Fe2Si5-based alloys
have the same conduction mechanism with stoichiometric FeSi2
alloys doped with Mn and Co, respectively. Semiconducting b-
FeSi2 bulks without and with Mn and Co doping were fabricated by
using PECS [399]. The possibility of a direct bonding of n-type b-
FeSi2 to form a pn junction structure was also explored. While n-
type and p-type bulks were strongly joined, the electrical
characteristics of the pn junction was not obtained. Thermo-
electric materials of Fe0.91Mn0.09Si2 were produced with HP and
SPS by Nogi and Kita [400] and their thermoelectric properties
were compared. The relative density of the SPS specimen reached
90% in ve minutes at 1173 K, while the HP specimen reached 90%
in thirty minutes at 1173 K. The optimum condition of the heat
treatment was found to be for 3.6 ks at 943 K for the transforma-
tion to the b-phase. The peritectoid reaction (a + e ! b) mainly
occurred at and above 953 K, and the eutectoid reaction mainly
occurred at 943 K. The b-phase ratio of the HP specimen was larger
than that of the SPS specimen because the peritectoid reaction
173
Fig. 60. Temperature dependence of Seebeck coefcient of Fe0.91Mn0.09Si2 when
varying mass%Cu. Adapted from Nogi and Kita [401].
occurred during longer cooling period from 1173 to 943 K.
Consequently, the Seebeck coefcient of the SPS specimen was
slightly smaller than that of the HP specimen. When copper is
added to the starting mixture, liquid phase sintering probably
occurred since the specimen was better densied [401]. The
relative density of the specimen with 1.5%Cu was 94%, while that of
the specimen without copper was 90%. Copper was also found to
promote transformation to the b-phase. The temperature depen-
dence of thermoelectric properties has been also investigated (cf.
Fig. 60 from Nogi and Kita [401] for Seebeck coefcient behavior as
the Cu content was varied).
2.6.3. Other silicides
Fully densied bodies of Si3Zr5 and Si3Ti2Zr3 were obtained by
PECS method from powders produced by electric arc melting and
crushed by planetary ball mill for 3 h [402]. After 5 min of sintering
at 1600 8C under 50 MPa, Vickers hardness of Si3Zr5 and Si3Ti2Zr3 at
room temperature were 14.9 and 15.9 GPa, respectively, while
fracture toughness were 2.5 and 3.6 MNm1/2, respectively.
Synthesis and sintering of single-phase ReSi1.75 were simulta-
neously performed by SPS using the mixed powders of elemental
Re and Si [403]. In addition, from oxidation tests carried out in air
at temperatures ranging from 773 to 1473 K, the formation of a
protective silica layer was observed at 1273 K and above.
Poly- and single-crystalline NbSi2 specimens with different
microstructures were prepared by arc-melting, SPS and optical-
heating oating zone melting for oxidation experiments at 1023 K
[404]. For arc-melted poly-crystalline specimens containing
microcracks, NbSi2 fully turned into powders after 3 h exposure
at 1023 K, which is known as the pesting phenomenon. As a
comparison, no pesting was found in the dense SPS poly-crystalline
specimens and single crystals after 89 h [405].
NbSiAl and NbSiN ternary phase diagrams were con-
structed by investigating microstructures of spark plasma sintered
compacts of these systems [406]. The microstructure, mechanical
properties, and oxidation behavior of compacts with some
different compositions in the two systems were examined.
Nb3Si5Al2 matrix compact was characterized by extremely good
oxidation resistance at 1573 K, although the compact showed poor
oxidation resistance at 1023 K.
The incorporation of Mg into the Si sub-lattice of molybdenum
disilicide was also discussed by Woolman et al. [407]. It was found
174 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
that through a combination of mechanical milling and FAPAS
synthesis, magnesium was successfully incorporated into the
silicon sub-lattice of the silicide.
Consolidation of the Mg2Si powders obtained by room
temperature MA of Mg66.7Si33.3 powders for 60 h, subsequently
annealed at 620 8C, was performed in a SPS machine using graphite
dies up to 800900 8C under 50 MPa [408]. SPS compact from 60 h
MA powders consolidated up to 800 8C consisted of only
nanocrystalline Mg2Si compound with a grain size of 100 nm.
Mg2Si compounds were formed in the solid-state by SPS of
elemental powder mixture of Mg33.33 mol%Si [409]. The relative
density of the composite alloys was found to decrease with
increase in the amount of Mg2Si particles because the Mg2Si
dispersoids cause not only pores at primary particle boundaries,
but poor sinterability between magnesium alloy powder due to
their thermal stability. Repeated plastic working SPS was also
performed to synthesize and sinter magnesium disilicide at 1100 K
[410,411].
Crystals of MnSi1.73 were prepared by SPS technique [412]. It
was found that the MnSi powders partly formed MnSi1.73 crystals
at 912937 K under the mechanical pressure of 20 MPa in low
vacuum (about 5.0 Pa), and fully formed MnSi1.73 crystals after
sintered at 1173 K for 15 min under 40 MPa.
After high-energy ball milling of a TiSi powder mixture, SPS was
used to consolidate the granules into a ultra-ne grained titanium
matrix by Handtrack et al. [413]. XRD, SEM and TEM were used to
investigate the mechanism of formation of Ti5Si3 dispersoids during
SPS at various sintering temperatures and sintering times and,
furthermore, to characterize the microstructure with regards to
titanium matrix grain size, dispersoid size and distribution. The new
material showed high hardness, strength and improved wear
resistance in comparison to other titanium materials.
Electrical conductivities, Seebeck coefcients and thermal
diffusivities were measured for Ru2Si3 samples with different den-
sities prepared by spark plasma sintering method [414]. Specically,
it was found that electrical conductivities, Seebeck coefcients and
thermal diffusivities increased with sample density.
MgNiSi alloy powders were synthesized by mechanical
alloying, and subsequently bulk samples were consolidated by
pulsed current sintering [415]. Also, sample corrosion behavior
was investigated by measuring the corrosion rate. An amorphous
phase was formed in powders with up to 80 at.% Mg by milling for
2520 ks. These powders contained Si particles and nanocrystals in
addition to the amorphous phase. When bulk alloys were sintered
from the amorphous powder at 473 K, i.e. below the crystallization
temperature, the amorphous phase was maintained, but Mg
crystals grew in the alloy. Subsequently, reduced bulk amorphous
alloy corrosion was observed due to exposure to 5 mass% NaCl
solution for 96.4 ks (24 h) because that exposure formed a black
layer like a passive lm on the amorphous alloy surface.
2.7. Oxides
2.7.1. Titanates
Na0.21Nd0.60TiO3 textured ceramic containing plate-like parti-
cles was fabricated by SPS (515S, Sumitomo Coal Mining Co.) at
1250 8C for 5 min under a pressure of 40 MPa [416]. Starting
Na0.21Nd0.60TiO3 powders were synthesized by soft chemical of
layered Na2Nd2Ti3O10. The SPS sample exhibited {0 0 l} orientation
degree of 9% and anisotropy in the dielectric properties in the
directions parallel and perpendicular to c-axis of the applied
pressure.
Dense Ca1xSrxTiO3 (0.1  x  0.4) ceramics with and without
(0.51.5 wt.%) Li2Si2O5 as additive were obtained by SPS at 1170 8C
for 4 min at 40 MPa [417]. A relative density of 96% of the
theoretical value was obtained for samples containing 0.5 wt.%
Li2Si2O5. Sintered samples consisted of single-phase solid solution
Ca1xSrxTiO3 along with a mixture of TiO2 and Srn+1TinO3n+1 were
obtained when sintering was performed in the absence of Li2Si2O5.
In general, the bending strength, the fracture toughness, and the
Vickers hardness were found to increase by adding 0.5 wt.%
Li2Si2O5 as compared to Ca1xSrxTiO3. Also dielectric properties
resulted improved.
Fully dense (100%) (Li,La)TiO3 ceramics were prepared by SPS
(515S Sumitomo Coal Mining Co.) at 11001200 8C, under a
pressure of 39 MPa [418]. The SPS samples obtained at 1100 8C
showed high lithium ion conductivity (103 S/cm1 at 22 8C).
Dense BaTiO3 ceramics with ne (<0.6 mm) grain size were
obtained by SPS (515S, IZUMI Technology, Japan) starting from ultra-
ne (0.06 mm) hydrothermally prepared powders. Sintering was
performed by applying an electric current of about 1000 A under a
pressure of 50 MPa [419,420]. The temperature was increased to
900, 1000, 1100, and 1200 8C, at a heating rate of about 160 8C/min,
and then maintained for 5 min. Relative density higher than 95%
were obtained at temperature greater than 1100 8C. Sintered
samples exhibited ne microstructure with average grain size of
less than 0.5 mm. Low permittivity of 3003500 was measured over
the temperature range 25300 8C. This nding was attributed to
poor development of ferroelectric domains in the ceramics.
It was also reported that when using SPS (515S Sumitomo Coal
Mining Co.) to consolidate 0.1 and 0.5 mm sized BaTiO3 powders,
for 5 min over the same temperature range (T = 9001200 8C)
adopted for 0.06 mm BaTiO3 but at lower pressure (39 MPa),
relative densities higher than 95% were obtained above 1000 and
1100 8C, respectively [421]. Sintered samples mainly consisted of
submicrometric grains in the range 0.31 mm depending on
sintering temperature and, in general, grain size increased with
temperature. In contrast, samples sintered by conventional heating
in a furnace mufe showed lower density (8092%) and grain sizes
were found to exceed 1 mm. From XRD investigations it was found
that cubic BaTiO3 phase coexisted with tetragonal phase in the SPS
samples at room temperature to indicate that SPS is effective in
stabilizing metastable cubic phase. On the contrary conventionally
sintered samples exhibited a clear splitting of tetragonal signals.
Moreover, xed frequency permittivity measurements showed
slightly higher permittivity for SPS ceramics obtained from 0.5 mm
sized BaTiO3 as compared to those obtained when sintering 0.1 mm
sized BaTiO3, thus reecting the difference in the tetragonal phase
content, which was found to reach higher values for samples from
0.1 mm sized BaTiO3. Higher differences were found when
comparing permittivity of SPS (about 7000 at 1100 8C) and
conventionally sintered samples (about 5000). The higher per-
mittivity of the SPS ceramics was attributed to their higher density
and restricted grain growth.
Starting from powders prepared by solcrystal method, dense
ne-grained BaTiO3 was also sintered by SPS (2040 IZUMI
Technology, Japan) at 900 and 1000 8C (200 8C/min heating rate)
for 3 min at 39 MPa [422]. For the sake of comparison, the same
ceramic powders, cold pressed under a pressure of 190 MPa, were
sintered by conventional method in air for 2 h at 1000, 1200, 1300
or 1400 8C. Samples with average grain size less than 1 mm were
obtained. Relative density higher than 95% was achieved by SPS,
while conventionally sintered sample showed lower density (72
94%) when sintered at 10001300 8C, being 97% relative density
achievable only at 1400 8C. High permittivity of 10000 was
obtained at room temperature for SPS samples sintered at 1000 8C.
When starting from BaTiO3 powders with 0.1 and 0.5 mm
particle sizes in the weight ratio 2:5, dense (99.6%) BaTiO3 targets
for pulsed laser deposition were produced by SPS at 1423 K for
10 min [423].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Dense BaTiO3 ceramics with 50 nm average grain size was
prepared by SPS (Dr. Sinter 2050 Sumitomo Coal Mining, Co.) at
800 8C (heating rate 200 8C/min) for 2 min at 100 MPa [424426].
Dense translucent sintered ceramics with 97% relative density
were obtained. From Raman activity investigations it was found
that sintered specimens exhibited a low tetragonality, resulting in
a reduced polarization and in the lowering of dielectric constant. A
broad ferro-para phase transition with a maximum permittivity of
1100 took place at 390 K and 1 kHz. A progressive tetragonal
distortion was also observed when comparing dense compacts
having average grain size of 30, 50 and 100 nm. The heat of
transition from tetragonal to cubic phases decreased accordingly.
The AFM piezo-response measurements showed that at 50 nm
BaTiO3 was still ferroelectric and critical grain size for the
ferroelectric behavior in dense BaTiO3 nanocrystalline ceramics
was found to be below 50 nm.
Fine (2030 nm) BaTiO3 powders, obtained by SHS and
subsequent ball milling, were recently sintered by SPS (515S
Sumitomo Coal Mining Co.) at 700 A, for different periods of time in
the range 70140 s, under a pressure of 40 MPa [427]. Sintered
compacts with relative density in the range 6699%, depending on
the sintering duration, were obtained. Regarding grain growth
during the consolidation stage performed by SPS, it is seen that
when electric current was applied for a period of time equal or less
than 100 s, BaTiO3 grain sizes were maintained below 50 nm, so
they were affected only modestly by SPS treatment. The observed
dielectric properties were typical of nanocrystalline BaTiO3
ceramics. The Curie temperature was shifted to lower tempera-
tures (108 8C) and the relative dielectric constant was signicantly
depressed by dilution effect due to the presence of a non-
ferroelectric low permittivity grain boundary layer. Results
conrmed the existence of remarkable size and grain boundary
effects in ne-grained barium titanate ceramics.
Ultra-ne pure BaTiO3 synthesized by oxalate precipitation
method was used as starting material to fabricate polycrystalline
(20100 nm grain size) dense (9599% relative density) BaTiO3
through SPS (Dr. Sinter 2050 Sumitomo Coal Mining Co.)
apparatus, at 800850 8C (273420 8C/min heating rate) for 2
7 min under a uniaxial pressure of 70 MPa [428]. Maximum
density (99%) was achieved when sintering at 820 8C for 3 min at a
heating rate of 410 8C/min and when sintering at 850 8C for 7 min
with a heating time of 283 8C/min, respectively. The corresponding
grain sizes were 60 and 100 nm. It was also reported that the
critical grain size for ferroelectricity was 20 nm for dense BaTiO3.
Nanoindentation method was also employed to test the
hardness of 50 nm grain size dense BaTiO3 obtained by SPS. In
general, it was found that the hardness of the 50 nm BaTiO3
increased by 82% as compared to that of the 1.2 mm sized ceramic
fabricated by conventional sintering process [429].
Dense ne-grained ceramics were also obtained by SPS starting
from solgel synthesized BaTiO3 nanocrystalline (13 nm) powders
[430,431]. Densication was performed at different temperature in
the range 700900 8C (200 8C/min heating rate) under a pressure of
50 MPa, for duration times ranging from 0 to 3 min. The maximum
relative density of 99% was achieved when sintering at 900 8C for
3 min. The SPSed compacts exhibited ne and homogeneous
microstructure consisting of tetragonal BaTiO3 with small amount
of the cubic phase. The effect of the holding time on grain size
growth was investigated. Fine-grained BaTiO3 ceramics having
grain size of about 200 nm were obtained by SPS at 900 8C without
holding time. When increasing the holding time, from 1 to 3 min,
grain size increased from 340 to 370 nm. A clear dependence of the
dielectric constant on grain size was observed. For the sake of
comparison consolidation was performed also by cold isostatic
pressing (CIP). Specically lower density (9395%) was achieved
175
by CIP at 400 MPa even when sintering at 1250 8C1350 8C, for 2 h.
Furthermore, much larger (2 mm) average grain size and inho-
mogeneous microstructure were also observed for conventional
sintered specimens.
A detailed investigation over the factors which may have
important effects on SPS process for the densication of the BaTiO3
ceramic was recently reported [432434]. Specically, the
inuence of synthesis method, heating rate, sintering temperature
and holding time on densication microstructure were considered.
BaTiO3 nanopowders were synthesized by solgel acetate, oxalic
acid precipitation, citric acid and methanol methods and subse-
quently sintered by SPS without holding time at 920 8C with a
heating rate 400 8C/min under a pressure of 2040 MPa. It was
found that the oxalic precipitation and citric methods were more
effective in obtaining relative smaller grain size and higher density
as compared to the other ones. The synthesis method was found to
affect also grain shape. Round grains were observed for methanol
and citric methods, while nearly tetragonal grains were observed
for solgel and oxalic precipitation methods. The inuence of
heating rate on microstructure was investigated by heating BaTiO3
from citric acid method at 50, 100, 150, 250, 400 8C/min, at 950 8C
with a holding time of 1 min. All samples reached a relative density
higher than 90%. Beyond 150 8C/min, density curve kept constant,
while for heating rate lower than 100 8C/min density increased
with the heating rate (cf. Fig. 61a). Grain growth was reduced only
for heating rate higher than 250 8C/min (cf. Fig. 61b). In order to
investigate the effect o f sintering temperature, BaTiO3 nanopow-
ders obtained by oxalic acid method were sintered for 1 min
between 800 and 1200 8C. Both density and grain size were found
to increase with increasing sintering temperature as shown in
Fig. 62, where the comparison with conventional sintering is also
reported. Samples with relative density of 95% with grain size of
about 200 nm were obtained when sintering at 900 8C. The holding
time effect was discussed for samples from oxalic acid method
when SPS was conducted at 920 8C with a heating rate of 400 8C/
min and holding time was varied from 0 to 5 min. Both grain size
and density increased with holding time. When the latter one was
below 3 min round grains were obtained, while at 5 min the grains
Fig. 61. Density (a) and grain size (b) of BaTiO3 as a function of heating rate. Adapted
from Li et al. [433].
176 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 62. Grain size (a) and density (b) of BaTiO3 as a function of sintering temperature. Adapted from Li et al. [433].
had a ake shape. The grain growth rate was also considered for
different SPS conditions. It was found that in order to obtain dense
BaTiO3 with submicron grain size the sintering temperature should
be lower than 1100 8C, the heating rate higher than 250 8C/min and
the holding time lower than 2 min.
Dense (94.697.8%) BaTiO3 ceramics with different grain size
ranging from 80 nm to several micrometers were prepared by
controlling SPS conditions [435]. The relationship between grain
size and dielectric properties were also investigated. It was found
that grain size strongly affect phase composition of the sintered
specimens. In particular, the amount of tetragonal phase decreased
with smaller grain size. Correspondingly, investigation upon the
temperature dependence of relative permittivity indicated that the
dielectric constant decreased with decreasing tetragonal content
and Curie temperature shifted to lower values when grain size
were reduced.
PECS method was used to fabricate nanocomposite ceramics
containing dispersed perovskite type ferroelectric particles.
Specically, MgO/BaTiO3 powders with BaTiO3 volume fraction
varying in the range 580 vol.%, were sintered by SPS apparatus
(320 MK-IV, Sumitomo Coal Mining Co.) at 12001300 8C (heating
rate 100 8C/min) for 5 min at 30 MPa [436]. The obtained samples
consisted of MgO and tetragonal BaTiO3. Fine BaTiO3 particles were
homogeneously distributed within the MgO matrix grains as well
as grain boundaries. Moreover, the relative density reached its
maximum value by the adding 40 vol.% BaTiO3 and then it
decreased when BaTiO3 content was further augmented. In
general, near full-dense specimens were obtained after PECS
sintering at lower temperatures and in shorter time as compared to
HPed samples. For example, hot pressed MgO/10 vol.% BaTiO3
nanocomposites were 98% dense after sintering at 1350 8C for 1 h.
Whereas, the same density was obtained after PECS sintering at
1200 8C for 10 min.
SPS was successfully used to consolidate BaTiO3/MgO (pre-
sintered)/BaTiO3 laminate composites at 1300 8C with a holding
time of 5 min under a pressure of 35 MPa [437]. Effect of cycle
stress and stress intensity factor on the voltage response of the
laminated specimens were also investigated in order to conrm
the crack detecting capability.
A SPS apparatus (Dr. Sinter 2050 Syntex Inc., Sumitomo Coal
Mining Co.) was recently used to investigate the sintering behavior
of BaTiO3, SrTiO3, Ba0.6Sr0.4TiO3 and a mixture of composition
(BaTiO3)0.6/(SrTiO3)0.4, all having particle sizes in the range 60
80 nm [438,439]. SPS experiment were carried out at different
temperatures, using a heating rate of 100 8C/min and an applied
pressure of 50 MPa. It was found that densities exceeding 95% of
the theoretical values were obtained at 900 and 925 8C for BaTiO3
and SrTiO3, respectively, using a holding time of 2 min. By applying
a pressure of 100 MPa the same densication level was reached for
SrTiO3 at 900 8C. When sintering Ba0.6Sr0.4TiO3 and (BaTiO3)0.6/
(SrTiO3)0.4 mixture at 925 8C under a pressure of 50 MPa, density
higher than 95% was still achieved in 2 min. Microstructures and
the grain growth evolution with increasing sintering temperature
allowed the determination of a kinetic windows dened as the
temperature interval within which the densication process can be
kinetically separated from the grain growth one. Specically,
BaTiO3 and SrTiO3 exhibited a narrow kinetic window of 25 8C
between 900 and 925 8C, being the corresponding relative density
and grain size in the range 97.598.6% and 0.240.26 mm,
respectively (cf. Fig. 63a and b). No kinetic window was
determined for Ba0.6Sr0.4TiO3. On the other hand, a broad kinetic
window of 125 8C was observed for the (BaTiO3)0.6/(SrTiO3)0.4
mixture with temperature ranging from 925 to 1050 8C, relative
density from 99 to 98.2% and grain size from 0.13 and 0.28 mm.
Moreover, Ba0.6Sr0.4TiO3 was found to be formed during densica-
tion of the (BaTiO3)0.6/(SrTiO3)0.4 mixture. Specically, a solid-state
reaction occurred within a fully dense body, through which the
BaTiO3 and SrTiO3 constitutional phases were supposed to have a
self-pinning effect on grain growth.
Relationship between grain size and dielectric properties was
investigated for Ba0.6Sr0.4TiO3 samples fabricated by both SPS (Dr.
Sinter 2050 Sumitomo Coal Mining) and pressureless sintering
methods [440]. A mixture of BaTiO3 and SrTiO3 was used as
starting material. SPS was performed at temperatures in the range
1001250 8C for 3 min at 50 MPa. It was found that, with
increasing sintering temperature, a gradual transformation of
BaTiO3 and SrTiO3 to Ba0.6Sr0.4TiO3 solid solution occurred, until
reaction completion was reached at temperature greater than
1200 8C. The SPS sintered ceramic exhibited a duplex micro-
structure with Ba0.6Sr0.4TiO3 (13 mm) surrounded by submicron
BaTiO3 and SrTiO3 grains. In contrast, samples sintered by
pressureless method at 1450 8C for 4 h showed structure with
grain boundaries and large grain size (10 mm). Signicantly
diffused transitions in the permittivity and reduced dielectric
losses in the ferroelectric region have been observed for SPSed
samples as compared to conventionally sintered ceramics, due to
the large difference in the grain size and domains structure.
Fully dense ne-grained Ba1xSrxTiO3 (x = 0, 0.25, 0.5, 0.75 and
1) ceramics were obtained by SPS (Dr. Sinter 2050, Sumitomo Coal
Mining, Co.) from both mechano-chemically synthesized nano-
crystalline powders, and powders obtained through traditional
ceramic routes [441]. SPS treatment was carried out under
different sintering conditions. Specically, both Ba1xSrxTiO3
powders were rstly heated to 600 8C under a pressure of 30
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 63. Relative densities and grain sizes of (a) BaTiO3 (BT) and SrTiO3 (ST), and (b) Ba0.6Sr0.4TiO3 (BST64) and Ba0.6Sr0.4TiO3 from milled BT and ST powders (MBST64) plotted
vs. sintering temperature. The kinetic windows within which fully dense nano-sized ceramics were obtained are marked. In both gures, the upper two lines represent
relative densities (TD%), and the lower two lines represent the evolution of the grain size with temperature (Tgg represents the temperature at which grain growth suddenly
occurs). Adapted from Liu et al. [439].
50 MPa, and then further heated to sintering temperature at a
heating rate of 100 8C/min. When starting from mechano-
chemically synthesized Ba1xSrxTiO3, the sintering temperature
was varied from 985 to 1300 8C at 50140 MPa. Soaking time was
varied in the range 08 min. Sintering temperature and all
sintering conditions adopted yielded densities corresponding to
98100% even for temperature as low as 985 8C. Dense homo-
geneous microstructure with grain size in the range 100200 nm
were obtained. On the other hand when sintering Ba1xSrxTiO3
powders from traditional ceramic route sintering temperature was
set to 12001400 8C under a pressure of 100 MPa with a soaking
time of 5 min. Dense (97.2%) ceramics were obtained only at
1400 8C for x = 0.25 (Ba0.75Sr0.25TiO3). Dielectric properties of the
fully dense Ba1xSrxTiO3 obtained from mechano-chemically
synthesized powders were also investigated.
Ultra-ne crystalline Ba0.5Sr0.5TiO3 dense ceramics were
obtained through SPS from ultra-ne powders synthesized by
citratenitrate combustion process. Sintering was carried out at
1050 8C/min (100 8C/min heating rate) for 2 min at 20 MPa [442].
Grains with small size (1001000 nm) were observed from SEM
fractographs. At 25 8C dielectric constant and dissipation factor of
1533 and 0.0063 at 10 kHz were measured.
Dense BaTiO3/SrTiO3 composites (9:1 and 8:2 molar ratio) were
fabricated by SPS (SPS 515 Sumitomo Coal Mining Co) starting
from BaTiO3 and SrTiO3 powders having irregular shaped granules
with average grain size of 1.8 and 0.3 m, respectively [443]. When
applying an electric current of about 1000 A, temperature was
increased to 1200 8C at the rate of about 170 8C/min, and then
maintained for 330 min. The better results were obtained at
1200 8C for 30 min and full densication was achieved (9899%)
for both BaTiO3/SrTiO3 = 9:1 (99% relative density) and BaTiO3/
SrTiO3 = 8: 2 (98% relative density) composites, respectively. In
contrast, when sintering by conventional method at 1300 8C for
2 h, lower density was reached (8890%). Permittivity of dense
BaTiO3/SrTiO3 = 9:1 showed a at temperature dependence within
the range 30110 8C, due to the multicomponent microstructure of
the samples, where BaTiO3 was present as the main phase with
small amount of (Ba,Sr)TiO3 solid solution.
Locally graded (coreshell) dense dielectric structures have
been recently obtained by SPS (Dr. Sinter 2050, Sumitomo Coal
Mining Co.) starting from BaTiO3 particles coated with SrTiO3
perovskite [444]. Densication (97% of the theoretical density) of
the coreshell BaTiO3SrTiO3 particles was achieved at 1100 8C
(200 8C/min heating rate) under a pressure of 100 MPa, with a
dwelling time of 2 min. SEM observations on fractured surfaces
177
revealed a dense homogeneous microstructure with grain size
close to the diameter of the starting BaTiO3 powders (about
200 nm) and limited interdiffusion between core and shell regions.
Dielectric behavior supported the existence of the coreshell
structure. In particular, it was found that dielectric constant could
be modulated by varying the size of the core particles and the
amount and composition of the coating materials.
SPS was applied to the production of non-lead ferroelectric
Bi4Ti3O12 ceramics, starting from both co-precipitated precursors
and commercially available Bi2O3 and TiO2 powders [445]. In both
cases a powder compact of a calcined oxide mixture was
embedded in a mixture of ZrO2 and Sb-doped SnO2 to minimize
the reduction of Bi3+ and then two different heating schedules
were employed. One consisted in heating the starting mixture at a
constant rate of 50 8C/min to 800950 8C, with a holding time of
30 min and under an applied pressure of 39 MPa. The other
schedule was performed under a constant current of 450 or 700 A
for 6 or 2.5 min, respectively, until the completion of sample
shrinkage (at about 750900 8C). The optimum result, in terms of
reproducibility of sintering conditions as well as of the density of
the sintered samples, was obtained by using the second heating
schedule above. When using commercially available powders, this
process led to the rapid densication of the sample (9495% of the
theoretical value), with the simultaneous elongation and coarsen-
ing of grains (3050 mm) in the sintered body. On the other hand,
when ne (200 nm) co-precipitated precursor were used as the
starting powders, a high dense (98%) and grain-oriented sample
was readily obtained by the SPS method. A strong anisotropy in
electrical properties was also observed for the grain-oriented
Bi4Ti3O12 ceramics.
Dense (>99% of the theoretical value) textured Bi4Ti3O12
ceramics were produced by SPS (1050 Sumitomo Coal Mining
Co.) at 800 8C for 5 min at pressure of 25 MPa, starting from plate-
like Bi4Ti3O12 particles prepared by the molten salt method [446].
Sintered samples showed grain orientation and anisotropic
dielectric properties in the direction parallel and perpendicular
to the pressing direction.
Bi4Ti3O12 powders were sintered by SPS (Dr. Sinter 2050,
Sumitomo Coal Mining Co.) and the sintering behavior of the
oxides was investigated [447]. It was found that the densication
occurred within a very narrow temperature interval ranging from
650 to 850 8C. Fully dense Bi4Ti3O12 compacts were fabricated at
800 8C (100 8C/min heating rate) under 75 MPa with a holding time
of 5 min. A ne Bi4Ti3O12 microstructure constituted of equiaxed
nano-sized grains (150 nm) was obtained.
178 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
SPS (Dr. Sinter 2050 Sumitomo Coal Mining Co.) was also used
to consolidate well crystallized (average particle size of 100 nm)
Bi4Ti3O12 powders synthesized by hydrolysis and subsequent
calcination of precursors [448]. Densication was performed at
different temperatures in the range 8001100 8C (200 8C/min
heating rate), under a pressure of 50 MPa. An almost constant high
density of >99% was obtained in the whole temperature range
between 800 and 1100 8C, and only a slight decrease in density was
observed for samplers sintered above 900 8C. In contrast, when
sintering was performed by pressureless method at 9001000 8C
for 2 h, the density attained was 13% lower as compared to SPS
samples. Moreover, an homogeneous microstructure containing
ne equiaxed grains (200 nm) was obtained after SPS at 900 8C. It
was also found that Bi3+ volatilization was prevented during SPS,
thus suppressing dielectric relaxation and reducing dielectric
losses in the sintered ceramics.
Dense PbTiO3 with submicrometric grain size (<0.1 mm) was
prepared by SPS (515S Sumitomo Coal Mining Co.) starting from
hydrothermally synthesized ne PbTiO3 powders (0.1 mm) [449].
Sintering was performed at different temperatures in the range
8001100 8C (150 8C/min heating rate) with holding time of 1
3 min at 39 MPa. Annealed SPS samples mainly consisted of
tetragonal PbTiO3 and a relative density of 98% of the theoretical
value were obtained at 900 and 1000 8C for 3 min holding time.
Average grain size ranged between 0.2 and 0.9 mm depending
upon sintering temperature and time. On the other hand, when
sintering was performed by conventional method, at 1100
1200 8C for 2 h under a pressure of 190 MPa, a much lower
density was measured (6976%) with an average grain size larger
than 1 mm.
PbTiO3 sputtering targets (8 cm diameter) were also success-
fully prepared by SPS starting from submicrometric PbTiO3
powders with a relative large size distribution [450]. Specically,
when sintering was performed at 800 8C for 2 min at 40 MPa, a
relative density of 8890% of the theoretical value was achieved
and cracks free tetragonal PbTiO3 compacts were obtained.
It has been recently reported [451] that a stable SPSed sintered
body of PbTiO3 could not be obtained from an equimolar mixture of
PbO and TiO2. In particular, it was seen that sintered samples
crumbled under the stress resulting from phase change between
cubic form, taking place at sintering temperature and tetragonal
one, at room temperature. Stable PbTiO3 compacts were obtained
by SPS (T = 800 8C, 5 min holding time, P = 29 MPa) only when the
stoichiometric ratio (PbO/TiO2 = 1) was decreased. This allowed
one to prevent grain growth and also caused a decrease in the bulk
density. The optimal value of PbO/TiO2 ratio was found to be 0.9.
Dense (99% relative density) Pb(Zr0.52Ti0.48)O3 piezoelectric
ceramics were fabricated by SPS at 950 8C (400 8C lower than
pressureless sintering), thus obtaining a microstructure character-
ized by ne submicrometric grains. Better piezoelectric properties
with respect to pressureless-sintered samples were observed
[452].
Pb0.97La0.02(Zr0.76Sn0.11Ti0.13)O3 powders synthesized by
solid-state reaction were sintered by SPS (Dr. Sinter 2050
Sumitomo Coal Mining Co.) at 950 8C (100 8C/min heating rate)
for 5 min at 100 MPa [453]. Samples with relative density of 98%
were obtained. For comparison Pb0.97La0.02(Zr0.76Sn0.11Ti0.13)O3
powders were also densied by conventional sintering methods
and a relative density of 98% was obtained at 11001250 8C
with a holding time of 2 h, after being cold isostatic pressed
at 200 MPa. It was found that SPSed samples exhibited a
different fatigue behavior, as compared to conventionally
sintered specimens.
Pb0.97La0.02(Zr0.77Sn0.14Ti0.09)O3 composition, close to the
phase boundary between anti-ferroelectric tetragonal and ferro-
electric rhombohedral phases observed in the ternary phase
diagram, was also investigated by SPS [454]. Specically, sintering
was performed at 900 8C for 3 min and at 950 8C for 1 min under a
pressure of 50 MPa. After sintering, samples were also annealed at
800 8C for 1 h to recover the potential reduced status, residual
stress and carbon contamination from the graphite die. Full-dense
(>99.5%) ceramics with nearly identical grains sizes (about
300 nm) were obtained for both the sintering conditions adopted,
but some differences were observed in grains morphology. In fact,
grains of the specimens sintered at 900 8C were rather round,
similar to the starting particles morphology, while grains with
faceted morphology of crystals were observed in the specimens
obtained at 950 8C. For comparison ceramics with relative density
of 98.5% and average grains size of about 6.5 mm were prepared by
conventional cold isostatic pressing at 200 MPa and then sintered
at 10001250 8C for 2 h. The differences in the dielectric proper-
ties of SPSed and conventionally sintered samples were also
discussed.
Pb(ZrxTi1x)O3 system was quickly sintered by SPS (515S
Sumitomo Coal Mining Co.) at 900 8C, under a uniaxial pressure of
29 MPa for 10 min thus obtaining a dense body of 97% of the
theoretical density, without signicantly change in the composi-
tional distribution during sintering [455]. It was also found that
compositional uctuation strongly affect dielectric properties
of Pb(ZrxTi1x)O3 [456]. In particular, it was seen that dense
Pb(Zr0.3Ti0.7)O3 ceramics sintered at 900 8C for 5 min and subse-
quently heat treated at 1100 8C for 1 h exhibited a large
compositional uctuation and a large peak width at 2/3 maximum
dielectric constant. By further increasing heat treatment duration,
the dielectric constant was found to increase. In addition, when
sintering the perovskite ternary systems xPb(Zn1/3Nb2/3)O3-
yPbZrO3-(1-x-y)PbTiO3 by SPS at 800 8C for 10 min starting from
a mixture of three different compositions, i.e. (A: x = 0.1, y = 0.9; B:
x = 0.75, y = 0.9; C: x = 0.5, y = 0.9) characterized by different
pyroelectric peaks, the compositional distribution of the starting
mixture and high at pyroelectric coefcient were retained. A
combination of pyroelectric properties over a wide range of
temperature was attained using a suitable compositional gradient.
A mixture of 0.9PbZrO3xPbTiO3(0.1  x)Pb(Zn1/3Nb2/3)O3 cera-
mics powders with x = 0.025 and x = 0.05, pre-sintered at 1100 and
1150 8C for 1 h, respectively, were consolidated by SPS (515S, SCM,
Izumi Technology, Japan) at 800 8C for 10 min, under a pressure of
29 MPa [457]. Sintered samples exhibited a relative density higher
than 98% of the theoretical value, which is much higher than that of
the samples obtained by conventional sintering at 1200 8C for 1 h.
Moreover, SPS specimens consisted of ne-grained microstructure
with no detectable pores. Heat treatment after SPS process was
also performed to control the diffusion between the original
compositions and pyroelectric properties.
In addition, full-dense optically transparent 0.9PbZrO3xPb-
xPbTiO3(0.1  x)Pb(Zn1/3Nb2/3)O3 ceramics with x = 0.025 were
obtained by SPS at 900 8C for 10 min at 29 MPa and subsequent heat
treatment at 900 8C, starting from 0.9PbZrO3xPbTiO3(0.1  x)
Pb(Zn1/3Nb2/3)O3 powders calcinated at 800 8C for 1 h [458].
Transparent lanthanum-doped lead zirconate titanate
Pb0.92La0.08(Zr0.65Ti0.35)0.98O3 ceramics were fabricated by SPS
(515S, SCM, Izumi Technology, Japan) at different sintering
temperature ranging from 700 to 950 8C for 10 min at the applied
pressure of 29 MPa and subsequently heat treated at 7001000 8C
for 1 h [459]. Sintered samples had high relative density in the
range 97.9 and 99.6% of the theoretical value depending on SPS and
heat treatment temperatures. Moreover, SPSed specimens exhib-
ited ne microstructure with average grain size less than 1 mm.
Samples sintered in SPS at 900 8C and subsequently heat treated at
800 8C showed the maximum transmittance of 31%.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Dense Pb(Mg1/3Nb2/3)O335 mol% PbTiO3 ceramics were
obtained by sintering in SPS at 900 8C for 5 min at 30 MPa starting
from Pb(Mg1/3Nb2/3)O3PbTiO3 synthesized using the columbite
precursors technique [460,461]. High dense (99% of the theoretical
value) samples exhibiting homogeneous microstructure with
average grains size of 1.1 mm were obtained. These results were
quite different from that attained during conventional sintering at
1200 8C for 10 h at 150 MPa, where lower density (92.0%) and
larger grain sizes (23.2 mm) were observed. Specimens with
retained high density (98.3%) and coarse-grained (24 mm) micro-
structure were obtained when heat treating SPSed samples at
1200 8C for 10 h. The higher density of SPSed Pb(Mg1/3Nb2/3)O(3
3.5 mol%)PbTiO3 resulted in better dielectric and piezoelectric
properties.
Fully dense 0.7Pb(Mg1/3Nb2/3)O30.3PbTiO3 perovskite cera-
mics were also fabricated by SPS within 3 min at 800 8C (100 8C/
min heating rate), under a pressure of 20 MPa [462]. Sintered
samples exhibited a pore free microstructure with grain sizes
varying between 10 and 5 mm. Some pyrochlore phase was also
detected after sintering, as a consequence of perovskite decom-
position induced by lead volatilization during sintering.
(1  x)Pb(Mg1/2Nb2/3)O3xPbTiO3 solid solutions with x = 0.25,
0.32 and 0.4, were consolidated by SPS (Dr. Sinter 2050 Sumitomo
Coal Mining Co.) at 950 8C (100 8C/min heating rate) for 2 min,
under uniaxial pressure of 50 MPa [463]. It was also found that the
crystal structure of the calcinated stating powders changed from
rhombohedral to tetragonal with increasing PbTiO3 content and
the obtained structure was retained after SPS sintering. All sintered
samples exhibited high relative density, varying from 99.5 to 99.1
with increasing the PbTiO3 content. A slightly lower density (98.5
98%) was achieved when sintering was done by conventional
method in a tube furnace at 1200 8C for 4 h. Dielectric properties
and piezoelectric behavior for both SPS and conventionally
sintered samples were investigated.
2.7.2. Ferrites
Laminated cores composed of MnZn or NiZnCu ferrite and
permalloy layers were prepared by SPS (1050 IZUMI Tech. Co.,
Japan). Specically, MnZn ferrite powders (Fe2O3:MnO:Z-
nO = 53.5:32.2:14.3 mol%) were sintered at 1000 8C, under a
pressure of 0.16 tf/cm2 for 30 min. Ferrite specimens with smooth
surface and without vacancies were obtained [464]. In order to
prepare the ferrite/permalloy laminated cores, 45 permalloy
ribbons, used as metallic magnetic materials, were put in a
conductive graphite die and MnZn ferrite was then spread on it.
This operation was repeated several times and nally the
permalloy ribbons were put on the top of the lamination.
Ferrite/permalloy laminated cores consisted of permalloy layers
which were sandwiched by the ferrite layers with uniform spacing.
Fig. 64. (a and b) SEM image of M-type barium ferrite nanobelts synthesized by SPS. Adapted from Zhao et al. [465].
179
Moreover, laminated layers were strongly bonded. A laminated
core was also fabricated using permalloy and NiZnCu ferrite at
the sintering temperature of 900 8C. The MnZn ferrite core
exhibited superior soft magnetic properties. The laminated cores
had large saturation magnetic ux density and high permeability
at high frequency.
M-type barium ferrite was synthesized by SPS (Dr. Sinter 1050,
Japan) in one step starting from BaFe12O6, Fe(OH)3 and BaCO3 co-
precipitated nanoparticle precursors [465,466]. M-type barium
ferrite, along with a minor amount of BaFe0.24Fe0.76O2.88, was
obtained heating precursors at 800 8C for 10 min. Microstructure in
the holes of the sintered samples was characterized by nanobelts of
100300 nm in width and several micrometers in lengths (cf.
Fig. 64). Nanobelts consisted of Fe-rich and Ba-rich domains and
were not stoichiometric, being their composition expressed as
BaFe12+xO19+1.5x (4.77  x  6.50).
Fe2CoO4 soft chemistry powders, synthesized by co-precipita-
tion method, were consolidated by SPS (515S Sumitomo Coal
Mining Co.) at 8001000 8C (100 8C/min heating rate) for 5 min
under a pressure of 40 MPa [467]. After sintering, nanocrystalline
Fe2CoO4 with a spinel structure was obtained with a small amount
of CoO phases, from both as processed and thermal treated co-
precipitated powders. Although the as processed powders were
sintered at lower temperature (700 and 800 8C), and resulted in
higher density (9998% of the theoretical value), the crystallite size
of the spinel phase obtained after SPS was larger (67 and 133 nm,
respectively) than that obtained for the heat treated powders (31
and 28 nm at 800 and 900 8C, respectively). Specically, specimens
obtained from powders sintered at 900 8C displayed the best
compromise in terms of density (91%), grain size (28 nm) and
structure.. Magnetic behavior was also investigated.
Dense (NiZn)/Fe2O4 with uniform and ne grain size were
fabricated by SPS (Dr. Sinter 1050T, Sumitomo Coal Mining Co.) by
using an electric current of 600 A under a pressure of 20 MPa [468].
During this procedure temperature increased to 900 8C at a rate of
about 30 8C/min (controlled by the applied current) and was kept
constant for 05 min. A relative density higher than 98% of the
theoretical value was achieved for all the obtained samples. This
result was quite different from that obtained by conventional
sintering, where the density attained was only 95% after 4 h at
1150 8C. Grain size of the SPS specimens were found to increase
with holding time. Thus, a short holding time was an essential
factor to obtain dense (NiZn)/Fe2O4 with uniform and ne grains.
High saturation magnetization and high coercivity were obtained
at 900 8C for 5 min.
SrLaCo M-type ferrite sintered magnets were prepared by
SPS using powders obtained by mechanical compounding (MC)
[469]. Specically, SrO6.0Fe2O3 with 1.0 wt.% of La2O3 and
0.1 wt.% of Co3O4 as additives were sintered at 9501100 8C for
180 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
520 min under a pressure of 50 MPa. Regarding the magnetic
properties of the SPSed samples, better results were obtained at
1100 8C for 5 min of sintering time. Density was found to be
5.15 Mg/m3.
2.7.3. (Na/K)NbO3
High dense (Na1xKx)NbO3 (x = 0.5,0.6 and 0.7) was successfully
prepared by SPS (1030 Sumitomo Coal Mining Co.) at 1100 8C
(150 8C/min heating rate) for 3 min under an applied pressure of
about 60 MPa [470]. After annealing in air at 950 8C for 5 h, a cream
white sample with orthorhombic structure and a relative density
of 98% was obtained. The grain size showed distribution in the
range 27 mm. With increasing the potassium content x, the
average grain size was found to increase. As compared to hot
pressed samples, the SPS sintered specimens showed better
dielectric and piezoelectric properties.
Lead free piezoelectric Na0.5K0.5NbO3 ceramic was recently
prepared by SPS at 920 8C (100 8C/min heating rate), under a
pressure of 50 MPa [471]. Dense (>99% of the theoretical value)
samples with perovskite structure characterized by an average
grain size in the range 200500 nm were obtained. By post-
annealing treatment in air, the SPS Na0.5K0.5NbO3 ceramic showed
typical ferroelectric and piezoelectric characteristic.
When considering NaxK1xNbO3 ceramic with x varying in the
range 2080 mol%, densication was still achieved in SPS (Dr.
Sinter 1020 Sumitomo Coal Mining Co.) at 920 8C (100 8C/min
heating rate) and 50 MPa after 5 min holding time, and all sintered
samples exhibited the same orthorhombic structure [472] In
general, the relative density of NaxK1xNbO3 ceramic decreased
with increasing Na content, from 99% for the K rich to 92% for the
Na rich compositions. The grain size was in the range 200500 nm
and tended to decrease with increasing Na content.
It was also reported that NaNbO3, (Na0.5K0.5)NbO3 and KNbO3
powders synthesized through conventional ceramic processing
were successfully consolidated by SPS, under an applied pressure
of 30 MPa [473]. Specically, NaNbO3 was sintered at 1200 8C
(heating rate: 80 8C/min from 600 to 1000 8C and 20 8C/min from
1000 to 1200 8C) for 5 min. (Na0.5K0.5)NbO3 was heated up to
1050 8C (heating rate: 60 8C/min from 600 to 900 C and 30 8C/min
from 900 to 1050 8C) and held at this temperature for 10 min.
KNbO3 powders were consolidated at 1000 8C for 10 min (heating
rate: 60 8C/min from 600 to 900 8C and 20 8C/min from 900 to
1000 8C). The relative densities of the resultant NaNbO3,
(Na0.5K0.5)NbO3 and KNbO3 ceramics were 97.5, 98.7 and 99.7%,
respectively. The average grain size of NaNbO3 was about 2 mm,
while (Na0.5K0.5)NbO3 and KNbO3 ceramics showed larger grain
size. Moreover, all sintered ceramics exhibited hysteresis loops
characteristic of ferroelectrics.
2.7.4. Al2O3-based oxides
Al2O3 ceramics were super-fast densied by SPS (Dr. Sinter 1020,
Sumitomo Coal Mining Co.) at temperatures ranging between 1350
and 1700 8C (600 8C/min heating rate) at 40 MPa, without selecting a
holding time [474]. A comparison with pressureless sintering was
also made. It was found that high densities were achieved in very
short duration time (<3 min). Furthermore, for temperature below
1550 8C, SPS samples were denser than that consolidated by
conventional pressureless sintering (PLS) at the same sintering
temperature but for longer duration time (2 h). In general, at low
sintering temperatures high dense ceramics were obtained by SPS at
temperature levels 100 8C lower as compared to PLS, being such
difference gradually decreasing with increasing temperature. Above
1550 8C almost no difference was observed. However, samples
obtained by SPS exhibited more homogeneous microstructure and
better mechanical properties.
PACS method was used to investigate sintering of nanocrystal-
line g-Al2O3 over a temperature range of 15731943 K, under a
uniaxial pressure of 2966 MPa. Total duration of PACS treatment
was lower than 10 min [475]. During sintering a phase transfor-
mation from g to a Al2O3 was found to occur at all temperatures
and strong texture was detected in the sintered specimens. The
relative density varied in the range 5796% of the theoretical
value, depending on the sintering temperature and applied
pressure. In general, it was found that density increased with
increasing both temperature and pressure. However, a signicant
grain growth (>300 nm) was observed in specimens with relative
density of 87 and 96%, sintered at 1943 under 66 MPa and at
1823 K under a pressure of 58 MPa, respectively. Thus, consider-
ing that the aim was to obtain dense nanocrystalline Al2O3, the
best combination of density (76%) and grain size (80 nm) was
attained at 1833 K and 66 MPa.
It was also reported that the application of electric pulsing
enhanced the densication of Al2O3, and that the level of
enhancement depended on the pulsing sequence [110,476,477].
Specically, when using a multiple pulse cycle at 293, 473, 773
and 1273 K, pure a-alumina specimens with relative density of
98% of the theoretical value were obtained in 8 min at 1573 K. The
sintered samples exhibited submicrocrystalline structure, with
average grain size of 0.7 mm. Also the effect of the starting Al2O3
crystal structure was investigated. Specically, a-Al2O3 powders
were found to consolidate more rapidly as compared to g-Al2O3
even though g-Al2O3 were ner. This fact was related to the
development of the vermicular structure during transformation of
g-Al2O3 powders. Similarly to monolithic a-Al2O3, g-Al2O3(10
20 vol.%)TiO2 composite was consolidated by electric pulsing
assisted sintering to 99% of the theoretical density at 1673 K
within 6 min.
Al2O3 powders with four different particle sizes (31.40, 3.46, 0.4
and 0.33 mm) were densied by SPS (1050 Sumitomo Coal Mining)
at 1550 8C, with heating rate varying from 20 to 300 8C/min for 0 to
30 min and at applied pressures of 20 to 40 MPa [478]. It was found
that particle size of the starting powders played an important role
in the SPS process, since relative density increased with reducing
particle size under unchanged sintering conditions. The relative
density was also found to increase with increasing holding time. In
particular, when sintering at 1550 8C (200 8C/min heating rate)
under 30 MPa, without holding time, relative density increased
from 92 to 99% of the theoretical value, as particle size decreased
from 3.46 to 0.33 mm, respectively. In addition, relative density of
the samples (starting powders: 3.46 mm) increased from 92 to 98.7
and 99.4% as the holding time was increased from 0 to 10 and
30 min. Microstructure inhomogeneity was observed, being the
edge denser than the inside of the samples sintered at 1550 8C for
shorter holding time (10 min). The effect of the heating rate and
the applied load on densication behavior of Al2O3 was also
examined. Abnormal grain growth was observed when a slower
heating rate was applied. In particular, specimens obtained from
0.33 mm powders exhibited large plate-like Al2O3 grain growth
(>180 mm in the upper edge and 60 mm in the side edge) when
sintered at 1550 8C, at 30 MPa and at a heating rate as low as 5 8C/
min, while a heating rate of 200 8C/min inhibited grain growth,
resulting in more homogeneous equiaxed grains. Increasing
mechanical pressure was found to enhance densication.
Porous Al2O3 ceramics with high strength were successfully
fabricated from Al2O3 with different graphite content by SPS (Dr.
Sinter 1020 Sumitomo Coal Mining) and subsequent burning out
graphite [479]. High porosity of 5057% was obtained for samples
containing 1030 vol.% graphite when sintering at 1100 8C under a
pressure of 30 MPa for 3 min, at a heating rate of 80 8C/min. Pores
with submicron sizes were found to decrease with increasing
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
sintering temperature from 900 to 1100 8C. In addition, open
porosity and open pore sizes in submicron region increased with
graphite content. Porous alumina ceramics prepared by the
addition of 1030 vol.% graphite showed the high compressive
strength of 20055 MPa, that was 35 times higher than those
obtained by pressureless sintering, and 2.5 higher than those
sintered by hot pressing.
In order to investigate the effect of sintering parameters
(temperature, pressure and heating rate) on the properties of
porous Al2O3, several PECS experiments [480] were carried out
starting from a mixture of submicron Al2O3 (0.23 mm) and 10 wt.%
carbon black (20 nm), at the following sintering conditions: (1)
temperature 1400 8C, soaking time 5 min, pressure 5.5 MPa and
heating rate 100 8C/min; (2) temperature 1500 8C, soaking time
5 min, pressure 5.5 MPa and heating rate 100 8C/min; (3)
temperature 1500 8C, soaking time 5 min, pressure 15 MPa and
heating rate 100 8C/min; (4) temperature 1500 8C, soaking time
5 min, pressure 15 MPa and heating rate 200 8C/min. The vacuum
sintered compacts were then post-heat treated in air at different
temperatures between 800 and 1300 8C, for more than 10 h. As
previously reported, during PECS process Al2O3C system of low
porosity was obtained and during post-heat treatment in air,
carbon particles present in the Al2O3C system burnt out to form
highly porous Al2O3. It was observed that when the applied
pressure was as low as 5.5 MPa, an increase in temperature from
1400 to 1500 8C did not enhance the densication of Al2O3C
ceramics, and their relative density (75% of the theoretical density)
remained the same. In addition, an increase in either pressure and/
or heating rate, did not affect signicantly densication and the
relative density of the Al2O3C ceramics which changed from 83%
to 86% of the theoretical value with pressure and heating rate
varying from 5 to 15 MPa and from 100 to 200 8C/min, respectively.
When the compacts were post-heat treated in air at different
temperatures the porosity varied from 28 to 39% depending on the
sintering parameters. Moreover, the pore size distribution as well
as the mechanical properties did not change with post-heat
treatment temperature.
A systematic study of various SPS parameters (temperature,
holding time, heating rate, pressure, and pulse sequence) was also
conducted to investigate their effect on the densication, grain
growth kinetics, hardness and fracture toughness of a commer-
cially available submicrometer-sized (0.4 mm) Al2O3 powder
[481]. It was found that the SPS process enhances both
densication and grain growth and that was possible to retain
the original ne-grained structure in fully densied bodies by
avoiding a too high sintering temperature. Specically, fully dense
(99.3%) samples were obtained by SPS (2050 Sumitomo Coal
Mining Co.) at 1250 8C (heating rate 150200 8C/min), with a
holding time of 3 min, under a pressure of 50 MPa. For sintering
temperature lower than 1250 8C a limited grain growth occurred
(0.81 mm), while at higher temperature grain size signicantly
increased from 1 to 27.5 mm. On the other hand, the presence of
0.1 wt.% MgO markedly hindered grain growth at T > 1250 8C (0.9
16.5 mm).
Regarding the time effect, it was reported that sintering at
1200 8C with or without 3 min holding time yielded samples with
density of about 95%, while full density was achieved with a
holding time of 10 min or longer. In contrast, all samples sintered
at 1300 8C were fully dense, independently on sintering time [481].
Moreover, as the holding time was increased from o to 40 min at
1300 8C (P = 50 MPa), grain sizes varied in the range 37 mm, as
compared to samples sintered at 1200 8C where grain size changed
from 0.5 to 2 mm. For both temperatures considered, most of the
grain growth was found to occur during the rst 10 min holding
time, i.e. from 0.5 to 1.5 mm and from 2.7 to 6 mm at 1200 and
181
1300 8C, respectively. With the applied pressure of 200 MPa, fully
dense compacts were obtained at 1150 8C, i.e. at 100 8C lower
temperature with respect to samples densied at 50 MPa. At
temperature above 1250 8C grain growth was found to become
more rapid under high pressure. In addition, when applying
pressure at the maximum temperature, samples exhibited ner
grain structure as compared to those sintered with pressure
applied throughout the entire sintering cycle. Grain size was also
found to decrease with increasing heating rate (from 50 to almost
600 8C/min), being the effect more evident at high temperature.
The pulse sequence seemed not have effect on grain size at 1200 8C,
whereas at 1300 8C the observed grain growth decreased with the
pulse on/off ratio decrease. Hardness values in the range 21
22 GPa and fracture toughness values of 3.5  0.5 MPa m1/2 were
found for the compacts containing submicrometer-sized Al2O3 grains.
Further PECS experiments were performed in order to
investigate the effect of heating rate on densication and grain
growth of Al2O3 and conicting results were reported by different
research groups, probably due the difference in particle size,
heating rate and sintering temperature.
For example, PECS apparatus (SPS-1050 Sumitomo Coal Mining
Co.) was recently employed to consolidate two kinds of a-Al2O3
powders with average particles size of 0.15 and 0.7 mm.
Densication was carried out at 1200 and 1400 8C, under a
pressure of 40 MPa, with a heating rate of 50 or 300 8C/min,
without holding time [133,482]. It was found that, when ne
powders (0.15 mm) were sintered at 1200 8C with 50 8C/min
heating rate, a density of 98.7% was attained, and grain sizes were
found to be four times larger (0.58 mm) than that of the starting
powders. At faster heating rate (300 8C/min) a lower density
(96.3%) and smaller grain size (0.46 mm) were achieved. In
contrast, for the coarse starting powders (0.7 mm), heating to
1200 8C resulted in density lower than 75% and almost no grain
growth (0.740.72 mm). The fast heated specimens exhibited
higher density (74.4%) than the slow heated ones (72.8%). When
sintering was performed at 1400 8C ne Al2O3 powders led to fully
dense compacts (99.4 and 99.3%, respectively) for both slow and
fast heating processes (cf. Fig. 65). However, the grain sizes of
Fig. 65. Relative density and average grain size of a-Al2O3 as function of maximum
heating temperature. Adapted from Zhou et al. [482].
182 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
samples heated at 50 and 300 8C/min were about 50 and 15 times
larger (7.6 and 2.4 mm, respectively) as compared to the starting
powders.
In contrast, when sintering coarse powders, a density over 97%
but below 99% was attained and the average grain size were about
6 and 4 time larger than that of the starting powders. In general, for
both ne and coarse Al2O3, a faster heating rate resulted in less
grain growth.
PECS experiments performed on ne a-Al2O3 powders,
between 1000 and 1400 8C, allowed to clarify the densication
and grain growth behavior at different sintering stage [482]. In
particular, it was found that, at the early stage, fast heating greatly
promoted the formation of necking between particles and resulted
in higher densities with respect to slow heating; at the
intermediate stage, fast heating was found to enhance both
densication and grain growth; at the nal one, fast heating
resulted in smaller grain sizes with respect to slow heating.
PECS method was used to obtain alumina ceramics with high
relative density (99%) starting from calcined transition alumina
powders (a mixture of x- and g-alumina or a single-phase of g-
alumina powders) with different purity [483]. Specically, high
pure powders were ground using a planetary ball mill with high
pure pot and balls. On the other hand, less pure powders were
ground using 93% pure alumina pot and 99.9% pure alumina balls.
In the less pure powders contamination occurred due to inclusions
of SiO2 and CaO released by the grinding media. The effect of these
inclusions on microstructure of the sintered ceramics was
investigated. Sintering was performed by PECS at different
temperatures ranging from 1250 to 1550 8C (90 8C/min heating
rate), at 3040 MPa, with a holding time of 3 min. Full densication
was achieved at 1350 8C and 30 MPa when sintering high pure
powders calcined at 900 8C for 3 h. In contrast, for less pure
powders, calcined under the same conditions of the pure ones,
higher sintering temperature was needed to achieve the same
densication level. This nding was explained with the presence of
SiO2 inclusions inhibiting grain growth and shifting densication
temperature of less pure powders to a higher temperature range.
When the applied pressure was increased from 30 to 40 MPa no
signicant change in bulk density were observed when sintering
high pure powders at 1350 8C. On the contrary, when the
temperature was 1300 8C or lower the higher applied pressure
resulted in higher density. It was also found that high pure
powders provided alumina ceramics with higher bending strength
(860 MPa) as compared to those obtained from less pure powders
(746 MPa).
Powders compacts consisting of 1040 mass% of leucite and
alumina were recently sintered by PECS at 1400 8C and 30 MPa for
3 min [484]. A relative density higher than 98% of the theoretical
value was achieved. In the case of 40 mass% of leucite-containing
alumina samples the bending strength, Vickers hardness and
elastic modulus of the sintered samples were 360 MPa, 9 and
152 GPa, respectively. Values of Vickers hardness, strength, and
elastic modulus were close to those ones of the natural bone.
Two kinds of the eutectic composition powders of Al2O3
Y3Al5O12 (YAG) with particle size in the range 344 and 64
124 mm were consolidated by SPS (1050 Sumitomo Coal Mining
Co.) at 16901710 8C for 560 min, under a pressure of 40 MPa
[485]. From microstructure investigations it was found that the
eutectic structure was retained. However, new coarse crystals
were formed especially in eutectics prepared from 64 to 124 mm
powders. A relative density of 99.5% of the theoretical value was
achieved for both eutectics prepared from 344 and 64124 mm
powders. Mechanical properties of the consolidated eutectics were
also measured at room temperature. It was seen that Vickers
hardness (16.917.1) GPa, Youngs modulus (334 GPa) and Pois-
sons ratio (0.25) were almost the same for all samples. The
strength of the consolidated samples was 424 and 328 MPa for the
eutectic powders of 344 and 64124 mm at room temperature,
respectively.
Eutectic Al2O3GdAlO3 solid structure was reproduced by SPS
(1050 Izumi Technology Co. Japan) treatment at 1620 8C for 5 min,
starting from eutectic powders (3125 mm) [486]. The structure of
the sintered eutectic composites was a mixture of ne and coarse
textures. The ne structure was conned at the matrix of the
coarse crystals, which was affected by the heat treatment in SPS.
The matrix was reported to prevent ne crystals from growing. No
cracks or pores were observed in the eutectic compacts.
Porous a-Al2O3 and a-Al2O3/5 vol.% b-SiC nanocomposites
with improved mechanical properties were prepared by PECS at
temperatures between 800 and 1500 8C (30 8C/min heating rate),
for various sintering time, under a pressure of 5.5 MPa [487].
Microstructures with ne grains and enhanced neck growth were
achieved. By the incorporation of ne SiC particles, the fracture
toughness of the porous Al2O3 matrix was signicantly increased.
Al2O3 powders doped with MgO were consolidated by PAS at
1150 8C for 1015 min [488]. Specically, PAS sintering was
performed in air using a two steps processing schedule: (1)
powders surface activation, through the application of a DC electric
discharge (25 V, 750 A, 3060 ms on, 3060 ms off); (2) densica-
tion by resistance heating using a 1500 A DC current. A relative
density of 99.2% of the theoretical vale was achieved without
signicant grain growth. Moreover, sintered samples exhibited
excellent grain to grain contact and structurally clean grain
boundaries.
Mica ceramics were fabricated from alumina-pillared uorine
micas by PECS (SPS-2050, Sumitomo Coal Mining Co.) at 600
1035 8C (200 8C/min heating rate) and at 1030 MPa [489]. It was
found that the microporous mica ceramics obtained at lower
temperature (600 8C) and at lower applied pressure (10 MPa)
retained the pillared structure of the starting alumina-pillared
micas and exhibited a maximum specic area of 323 m2/g as
compared to those obtained at higher temperature and pressure.
As the sintering temperature and/or the loading pressure
increased, specic surface area decreased until complete collap-
sing of the pillared structure occurred. Macroporous ceramics with
retained mica structure were obtained at 8001000 8C. Fully dense
mica ceramics were obtained by reaction sintering at 1035 8C, at
1030 MPa.
a-Al2O3/b-Al2TiO5 ceramics were prepared by SPS starting
from Al2O3 nanopowders (40 nm) containing 12 wt.% TiO2,
synthesized through ame pyrolysis technique. SPS was performed
at 1450 8C for 3 min under a pressure of 40 MPa. In order to prepare
a coarse-grained ceramic, the same Ti-doped Al2O3 starting
nanopowders were pressed at 350 MPa and pressureless sintered
at 1500 8C in a furnace [490]. After SPS, dense (99%) ultra-ne-
grained a-Al2O3/b-Al2TiO5 ceramics (400 nm grain size) were
obtained. On the other hand, conventional pressureless sintering
resulted in a coarse-grained ceramics (2.2 mm grain size). The
ultra-ne-grained ceramics were found to possess higher hardness
(17.6 GPa) compared to the coarse-grained counterparts
(15.3 GPa). An improved wear resistance was also observed for
ultra-ne-grained samples.
Mg2+-doped transition alumina powders (00.5 mass%) MgO/
Al2O3, were densied by PECS (SPS-2050 Sumitomo Coal Mining
Co.) at 12001300 8C (200 8C/min heating rate), for a holding time
of 5 min under a uniaxial pressure of 4080 MPa [491]. Densica-
tion was found to strongly depend on MgO content at lower
sintering temperature. Specically (0.3 mass%)MgO/Al2O3 and
(0.5 mass%)MgO/Al2O3 were densied to 99.0% of the theoretical
density at 1250 8C, while for powders with lower MgO content, i.e.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
0.05 and 0.1 mass %, were not and 50100 8C higher temperatures
were needed for reaching almost complete densication. Full
densication was achieved for all doped specimens at 1300 8C
under 40 MPa. The critical Mg2+ doping for suppressing grain
growth was found to be 0.1 mass% MgO. Furthermore, higher
loading pressure led to full densication at lower temperature,
resulting in a more uniform and ner microstructure. Full-dense
(>99.6%) alumina ceramics composed of ne grains with average
size of 0.47 mm were obtained by PECS when sintering at 1250 8C
and 80 MPa.
Superfast densication of ceramics Al2O3Y3Al5O12 compo-
sites [492] was carried out by SPS (1020 Sumitomo Coal Mining
Co.) starting from three different precursor mixtures, i.e.
(10 vol.%; 0.4 mm) Al2O3/(90 vol.%; 0.8 mm)Y3Al5O12, (45 vol.%)
Al2O3/(55 vol.%)Y3Al5O12, (45 vol.%) Al2O3 + CaAl12O19)/(55 vol.%)
Y3Al5O12. Full densication (>99%) was achieved at 1573 K
(600 K/min heating rate), at 40 MPa, without holding time. For
the sake of comparison the same powder were consolidated by hot
pressing and it was found that to attain full density a sintering
temperature of 1873 K and 1 h holding time with a pressure of
25 MPa had to be applied. It was also observed that SPSed
specimens exhibited ne microstructure with grains of the same
size and morphology of the precursor powders. On the other hand,
hot pressed specimens consisted of grains three times larger than
those observed in the SPS sintered samples.
It was also reported that a-Al2O3/(015 vol.%)BaTiO3 and g-
Al2O3/7.5 vol.%BaTiO3 nanopowders from high-energy ball milling
have been sintered to near full density trough SPS (Dr. Sinter 1050,
Sumitomo Coal Mining Co.) apparatus at 1150 8C (200 8C/min
heating rate), in only 3 min under a pressure of 63 MPa [493]. This
nding was quite different from the pressureless-sintered Al2O3/
BaTiO3 composite where temperatures higher than 1450 8C were
used to achieve the 92% of the theoretical density of alumina. Fine
microstructure were obtained and a mixture of fracture modes was
observed for a-Al2O3/(015 vol.%)BaTiO3 samples. Fracture tough-
ness was found to depend on the BaTiO3 content and tits maximum
value (5.36 MPa m1/2) was reached for 7.5 vol.% BaTiO3.
Dense Al2O3-based composites with different content of
dispersed BaTiO3 piezoelectric particulates (110 mol%) were
successfully prepared by SPS at sintering temperature in the
range 11001500 8C (100 8C/min heating rate) at 38 MPa [494]. It
was found that relative density increased with increasing
sintering temperature, while it decreased with increasing BaTiO3
content. The highest densication (95% relative density) was
achieved at 1300 8C for all BaTiO3/Al2O3 samples. Above 1300 8C
no successful densication was possible. Abnormal grain growth
was also observed in the sintered composite. However, the
fracture toughness of the BaTiO3/Al2O3 composites was im-
proved and the highest value of 6.04 MPa m1/2 was found for the
Al2O35 mol%BaTiO3 sintered at 1300 8C.
Dense nanocrystalline (10 nm) Li2OAl2O3SiO2 (LAS) ceramics
doped with luminescent Erbium were recently fabricated by SPS
(Dr. Sinter 1050 Sumitomo Coal Mining Co.) starting from solgel
synthesized precursors powders [495]. Specically, the composi-
tion taken into account was (7.71 mol%)Li2O(13.86 mol%)Al2O3
(77 mol%)SiO2(0.39 mol%)Er2O3 with a small amount of ZrO2
(1.04 mol%) added not only as nucleation agent but also because it
was found to be an excellent host for the luminescent ions.
Sintering was carried out under three different sintering condi-
tions: (a) 850 8C 35 MPa for 2 min; (b) 840 8C 53 MPa for 5 min; (c)
900 8C 53 MPa for 5 min. The heating rate was 200 8C/min for all
experiments performed. The maximum relative density (99% of the
theoretical value) was achieved under (a) conditions, while under
(b) and (c) ones a lower density (96%) was obtained. Only (c)
conditions gave rise to a marked crystallization (45 wt.%), while
183
samples obtained under (a) and (b) conditions were completely or
almost completely (99100 wt.%) amorphous. A erbiazirconia
solid solution with cubic uorite structure was observed in the
most crystalline sample obtained under sintering condition (c). In
addition, although the sintered samples were not transparent,
density and hardness of the most crystalline (c) sample was very
close to the values of the glass obtained by melting at 700100 8C.
A photoluminescence characterization was also performed.
Al2O3(6, 9, 14 vol.%)Nd2Ti2O7 powders were sintered by SPS
(Dr. Sinter 1050, Sumitomo Coal Mining) at different temperatures
between 1000 and 1150 8C (200 8C/min heating rate) under an
applied pressure of 63 MPa, for 13 min. Al2O36 vol.%Nd2Ti2O7
was consolidated to near full density (98.8%) at lower temperature
(1000 8C for 1 min) as compared to the pure Al2O3 (99.8% at
1150 8C for 3 min) [496]. Al2O39 vol.%Nd2Ti2O7 and Al2O3
14 vol.%Nd2Ti2O7 reached the densities of 98.2 and 99.5% when
sintered at 1100 and 1150 8C for 3 min, respectively. XRD results
showed the presence of a-Al2O3 as the major phase and the
coexistence of Nd2Ti2O7. No reaction was observed between the
two phases. Microstructure of all the samples consisted of
equiaxed grains. Hardness did not change signicantly with the
addition of the Nd2Ti2O7 second phase, while a signicant
improvement in toughness was observed. The highest toughness
was achieved for Al2O39 vol.%Nd2Ti2O7 composites and resulted
markedly higher (5.67 MPa m1/2) than that of pure a-Al2O3
(3.30 MPa m1/2).
2.7.5. Zirconia-based oxides
Several sintering conditions of SPS were also investigated to
obtain high-density 8-mol% yttria-stabilized-zirconia (YSZ) elec-
trolytes [497]. Specically, nano-sized YSZ raw powder (50 nm)
was densied to a relative density of 99.1% at 1400 8C, with an
applied uniaxial pressure of 23 MPa, and a total of four consecutive
sintering cycles at 3 min per cycle (cf. Fig. 66). For conventional
sintering, the green pellets were formed at 50 MPa and then was
heated up to 1450 8C in an electrical resistance furnace for 2 h. The
relative density achieved was 97% of the theoretical value (cf.
Fig. 66). The grain size of SPS samples was found to be marginally
larger but also more uniform than that of conventionally sintered
material. Moreover, ionic conductivity of the SPSed yttria-
stabilized-zirconia was improved as compared to conventionally
sintered specimens.
Freestanding 3 mol% (7 wt.%) Y2O3-stabilized-ZrO2 electrolytes
for solid oxide fuel cells (SOFCs) were prepared by plasma spray
and post-spray sintering by SPS (Dr. Sinter 1050 Sumitomo Coal
Mining) [498]. Specically, single and multiple cycles sintering
Fig. 66. Temperature dependence of relative density of SPS and conventionally
sintered yttria-stabilized zirconia samples (for SPS, samples were sintered at each
temperature for 3 min, four consecutive sintering cycles and with applied pressure
of 23 MPa. For conventional sintering, the samples were sintered at each
temperature for 2 h). Adapted from Chen et al. [497].
184 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
were performed at 1200, 1400 and 1500 8C, with a holding time of
3 min for each cycle. It was seen that SPS treatment improved the
density of plasma sprayed electrolytes. In addition density was
found to increase with increasing sintering temperature and the
number of sintering cycles. Moreover, increasing the number of
SPS cycles, with a relatively short duration, resulted more effective
in improving the mechanical properties of the plasma sprayed and
sintered specimens, as compared to the single SPS cycle, albeit with
longer exposure. The effect of SPS on enhancing the ionic
conductivity of the electrolytes was also investigated.
SPS was found to be an efcacious post-spray technique also
when considering plasma sprayed 20 wt.% Y2O3-stabilized-ZrO2
[499]. Specically, when sintering up to 1500 8C, with a single
3 min cycle, the relative density of the plasma sprayed electrolyte
increased from 85.2 to 98.2%. Moreover, the lamellar microstruc-
ture of the as sprayed electrolyte changed to granular structure (cf.
Fig. 67) with temperature increasing above 1200 8C, resulting in
the improvement of the ionic conductivity. Growth of granular
grains also occurred with increasing sintering temperature, and
exaggerated grain coarsening at 1500 8C for 3 min was found to be
a possible cause for cracks forming along grain boundary (cf.
Fig. 67), resulting in a sharp drop of the ionic conductivity.
SPS (2080, SPS Syntex Inc., Japan) was recently used to
consolidate commercially available granulated ZrO2 at tempera-
tures in the range 9501200 8C (50 8C/min heating rate), with
soaking time ranging from 5 to 180 min, under an applied pressure
of 100 MPa [500]. Three kinds of microstructure were obtained.
Porous materials, exhibiting open porosity, average grain size of
80 nm and with a relative density in the range 6190% were
prepared at temperature below 1050 8C, whatever the holding
time used, or at 1050 8C with holding time of 15 min. On the other
hand, dense materials characterized by closed porosity, average
grain size of 80 nm and high relative density (9098%) were
obtained when sintering at 11251200 8C or when the tempera-
Fig. 67. Fracture surface of SPS-treated plasma sprayed YSZ electrolytes: (a) SPS-treated at 1200 8C for 3 min; (b) SPS-treated at 1300 8C for 3 min; (c) SPS-treated at 1400 8C
for 3 min and (d) SPS-treated at 1500 8C for 3 min. Adapted from Khor et al. [499].
ture was set to 1050 8C with a holding time of 60 min. Finally, fully
dense samples with submicron grain sizes (160 nm) were
fabricated for a temperature of 1200 8C and 3 h holding time.
The mechanism controlling the densication behavior of granu-
lated ZrO2 was also proposed.
ZrO23 mol%Y2O3 (ZrO23Y) nanopowders synthesized by a co-
precipitation method were sintered by SPS (Dr. Sinter 1020
Sumitomo Coal Mining Co.) at 10501500 8C, at a heating rate of
600 8C/min, under a pressure of 40 MPa for 110 min [501]. High
density exceeding 98% was obtained when sintering at 1300 8C for
3 min, while the theoretical density was achieved at 1400 8C. It was
also found that a higher density (99%) was generally achieved by
SPS at lower temperature (1180 8C) and in shorter time (9 min
dwelling time) as compared to hot pressing (96% relative density,
T = 1250 8C, 30 min dwelling time) under similar pressure levels.
No densication gradient was observed at 1100 8C in the SPS
samples, as compared to that sintered at the same temperature by
rapid hot pressing (P = 80 MPa, dwelling time 10 min). Moreover,
when comparing SPS (3 min dwelling time) and pressureless
sintering (2 h dwelling time), grains size resulted smaller and the
grain growth speed much higher for SPSed specimens.
Nanocrystalline ZrO230 vol.%MgAl2O4 spinel composites were
synthesized by high-energy ball milling and subsequent densica-
tion through SPS [502,503]. The starting powders were high-purity
3 mol%-Y2O3-stabilized tetragonal ZrO2 and high-purity magne-
sium aluminate spinel (MgAl2O4), with average particle sizes of
270 nm and 360 nm for ZrO2 and for spinel, respectively.
Densication was conducted using SPS at 70 MPa, at a heating
temperature of 1573 K (100 8C/min heating rate) for 5 min. For
comparison, ZrO2-spinel composites were also pressureless-
sintered in air at 1673 K for 2 h. For the conventional conditions,
dense sintered bodies with the relative density >98% and the
average grain sizes of the two phases exceeding 300 nm were
obtained as shown in Fig. 68a. On the other hand, after SPS a dense
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 68. Typical SEM images of ZrO230 vol.% MgAl2O4 spinel composites: (a) pressureless-sintered in air at 1673 K for 2 h and (b)(d) SPSed at 1573 K for 5 min after 50, 250,
and 450 h high-energy ball milling, respectively. Adapted from Morita et al. [503].
nanocrystalline ZrO2spinel composite with relative density >98%
and grain size lower than 100 nm was successfully reached (cf.
Fig. 68bd). Moreover, the XRD prole of the dense nanocrystalline
ZrO2spinel composite showed t-ZrO2 and spinel phases sharp
peaks. No m-ZrO2 and c-ZrO2 phases were detected. The spinel
particles were homogenously dispersed among the ZrO2 matrix,
without detectable agglomeration. It was also observed that
nanocrystallization improved strength of the ZrO2-spinel compo-
site by a factor of 2.02.5. The maximum exural strength of the
nanocrystalline composite reached 2200 MPa.
Commercially available (8 mol%) Y2O3-stabilized-ZrO2 powders
were successfully consolidated near to theoretical density by SPS
apparatus (SPS 515 or SPS 3.20MK-IV, Izumi Technology, Japan)
under a pressure of 30 MPa, at much lower temperatures, in the
range 11001300 8C (160 8C/min heating rate) and for shorter
holding time, 510 min, as compared to conventional sintering in a
mufe furnace (T = 1600 8C, P = 190 MPa, 2 h holding time) [504].
Moreover, SPSed specimen exhibited higher bending strength
(400 MPa) at room temperature as compared to conventionally
sintered samples (250 MPa), mainly due to the small grain stru-
cture achievable in SPS.
Dense yttria-stabilized-zirconia ceramics with grains size of
about 10 nm were recently fabricated by SPS through the use of
high applied pressures (up to 1 GPa) and high heating rate (200 8C/
min) at temperatures signicantly lower than that mentioned
above [505]. Specically, high dense (>98%) Y2O3 (8 mol%)-
stabilized-ZrO2 were obtained when sintering for 5 min at
930 8C under a pressure of 850 MPa. Moreover, all sintered
specimens exhibited uniform microstructure and ne grain sizes
below 200 nm.
The sintering of fully-stabilized (8 mol% Y2O3) zirconia was
widely investigated by taking advantage of SPS (1050 Sumitomo
Coal Mining) technique under a uniaxial pressure ranging from 15
and 141 MPa, at different heating rates in the range 50300 8C/min
and at different sintering time and temperatures ranging from 0 to
185
25 min and from 600 to 1400 8C, respectively [506,507]. It was found
that maximum densication rate occurred at 1200 8C resulting in
fully dense zirconia with a crystallite size <100 nm. Heating rate and
sintering duration did not affect the nal density and the crystallite
size. In contrast, higher pressure resulted in higher density, without
affecting crystallite sizes for sintering temperatures of 1200 8C and a
holding time of 5 min. The maximum hardness (16 GPa) and fracture
toughness (2.5 MPa m1/2) were obtained for samples sintered at
1200 8C for 5 min at 106 MPa. Moreover, impedance measurements
and calculation of the activation energy for conduction were
performed.
Dense (>99%) yttria-stabilized (3 mol%)-zirconia were also
obtained by SPS (1050 Sumitomo Coal Mining) at about 1300 8C for
10 min under a pressure of 100 MPa, starting from nanocrystalline
powders synthesized using the reverse micelle method and
subsequently annealed at 800 8C for 2 h [508]. Sintered compacts
exhibited ne-grained microstructure with retained grain size
(about 250 nm) of the annealed starting powders.
SPS was also applied to investigate the effect of contaminants
such as SiO2 and Cr2O3 and sintering conditions on (8 mol%) Y2O3-
stabilized-ZrO2 electrolyte densication [509]. The addition of
0.5 wt.% SiO2 to the starting electrolyte powders was detrimental
for both densication and ionic conductivity as compared to pure
Y2O3-stabilized-ZrO2 and Cr2O3-doped-ZrO2. On the other hand,
the addition of 0.5 wt.% Cr2O3, while marginally reducing grain
boundary conductivity, resulted in the improvement of densica-
tion. In particular, it was reported that maximum relative densities
of 98, 96 and 99% were achieved within 3 min at 1500 8C under
30 MPa for pure, SiO2-doped-ZrO2 and Cr2O3-doped-ZrO2 Y2O3-
stabilized-ZrO2.
ZrO2TiN (60/40) composites were prepared by FAST (HP D 25/
1, FCT Systeme, Rauenstein, Germany) [510] through a six
segments temperature and pressure cycles which were performed
at different temperature and pressure combinations in order to
examine the densication behavior. It was found that densication
186 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
mainly took place between 1050 and 1400 8C. The evolution of the
current density and temperature in the punchdiesample set-up,
was also investigated through a nite element calculation.
12 mol% scandia-stabilized-zirconia (12SSZ) with ne crystal-
lite size (340 A) was sintered through the SPS (1030, Sumitomo
Coal Mining Co.) method at 10001150 8C (300 8C/min heating
rate), under a pressure of 30 MPa, with a holding time in the range
560 min [511]. It was found that dense compacts of cubic phase
were prepared by SPS at 1100 8C with almost retained ne
crystallite size (370 A). In contrast samples air sintered at 1500 8C,
displayed crystallite size as large as 650 A. In the temperature
range 400670 8C, the electrical conductivity of SPS specimen was
higher than that one of isostatically sintered samples at 100
1575 8C under 960 MPa, while this situation was reversed at a
higher temperature range (680800 8C). The discontinuity in
electrical conductivity around 670680 8C was eliminated since
the phase transition point was shifted closer to room temperature.
Cr2O3/(2.5 mol%)Y2O3-stabilized-ZrO2 mixtures with different
compositions in the Cr2O3-rich region (50100 mol%), synthe-
sized by hydrazine method, were sintered by SPS at 1300 8C
(100 8C/min heating rate) for 10 min at 30 MPa [512]. Dense
composites ceramics with relative density of 99.8% of the
theoretical value were obtained. Ceramics exhibited homoge-
neous microstructure, with ZrO2 average grain size of 0.2 mm for
all the compositions investigated. On the other hand, grain size of
Cr2O3 was dependent on the composition, resulting signicantly
decreased from 2.2 to 0.6 mm with increasing Y2O3-stabilized-
ZrO2 content. A high fracture toughness of 9.3 MPa m1/2 and
an excellent bending strength of 1290 MPa were achieved for
samples containing 50 mol% ZrO2.
MulliteZrO2 composites have been synthesized by SPRS (Dr.
Sinter 1020, Sumitomo Coal mining Co.) starting from a mixture of
ZrSiO4 (64 wt.%), Al (18.5 wt.%), Al2O3 (17.5 wt.%) with MgO
(1.8 wt.%) or TiO2 (7 wt.%) as sintering additives [513]. SPS was
performed at temperatures ranging from 1350 and 1640 8C for
ZrSiO4Al2O3, and from 1350 to 1460 8C for ZrSiO4Al2O3 with
MgO or TiO2.The applied pressure was 40 MPa, and the heating rate
was 500 8C/min. Mullite formation and full densication were
attained at 1540 and 1560 8C, respectively if MgO and TiO2 were
not used. When adding the latter ones, lower temperatures, i.e.
1460 8C, were required. Better mechanical properties were
obtained for the composites that were prepared without additives,
due to a larger retention of tetragonal zirconia particles that
activated the transformation toughening mechanism. It was also
found that, the mullitization reaction and densication were faster,
and complete mullite formation and full density were achieved for
the composites sintered in SPRS at 1580 8C under a pressure of
40 MPa using ner particles obtained by attrition milling [514].
SPS (1050 Sumitomo Coal Mining Co.) treatment was
performed at 9001500 8C (50 8C/min heating rate), for 5
10 min under a pressure of 40 MPa, starting from 8 wt.% Y2O3
partially stabilized ZrO2, CaF2 (30 wt.%) and Ag (1040 wt.%) [515].
It was found that, as the Ag content was augmented, density
increased while Vickers hardness decreased. For the case of
35 wt.% Ag and 30 wt.% CaF2 added to the ZrO2(Y2O3) matrix, the
formation of a well-covered lubricating lm, which reduces
friction and wear resistance, was promoted. The selected
temperature value to obtain ZrO2(Y2O3)CaF2Ag composites
was found to be 950 8C.
Self-lubricating ZrO2(Y2O3)(30, 50 wt.%)BaCrO4 composites
have been fabricated by SPS at 10501500 8C (50 8C/min heating
time), 40 MPa of pressure and 510 min holding time [516]. The
higher density and the higher Vickers hardness were obtained for
ZrO2(Y2O3)30BaCrO4 sintered at 1100 8C for 5 min. It was found
that the composites exhibited distinct improvements in effectively
reducing friction and wear over a wide temperature range, as
compared to the unmodied ZrO2(Y2O3) ceramics.
Mechanically alloyed amorphous ceramic powders with a
chemical composition of ZrO2(3 mol%Y2O3)26.2 mol%SiO2
3.4 mol%CeO2, prepared by a planetary ball mill, were consolidated
at the heating rate of 480 K/min under the applied pressure of
150 MPa using an electrical discharge consolidation system [517].
A marked increase in the relative density occurred in the
temperature range 11781315 K, until fully dense bulk sample,
which consisted of tetragonal ZrO2 solid solution and amorphous
SiO2, with average grain size of 15 nm, were sintered at 1315 K.
2.7.6. Alumina/zirconia oxides
The 5 wt.%SiC15 wt.%ZrO2(3Y)Al2O3 powders from hetero-
geneous precipitation method was super-fast densied through
SPS (Dr. Sinter 1020, Sumitomo Coal Mining). Densication was
carried out at different sintering temperatures in the range 1350
1600 8C, with a heating rate of 600 8C/min, under an applied
pressure of 40 MPa and without soaking time [518]. Nearly full
dense samples were obtained at 1450 8C, whereas a temperature of
1650 8C and a soaking time of 1 h were needed when sintering by
HP. Sample sintered at 1450 8C had the highest Vickers hardness
(18 GPa). The bending strength was 1.2 GPa, which is much higher
than that of monolithic Al2O3 as well as ZrO2(3Y)Al2O3 ceramics.
Moreover, from microstructure investigation nano-SiC particles
were found to be located mainly within the Al2O3 grains, while the
transgranular fracture mode was observed.
PECS method was used to fabricate nanograined 3 mol% Y2O3-
stabilized-ZrO2/10 mol% Al2O3 composites starting from solgel
synthesized powders [519]. Sintering behavior was investigated by
heating starting powders in a SPS unit (2080 Sumitomo Coal
Mining Co.) at temperatures ranging from 1100 to 1500 8C (100 8C/
min heating rate) for 10 min, under a pressure of 500 MPa. Fully
dense (>98%) composites were obtained above 1300 8C. It was also
found that dense composites with Al2O3 as second phase exhibited
ner matrix grain sizes (<100 nm) as compared to monolithic
Y2O3-stabilized-ZrO2 (>130 nm), due to the role of Al2O3 inclu-
sions in suppressing grain growth.
SPS method (Dr. Sinter 1020, Sumitomo Coal Mining) was
applied on nanocrystalline (15 nm) ZrO2(Y2O3)20 mol%Al2O3
powders at different temperatures ranging from 1250 to 1500 8C
(600 8C/min heating rate), under a pressure of 40 MPa [520]. Full
density was attained at 1350 8C within 2 min in SPS, i.e. at quite
different conditions as compared to conventional hot pressing,
where a relative density of 98% was achieved when sintering at
1400 8C for 45 min, under a load of 30 MPa. All SPS sintered
samples consisted of tetragonal ZrO2, a-Al2O3 and a few
monoclinic ZrO2, with grain size approaching 200 nm.
PECS (SPS-2080, Sumitomo Coal Mining Co.) was successfully
employed to consolidate Al2O3/3 vol.% ZrO2 composite [521]. Full
density (>99%) was reached at 1450 8C in less than 5 min
(P = 15 MPa), and independently from the heating rate. The
addition of 3 vol.% ZrO2 was effective in increasing the average
bending strength and fracture toughness of the monolithic Al2O3 to
827 MPa and 6.1 MPa m1/2, respectively.
A full dense 20 vol.% yttria-stabilized tetragonal zirconia
polycrystalline (3Y-TZP)/Al2O3 nanocomposites with nanocrystal-
line (<100 nm) matrix grain size was successfully consolidated
using SPS (Dr. Sinter 1050, Sumitomo Coal Mining) at 1100 8C for
3 min, with a heating rate of 500 8C/min [522]. 3Y-TZP/Al2O3
exhibited a fracture toughness (8.9 MPa m1/2), almost three times
that of the pure dense Al2O3 (3.03 MPa m1/2) consolidated at
1100 8C for 3 min. Ferroelastic domain switching without phase
transformation in nanocrystalline ZrO2 was considered to be
effective for the improved toughness.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Al2O3, Al2O3 (200 ppm MgO)/3 vol.% ZrO2, and Al2O3 (200 ppm
MgO, 1000 ppm TiO2)/3 vol.% ZrO2 powders were consolidated up
to various porosity levels (30 and 50%) by PECS (SPS-2080
Sumitomo Coal Mining Co.) at 10001300 8C (50 8C/min heating
rate) and at 5.5 MPa, with a holding time of 30 min [523]. For Al2O3
(200 ppm MgO)/3 vol.% ZrO2 composites densication rate was
much slower than for the monolithic Al2O3, as the addition of ZrO2
was reported to retard the densication behavior and to control the
grain growth of Al2O3. Similarly, MgO and TiO2 were found to
retard grain growth and also grain boundary mobility through a
solute drag mechanism. It was also observed that the incorporation
of dopants and secondary inclusions had a positive effect on the
improvement of the mechanical properties of porous ceramics, due
to grain neck growth dominating over densication.
Zirconia 3 mol% yttriaaluminaalumina magnesia spinel
nanoceramic composites were obtained by SPS (Dr. sinter 1050
Sumitomo Coal Mining Co.) at 1150 8C with a holding time of 3 min
under a pressure of 63 MPa from both plasma sprayed particles and
high-energy ball milled (HEBM) plasma sprayed particles [524]. All
sintered compacts had a relative density over 99%. It was found
that only compacts sintered from HEBM powders exhibited
superplasticity with apparent activation energy of 940 kJ/mol at
temperatures in the range 13001450 8C.
Al2O3/ZrO2 composites with ZrO2 content of 0, 2.7, 11.0 and
21.0 mass% were fabricated by PECS (SPS-2050, Sumitomo Coal
Mining Co.) at 12501550 8C (200 8C/min heating rate), under a
uniaxial press of 40 MPa, with a holding time of 3 min [525].
Starting powders, consisted of a mixture of x- and g-alumina and
tetragonal ZrO2, were prepared by a solgel route followed by
calcination at 8001100 8C for 6 h. In particular, the temperature,
at which full-dense Al2O3/(11 mass%) ZrO2 bodies were attained,
increased from 1300 to 1500 8C if decreasing calcination tem-
perature from 1100 to 800 8C. The difculty in densication of
Al2O3/ZrO2 calcined at lower temperatures was ascribed to the
highly dispersed ZrO2 particles, which hindered sintering and grain
growth of a-Al2O3 at the initial stage of sintering. Bulk density was
also found to increase with increasing ZrO2 content, being the
density of ZrO2 higher than that of Al2O3. The incorporation of ZrO2
into the alumina matrix was also found to be very effective in
inhibiting grain growth of alumina leading to ner microstructure.
Furthermore, when using composites powders calcined at 1000 8C,
the bending strength of the dense ceramics sintered at 1350 8C
reached 1.2 GPa for a ZrO2 content of 5.7 mass%.
Dense a-Al2O3/(5 vol.%)/t-ZrO2/(5 vol.%)Ni composites with a
Ni nanoparticles homogeneously dispersed on the surface of
Al2O3ZrO2 particles, were fabricated by SPS at 1350 8C (130 8C/
min heating rate) for 15 min, under a pressure of 20 MPa [526]. It
was found that, after 1 min at 1350 8C Al2O3 grain size of the
starting powders was retained, while it markedly increased from
0.31 to 2 mm as the holding time was increased from 1 to 5 min. It
was also observed that hardness of the sintered specimens
increased with increasing holding time.
A mullitezirconia ceramic composites were obtained by
reactive sintering through SPS (Dr. Sinter 1050 Sumitomo Coal
Mining Co.) at 1000, 1100, 1200 and 1300 8C with duration of 10 and
30 min, starting from plasma spheroidized zirconAl2O3 powders
mixture [527]. It was found that decomposition of zircon started at
1000 8C, with tetragonal ZrO2 and amorphous SiO2 being formed. At
1200 8C mullite formation was found to dominate the process,
resulting in signicant increase of microhardness, Youngs modulus
and fracture toughness, whose values after 30 min soaking time
were HV 1250, 208 GPa and 5.49 MPa m1/2, respectively.
Dense ZrO2Al2O3MgAl2O4 composites were fabricated by SPS
(Dr. Sinter 1050, Sumitomo Coal Mining Co.) at 1150 8C for 3 min,
under a pressure of 63 MPa, starting from g-Al2O3, 3 mol% Y2O3-
187
stabilized-t-ZrO2 and MgO powders [528,529]. The obtained
samples exhibited a nal density of 99.8% of the theoretical value
with microstructure showing ne equiaxed grain morphology and
average grain size of 100 nm. From XRD investigations it was also
found that starting MgO and g-Al2O3 reacted to form MgAl2O4, and
that g- to a-Al2O3 phase transformation occurred. Moreover,
plastic deformation of dense ceramics was successfully performed
with SPS at 1150 8C and 105 MPa pressure. No surface cracks were
observed and the nanocrystalline structure was retained.
2.7.7. SiO2
Transparent silica glass, and free from any visible bubbles, was
fabricated by PEC within 2 min at a uniaxial pressure of 20 MPa, in
the temperature range of 17731873 K, with a heating rate of 50 K/
min, and starting from ne particles (70 mm) of SiO2. Investiga-
tions on the physical, mechanical and optical properties revealed
that silica obtained through PEC method had the same density,
refractive index, elastic modulus and absorbance as those of fused
silica [530].
Amorphous La2O3:SiO2 = 25:75 lms, prepared by rapid
quenching are grounding were sintered by SPS (515S Sumitomo
Coal Mining Co.) obtaining dense compacts (97% of the theoretical
value) at 850 8C without soaking time [531]. In contrast, when
using conventional sintering methods crystallization occurred
before densication, thus preventing the obtainment of amor-
phous products.
2.7.8. Mullite
Dense, translucent mulliteamorphous composite was fabri-
cated by SPS at 1300 8C (100 8C/min heating rate), under an applied
pressure of 40 MPa, starting from metakaoline powders [532].
The obtained samples exhibited average crystallite size of
2030 nm, and translucence of 7080% under a wave length of
10002500 nm.
PEC technique was employed to consolidate MgO (0.2 wt.%)-
doped and SrO (0.5 wt.%)-doped mullite powders [533]. Sintering
was performed by means of SPS (1050 Sumitomo Coal Mining Co.)
at 1500 8C (100 8C/min heating rate) for 2 min under an applied
load of 15 MPa. Samples with relative density greater than 98%
were obtained for both MgO- and SrO-doped mullite. SrO-doped
mullite compacts exhibited a duplex microstructure consisting of
ne equiaxed and elongated grains, with a corresponding mixed
type of intergranular and transgranular fracture mode. On the
other hand, MgO-doped mullite consisted of equiaxed and
smoother grains, and showed a typical transgranular fracture
mode. Higher fracture toughness was measured for SrO-doped
mullite samples as compared to MgO-doped ones, due to the
development of an interlocking microstructure of elongated grains.
2.7.9. TiO2
Anatase nanopowders (9 nm) were consolidate by SPS (1050
Sumitomo Coal Mining Co.) at different temperatures ranging
between 600 and 1000 8C (50 8C/min heating rate) at holding time
varying between 10 and 30 min, under applied pressures of 10
60 MPa [534,535]. It was found that the relative density of anatase
increased with increasing sintering temperature and the 90% of the
theoretical density was attained at about 850 8C, with almost no
anatase to rutile phase transformation. High density (>95%) was
achieved above 850 8C but some rutile was formed. It was also
found that relative density increased with increasing applied
pressure. Furthermore, remarkable crystallographic preferential
orientation was found in the nanostructured anatase specimens
consolidated at 700800 8C.
TiO2 specimens with relative density of about 97% and ne
grain sizes (200 nm) were fabricated by SPS at 720 8C within
188 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 69. Relative density of TiO2 as a function of the sintering temperature. The SPS method displays a signicant increase of density compared to conventional sintering.
Adapted from Angerer et al. [538].

10 min holding time, under a pressure of 40 MPa, starting from
ultra-ne (<50 nm) rutile powders synthesized by solgel method
[536,537]. Near full-dense TiO2 compacts with retained ne grain
size (<300 nm) were obtained by slightly increasing the sintering
temperature to 760 8C for 10 min. In contrast, conventional sin-
tering method achieved the relative density of 99.2% at 1300 8C for
2 h, with an applied pressure of 100 MPa. Microwave dielectric
properties were also measured for both SPS and conventionally
sintered specimens after re-oxidizing process.
It has been also reported [538] that submicron (200 nm average
particle size) and nano (40 nm average particle size), structured
TiO2 (mainly anatase) powders were successfully consolidated by
SPS (1050 Sumitomo Coal Mining Co.) between 800 and 1000 8C
(100 8C/min heating rate) within 1 min holding time, under a
pressure of 715 MPa. Results were compared with those obtained
through conventional sintering in an electrical furnace between
600 and 1000 8C (20 8C/min heating rate) for 120 min after
compaction at 50 MPa. When the sintering temperature was
raised from 800 to 1000 8C, the relative density of nanostructured
and submicron samples varied in the range 9599 and 6597%,
respectively (cf. Fig. 69). Moreover, phase change to rutile was
found for all nanostructured SPS samples, while in the 200 nm
powder samples the anatase-rutile transition happened between
800 and 900 8C. The conventional sintering led to similar results. In
addition, grain growth in the conventional sintering was sig-
nicantly higher in comparison to SPS samples at an equivalent
rate of densication (cf. Fig. 70).
Full dense (99% of the theoretical value) TiO2 displaying a rutile
structure with an average grain size of 200 nm was obtained by SPS
at 700 8C (150 8C/min heating rate) for 1 h by applying a pressure of
62 MPa [539]. In contrast, when sintering was done by conven-
tional methods, theoretical density was attained above 900 8C for
1 h, with average grain size of 12 mm.
Anatase structured bulk samples were recently consolidated
[540] through SPS from nanocrystalline (7 nm) and microcrystal-
line (5 mm) anatase TiO2 at lower temperature, in the range 400
550 8C (90 8C/min heating rate), and at higher pressure, 555 MPa,
as compared to the SPS conditions reported above [538]. The

Fig. 70. Relative grain size of TiO2 as obtained by XRD, plotted as a function of the relative density. The SPS method shows a signicant smaller grain growth. Adapted from
Angerer et al. [538].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
consolidated nanocrystalline samples exhibited an anatase phase
only when the sintering temperature was as low as 400 8C, while
with rising temperature also rutile phase appeared. On the other
hand, microcrystalline TiO2 compacts consisted of both anatase
and rutile when sintered at 400 and 450 8C, while complete
anatase-rutile transformation was observed at 500 and 550 8C. The
relative density of the bulk anatase samples consolidated within
5 minutes was found to be 95.7% of the theoretical value. Further
increase in density was possible at longer holding time.
Mg[Ti2]O4 single-phase spinel structure was recently synthe-
sized [541], from Ti2O3 and MgO powders, by a new arc melting
method using SPS (3.20 MKII Sumitomo Coal Mining Co.) at
1300 8C (100 8C/min heating rate) within 1 h under a pressure of
4 kN (die inner diameter = 10 mm). The obtained sample had a
relative density of 99.3% of the theoretical value and exhibited ne
microstructure with average grain size of 200 nm.
Full dense ceramics were successfully prepared by SPS (Dr
Sinter 1050, Sumitomo Coal Mining) both from plasma sprayed
metastable Al2TiO5 and nanopowders of TiO2 and Al2O3 [542].
When performing densication at 1000 8C (heating rate 300 8C/
min) or between 1150 and 1250 8C for 3 min at 63 MPa, Al2TiO5
decomposed to/a-Al2O3 and TiO2, or resulted stable, respectively.
The addition of nano-MgO powders to both metastable Al2TiO5 and
nano-TiO2 and Al2O3 led to the formation of Mg0.3Al1.4Ti1.3O5 along
with MgAl2O4 spinel.
2.7.10. Ceria
A relative density of 85% was achieved when using SPS to
consolidate Dy-doped CeO2 powders at 10001200 8C (500 8C/min
heating rate) under a pressure of 60 MPa without holding time
[543]. On the other hand, dense Dy-doped CeO2 bodies with nano-
hetero structure were obtained by combining SPS and conven-
tional sintering. The design of nano-hetero structure was found to
be very important to improve conductive properties in doped CeO2
solid electrolytes for SOFCs applications.
Nanometric (35 nm) Ceria powders doped with 30 mol%
samaria, synthesized by the wet chemistry method, were fully
consolidated by SPS at 1000 8C under a pressure of 146 MPa [544].
When the pressure was increased to 530 MPa full density was
attained at 820 8C being grain size of 16.5 nm. It was found that
electrical conductivity depends on grain size.
High dense (>98%) samaria-doped-ceria (Ce0.7Sm0.3O2) cera-
mics with grains size of about 10 nm were recently fabricated in
5 min by SPS at 815 8C under 610 MPa and high heating rate
(200 8C/min) [505]. Uniform microstructure and ne grain sizes
below 200 nm were observed.
2.7.11. MgO
Superfast densication of nanocrystalline MgO powders was
carried out by SPS (Dr. Sinter 2050, Sumitomo Coal Mining Co.) at
temperatures ranging between 700 and 800 8C, under a pressure of
100 MPa [545,546]. Sintered samples exhibiting density in the
range 9196% of the theoretical value were obtained with 5 min
holding time. The corresponding grain sizes varied between 30 and
70 nm. In contrast, during pressureless sintering, signicant grain
growth started when the relative density was in the range 9095%,
for temperatures above 1250 8C and 5 h holding time. The most
important nding was a remarkable optical transparency obtained
above 775 8C for sintered samples obtained by both single and two
steps SPS process, in contrast with the opaque nature of MgO
samples obtained by hot pressing.
2.7.12. ZnO-based materials
Dense nanocrystalline ZnO ceramics were produced by SPS at
50 MPa and at different temperatures in the range 400750 8C
189
(200 8C/min heating rate) with 1 min holding time starting from
ne (20 nm) ZnO powders obtained by precipitation reaction
[547]. The highest density (98.5% of the theoretical value) was
achieved at 550 8C, with a grain size of 100 nm. A novel conduction
non-linearity was observed in specimens sintered at 500 8C, due to
the amorphous grain boundaries of nanocrystalline ZnO ceramic.
SPS (515S Sumitomo Coal Mining Co.) was used at tempera-
tures in the range 8001000 8C (100 K/min heating rate) for 4 min
under an applied pressure of 60 MPa to fabricate high tempera-
ture thermoelectric M-doped-ZnO ceramics (M = Al and/or Ni), i.e.
ZnO, Zn0.98Al0.02O, Zn0.98Ni0.02O and (Zn0.98Ni0.02)0.98Al0.02O,
starting from ZnO, a-Al2O3 and NiO [548]. All obtained samples
exhibited a relative density of 99% of the theoretical value. The co-
addition of Al2O3 and NiO was also found to improve the
performance of thermoelectric conversion because of the forma-
tion of a solidsolution ZnO phase with Al2O3. The presence of NiO
increased the electrical conductivity and decreased the thermal
one. The gures of merit of M-doped ZnO showed a higher value
than that for pure ZnO.
Nanocrystalline ZnO ceramics for optical applications were
fabricated by SPS (2040 Sumitomo Coal Mining Co.) at 550 8C
(120 8C/min heating rate) under a pressure of 50 MPa, with a
holding time of 2 min [549]. Samples with grain size of 8090 nm
were obtained. For comparison, consolidation was also performed
by pressureless sintering at 8001200 8C (5 8C/min heating rate)
for 2 h. Nanocrystalline ceramics (100 nm) were obtained when
heating at 800 8C for 2 h. The grain size rapidly increased to 5
8 mm at 1200 8C. Furthermore, excellent green emission properties
were obtained for the ZnO ceramics obtained by SPS and by
pressureless sintering at 1000 8C.
Green sheets of ZnO, obtained by an extrusion process, were
stacked one by one following the extrusion direction and
subsequently sintered by SPS at 1000 8C for 3 min under a load
of 50 MPa, thus obtaining near full-dense ZnO ceramics with
homogeneous microstructure displaying equiaxed grains of
several micron in size [550]. After SPS, highly c-axis preferred
orientation (ber texture) was observed for extruded samples.
ZnAl2O4 was fabricated by sintering Al2O3 and ZnO powders in
SPS at 1500 8C (200 8C/min heating rate) for 1 min under a pressure
of 30 MPa [551]. Some cracks were observed in the ZnAl2O4
sintered body, as a consequence of the structure mismatch because
of periodical temperatures during SPS.
2.7.13. CaCoO-based materials
Ca3Co4O9 ceramics were fabricated through SPS at 750 8C for
5 min under an applied load of 50 MPa, starting from pure
Ca3Co4O9 powders synthesized by solgel method and subse-
quently calcined at 800 8C for 2 h [552]. For comparison,
powders from the gel calcined at 600 8C were also sintered by
conventional method at 900 8C for 8 h. Plate-like grains of 1
2 mm were observed in both SPS and conventionally sintered
samples, while a pronounced grain alignment was observed in
the SPS specimens as compared to conventionally sintered ones.
The bulk density was 99% and 70% of the theoretical value for
SPS and conventionally sintered Ca3Co4O9 ceramics, respec-
tively. Moreover, SPS sintered ceramics exhibited improved
thermoelectric properties.
Single-phase Ca2Co2O5 textured ceramics were obtained by
SPS at 800 8C (100 8C/min heating rate) for 5 min at 30 MPa, using
the precursor powders calcined at 700850 8C for 2 h [553]. Sheet-
like grains well-oriented and perpendicular to the pressure
direction were found. The thermoelectric gure of merit ZT of the
SPS sample was estimated as 0.21 at 700 8C, which was found to be
much higher than that of the Ca2Co2O5 ceramics prepared by
solid-state method.
190 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
2.7.14. CaSiO3
Dense b-CaSiO3 ceramics were fabricated by SPS (Dr. Sinter
2040 Sumitomo Coal Mining Co.) at 700950 8C (150200 8C/min),
under a pressure of 40 MPa with a holding time of 5 min, using
chemically precipitated amorphous powders [554,555]. The
maximum density of the obtained b-CaSiO3 ceramics reached
about 2.60 g/cm3 with grain size of 100200 nm when sintering
was performed at 750 8C. The maximum bending strength was
190 MPa. The Youngs modulus and fracture toughness reached
62.8 GPa and 1.67 MPa m1/2, respectively. The SBF tests showed
that HA grains covered the surface of b-CaSiO3 ceramics
completely after 3 days immersion.
Wollastonite (CaSiO3) ceramics were recently prepared by SPS
(1050 Sumitomo Coal Mining Co.) in 5 min under a pressure of
30 MPa, at different temperatures ranging from 1100 to 1200 8C
and different heating rate, i.e. 100, 150 and 200 8C/min for each
temperature, using CaSiO3 ultra-ne powders as precursor [556].
The ceramics obtained at 1150 8C at a heating rate of 100 8C/min
exhibited the lowest occurrence of porosity with ne grain size of
about 37.6 nm and a relative density of 97.3%.
2.7.15. Oxynitrides
Silicon oxynitride (Si2N2O) powders synthesized by means of
the SHS process were densied in the presence of 5 wt.% CaO
Al2O3 by using SPS technique (Dr. Sinter 1050 Sumitomo Coal
Mining Co.) at 1600 8C with a heating rate of 400 8C/min and a
holding time of 2 min, under a pressure of 30 MPa [557]. The
density of the SPS sintered samples was 99% of the theoretical
value. The same value was achieved by pressureless sintering
methods at higher temperatures and at much longer time, such as
1900 8C for 4 h holding by hot isostatic pressing (HIP), 1750 8C for
45 h heating up and holding by HP, and at 16501670 8C for 3 h
holding. Morphology of the fracture surface showed that grains
were equiaxed and that the fracture occurred in transgranular
mode. Vickers hardness, fracture toughness and strength were
18.7 GPa, 3.3 MPa m1/2, and 363 MPa, respectively. Moreover,
sintered specimens exhibited excellent oxidation resistance at
high temperature up to 1500 8C.
Powder mixtures with composition corresponding to
RE2Si6N8O3 and RE2Si4Al2N6O5 with RE = Ce and La, were
consolidated by SPS (Dr. Sinter 1050 Sumitomo Coal Mining Co.)
[558]. The samples were heated up from 600 8C at a constant
heating rate of 200 8C/min, under a pressure of 50 MPa, to a
temperature at which full densication had taken place, which
varied with composition between 1350 and 1450 8C.
2.7.16. SnO2-based oxides
Both commercial (average particle 60 nm, large agglomerates of
800 nm) and dispersed synthesized (average particle 30 nm,
agglomerates of 70 nm) SnO2 powders were sintered by SPS at
1200 A and 37.5 MPa [559]. It was found that densication of
commercial SnO2 powders occurred at 1000 8C. The relative
density of the commercial SnO2 powders specimens reached the
maximum value of 95% of the theoretical density at 10001050 8C
after 50 min holding time, and then slightly decreased with further
increasing sintering temperature. Furthermore, the specimens
from commercial powders were observed to contain many large
voids. In contrast, samples obtained from well-dispersed synthe-
sized SnO2 showed enhanced densication without any large pores
and with a more homogeneous microstructure as compared to
samples prepared from agglomerated commercial powders. In
addition full densication (>99%) was achieved from dispersed
powders sintered at 1050 8C for 5 min.
The densication of SnO2(0.9 mol)Sb2O3 solid solution,
synthesized by conventionally solid-state method, was performed
by FAST at 890 8C for 10 min under 40 MPa [560]. A relative density
of 92.4% was attained and a consolidated microstructure with
essentially no pores was observed.
Antimony-doped tin oxide (ATO) ceramics (Sb/Sn molar
ratio = 5:100) with high conductivity were fabricated by SPS at
750, 800 and 850 8C for 4 min under an applied load of 40 MPa
starting from mono-dispersed ATO powders synthesized by the
hydrothermal method [561]. A relative density of 83.7% was
achieved at 750 8C, but it drastically increased to 96.7% as the
sintering temperature was raised to 800 8C. The relative density
further increased to 97.4% at 850 8C. Moreover, resistivity was
found to decrease with increasing sintering temperature and thus
relative density, due to the electron mobility in the ceramics.
Dense In2O3SnO2 (In:Sn = 90:10 molar ratio) ceramics for
sputtering targets applications were prepared by SPS (3.20 MK4,
Izumi Technology, Japan) at 9001000 8C under an applied load of
30 MPa with different heating rate, i.e. 16 or 50 8C/min and
dwelling time, i.e. 5 or 30 min [562]. For comparison the same
powders were also conventionally sintered in a mufe furnace at
10001600 8C for 2 h. Relative high density (91% of the theoretical
value) was obtained by SPS when sintering at 1000 8C for 30 min
with a relatively slow heating rate (16 8C/min). On the other hand,
conventional sintering resulted in much lower density (4045%).
2.7.17. La-based oxides
La2Mo2O9 ultra-ne (2050 nm) powders, synthesized by sol
gel method, were densied by SPS (Dr. Sinter 2040, Sumitomo Coal
Mining Co.) at 750900 8C (100 8C/min heating rate) 030 min, at
the applied pressure of 45 MPa [563]. It was found that with a
holding time of 5 min the relative density increased from 89.98 to
98.64 as the sintering temperature was increased from 750 to
800 8C, respectively. It was also noticed that the holding time at
900 8C strongly affect the nal relative density achievable. With
increasing holding time in the range 030 min the relative density
increased from 92.0 to 96.05%, respectively. Moreover, the
microstructure of the samples sintered at 800 8C for 5 min
consisted of round or hexagonal grains with average size 1
3 mm. The microstructure was observed to change in the speci-
mens sintered at 900 8C for 5 min, since the grains become of rod
type with length of about 8 mm. The unilateral alignment of the rod
type grains at high sintering temperature was responsible of the
anisotropy in oxygen ionic conductivity.
SPS at 1323 K was also applied to prepare compacts of relative
density higher than 98% of proton conducting Sr-doped LaPO4
[564]. No more than 94% relative density was achieved with
conventional pressureless sintering at 14731573 K. The SPS
samples prepared at 13231373 K exhibited a bending strength
of 240 MPa and a Vickers hardness of 6.7 GPa.
Full dense and transparent lanthanum silicate oxyapatite
La9.33Si6O26 ceramics for SOFC applications were successfully
obtained by spark plasma sintering starting from freeze dried ne
powders [565]. Sintering was performed in SPS (Dr. Sinter 2080) at
two different temperatures, 1200 and 1500 8C, by following two
thermal cycles. Specically, in both cases temperature was
increased up to 600 8C at a heating rate of 300 8C/min and held
at this temperature for 1 min, under a pressure of 100 MPa.
Subsequently temperature was further increased to the selected
sintering temperature at a heating rate of 50 8C/min. For the case of
1200 8C sintering temperature, both pressure and maximum
temperature were maintained for 3 min, and then pressure and
heating power were released. On the other hand, for the case of
1500 8C sintering temperature, the pressure and the heating power
were released when the desired temperature was reached. After
SPS sintering, samples were heat treated in air at 1000 8C for 12 h,
in order to remove carbon residuals. A single-phase product with
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
hexagonal apatite structure was obtained after both sintering
cycles. Furthermore, samples had a vitreous aspect and were
transparent with a relative density of 100%. Grain sizes in the range
100500 nm were found after sintering at 1200 8C for 3 min, while
samples consolidated at 1500 8C consisted of grains larger than
1 mm in the range 35 mm. On the basis of the obtained results it
was stated that SPS allows one to control the microstructure of the
samples maintaining a high level of densication. In addition, it is
stated that the initial powders, having a low level of particle
aggregation, strongly affected the entire densication process.
Thus the combination of spray drying and SPS methods was found
to be an interesting route to obtain very dense apatite samples, a
compound well known for its high resistance to densication.
2.7.18. MxV2O5 (M = Cu, Ag, Zn)
Fast diffusion of Cu into V2O5 was recently investigated by
means of CuV2O5 diffusion couples and the SPS technique [566].
Specically Cu powders were rst placed in a carbon die and
subsequently V2O5 powders were added to create a planar
interface between the metal and the oxide by taking a special
care to avoid powder mixing. The die was then heated to 520 8C
(100 8C/min heating rate) in SPS (Syntex 2080) while a mechanical
pressure of 75 MPa was applied. The holding time was varied in the
range 232 min under Ar atmosphere, which was also maintained
during quenching. The resulting compaction was found to be larger
than 95% of the theoretical density. Diffusion prole of Cu into
V2O5 and the growth of the CuxV2O5 were followed by back-
scattered imaging and energy dispersive spectrometry. In parti-
cular, it was found that two phases exhibit signicant growth at
520 8C. In the more Cu concentrated phase (e), the diffusion
coefcient was found to be equal to 3  108 m2/s, which is of the
order of magnitude of self-diffusion in liquid metals. A lower value
was found in the less Cu concentrated phase (b0 ). This nding was
assumed to be a consequence of the different mechanism of Cu
diffusion in the two phases: two-dimensional and one-dimen-
sional diffusion in e and b0 phase, respectively.
SPS was further employed with the aim to synthesize dense
vanadium oxide bronzes with general formula MxV2O5 (M = Cu, Ag,
Zn), whose structure and electric properties are interesting for
applications as electrode materials in lithium batteries [567].
Synthesis and consolidation were performed using a Dr. Sinter
2080 Syntex machine, at different temperatures (550 and 600 8C)
and mechanical loads (5075 MPa). In particular, a sandwich of
V2O5CuV2O5 powders was prepared in a carbon die, heated from
20 to 600 8C in 6 min under a pressure of 50 MPa and subsequently
held at the maximum temperature for 2 min, before a rapid
quenching takes place. After SPS treatment, a relative density of
95% was achieved. It was found that a fast reaction occurred
between the Cu layer and the V2O5 ones, with the formation of e
CuxV2O5 bronze.
In addition, a major development of the e CuxV2O5 phase, with
the corresponding decreasing of V2O5 and Cu slabs, was observed
by increasing the holding time to 6 min.
d AgxV2O5 bronze phase was also obtained under the same
experimental conditions adopted for the case of e CuxV2O5. Similar
experiments were also carried out to investigate the behavior of
pure Zn on V2O5. In this case the low melting point of Zn (420 8C)
made impossible, before metal melting, the occurrence of any
reaction with the oxide.
2.7.19. Other oxides
Bilayered ferritelead titanate zirconate (PZT) pellets were
sintered by SPS at 950 8C for 3 min under 50 MPa. Specically
submicron BaFe2O4 and NiFe2O4 were used as ferrite phases [568].
A distinct interface was obtained for NiFe2O4/PZT without
191
interphase diffusion and reaction zone. In contrast a visible
interphase diffusion zone of 20 mm width was seen between the
two layers for BaFe2O4/PZT. On the basis of this nding NiFe2O4/
(1  x) PZT magnetoelectric ceramics with x (volume fraction) in
the range 0.30.5 were fabricated at different temperatures
ranging from 900 to 1050 8C and pressure levels between 50
and 100 MPa. A relative density of 99% was achieved for
0.3NiFe2O4/0.7PZT, when sintering temperature was 950 8C. The
inuence of the SPS conditions on the magnetic dielectric
properties was also considered.
SPS was also employed to consolidate ne (100200 nm
particle size) powders of BaYxZr1xO3x/2 (x = 0, 0.08, 0.16) and
pure BaZrO3, starting from powders synthesized through solid-
state reaction [569]. Densication was carried out by heating at
200 8C/min up to sintering temperature at 105 MPa and then
holding at constant temperature (14001600 8C) for 05 min. After
sintering, samples were calcined at 1000 8C for 2 h. For BaZrO3 a
relative density of 96% was reached without signicant grain
growth after only 1 min at 1500 8C. Densication of BaYxZr1xO3x/
2 resulted more difcult, and a relative density higher than 95% was
attained only at 1600 8C. In particular, the optimum result was
obtained for x = 0.16, with a relative density of 97.6% and grain size
lower than 300 nm after 5 min at 1600 8C. Better densication as
compared to x = 0.08 (95% relative density, at 1600 8C for 5 min)
was attributed to the presence of yttria-stabilized-zirconia as a
precursor in the samples with x = 0.16. Non-isothermal fast
sintering resulted in 260 nm grain size and relative densities of
93% and <90% for BaZrO3 and BaYxZr1xO3x/2, respectively, when
sintering was performed at 1600 8C without holding time.
Dense Ba(Zn1/3Ta2/3)O3 with disordered perovskite structure
(Pm3m) was synthesized by SPS at 1150 and 1300 8C for 5 min at
30 MPa [570]. The disordered Ba(Zn1/3Ta2/3)O3 with high density
(7.62 g/cm3) exhibited signicantly high quality factor (53400 GHz),
ve times higher than that of low density (5.06.0 g/cm3) samples
synthesized by conventional solid-state reaction.
Ba63xSm8+2xTi18OP54 (x = 2/3) microwave dielectric dense
(98% relative density) ceramics with a tungsten bronze-type
structure were synthesized by SPS, at 1200 8C (200 8C/min heating
rate), in 5 min under a pressure of 60 MPa. Superior microwave
dielectric properties were measured [571].
Tungsten bronze Sr2xCxNaNb5O15 (x = 0.1) piezoelectric cera-
mics were prepared by SPS (1030 Sumitomo Coal Mining Co.) at
different temperatures in the range 10001200 8C (30300 8C/min
heating rate) with different duration times ranging from 5 to
60 min, under a pressure of 35 MPa [572,573]. Reagent-grade ball
milled SrCO3, Na2CO3, CaCO3 and Nb2O5 were used as starting
powders. A Sr2xCxNaNb5O15 (x = 0.1) tetragonal phase ceramic,
with pore-free uniform microstructure and grain sizes in the range
1.524.11 mm was obtained when sintering at 1200 8C for 5 min
with a heating rate of 300 8C/min. A relative density of 99.6% was
also achieved and similarly to other tungsten bronze materials the
Sr2xCxNaNb5O15 (x = 0.1) specimen become uniformly translu-
cent. The sintering parameters (temperature, heating rate and
soaking time) were found to strongly affect the electrical proper-
ties of Sr2xCxNaNb5O15 (x = 0.1) ceramics. Specically the
compacts sintered at 1200 8C was ferroelectric. In general,
electrical properties increased with increasing both heating rate
and soaking time.
Pirochromite (MgCr2O4) ceramics were prepared by SPS at
1400 8C (25 8C/min), for 5 min under a pressure of 30 MPa, starting
from MgCr2O4 powders synthesized by solgel method and
calcined at 1000 8C for 1 h [574]. The obtained ceramics had a
relative density of 99.5% of the theoretical value and average grain
size of about 2 mm. Fracture toughness and bending strength were
3.7 MPa m1/2 and 310 MPa, respectively.
192 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Dense (La0.9Sr0.1)CrO3 ceramics, for SOFCs applications, with
97% relative density were obtained by SPS (515S IZUMI Technol-
ogy) at 1500 8C (170 8C/min heating rate) under an applied
pressure of 39 MPa, with a dwell time of 5 min [83]. The adopted
sintering conditions were quite different from those used for
conventional sintering method (T = 1600 8C, P = 190 MPa, dwelling
time = 3 h) which allowed (La0.9Sr0.1)CrO3 to achieve only 50% of
the theoretical density. The SPSed samples consisted of ne grains
(0.2 mm) in close contact.
A series of columnar phases Ln2/3,&1/3[Bi12O14](MoO4)5, with
& = vacancy and Ln = La, Nd, Gd, Ho, Yb, was prepared by solid-
state reaction and then sintered in SPS (Sumitomo 2080) under
50 MPa, by heating from 20 to 600 8C in 3 min and from 600 to
700 8C in 2 min, with a holding time of 2 min at the maximum
temperature before a rapid quenching takes place [575]. Samples
with a relative density greater than 95% of the theoretical value
were obtained. The resulting structure along with the evolution of
anionic conductivity versus the ionic radius size of the Ln elements
were described. The maximum ionic conductivity (6.6  103 S/
cm) was obtained using Gd at 980 K.
SPS (515S Sumitomo Coal Mining Co.) was also recently
employed to fabricate polycrystalline high dense samples of
SrVO3d. Sintering was performed at 1773 K at a heating rate of
300 K/min from room temperature to 873 K and 100 K/min from
873 to 1773 K [576]. A high dense perovskite structure with
relative density of 95% was obtained.
It was also reported that, SrY2O4 powders, synthesized by
reacting Y2O3 and SrCO3 at 1273 K in air, were consolidated near to
full density (99%) by SPS (Dr. Sinter 1020 Sumitomo Coal Mining
Co.) at 1773 K for 3 min under nitrogen atmosphere [577]. Since it
exhibited high temperature stability and enough thermal expan-
sion, polycrystalline sintered SrY2O4 was found to be interesting
for thermal barrier coating materials.
BaY2O4 ceramics for thermal barrier coating applications were
prepared by SPS (515S Sumitomo coal Mining Co.), starting from
Fig. 71. Relative densities (a) and the corresponding microstructures of the SPS-processed BMN at (b) 800 8C; (c) 850 8C and (d) 900 8C for 3 min. Adapted from Shim
et al. [580].
polycrystalline powders synthesized by solid-state reaction [578].
Densication was performed at 1273 K under an applied pressure
of 30 MPa. The heating rate was set to 100 K/min from room
temperature to 873 K and 50K/min from 873 to 1273 K. The SPS
sample density was 88% of the theoretical one.
Dense NASICON (Na3Zr2Si2PO12) ceramics were obtained by SPS
at temperatures in the range 9001200 8C (100 8C/min heating
rate) for 30 min under a pressure of 62 MPa, starting from pre-
cursor synthesized by solid-state reactions [579]. The highest
relative density, close to the theoretical value, was achieved at
1150 8C by SPS, while signicantly lower density (74%) was
attained after conventional sintering at 1220 8C for 14 h. However,
in contrast to conventional sintering where an almost single-phase
was detected, the specimens prepared by SPS showed of a large
amount of ZrO2 in addition to Na3Zr2Si2PO12. The dominant
existence of ZrO2 was attributed to the volatilization of Na and P
during sintering, leading to ZrO2 segregation. At this respect, it was
found that ZrO2 formation could be suppressed by adding 5 mol%
excess of Na and P (5Na5P) to the starting powders. Moreover, for
the stoichiometric composition, SPS specimens showed fully
densied microstructure and smaller grain size than convention-
ally sintered samples.
Bi1.5MgNb1.5O7 microwave dielectric nanopowders (16 nm),
synthesized through the metal citrate process and calcined at
600 8C for 3 h, were sintered by SPS at temperatures ranging from
800 and 1000 8C (200 K/min heating rate), for 3 min [580]. The nal
sintered bodies were found to have relative densities of 96.5%
when sintering at 800 8C, 98.7% at 850 8C and 98.8% at 900 8C,
respectively (cf. Fig. 71a). The sintered specimens exhibited a
uniform and dense microstructures consisting of small grains with
uniform size distribution (cf. Fig. 71bd).
CaBi2Nb2O9 powders were sintered by SPS (Dr. Sinter 2050,
Sumitomo Coal Mining Co.) [447]. It was found that the
densication occurred within a very narrow temperature interval
ranging from 825 to 1000 8C. CaBi2Nb2O9 was sintered for 4 min at
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
925 8C (100 8C/min heating rate) and 100 MPa, thus attaining a
relative density of 95%. The microstructure of the CaBi2Nb2O9
compacts showed the presence of small platelet grains similar to
the starting powders (0.71 mm).
Ruthenium oxide nanopowders (30 nm) for cryogenic applica-
tions were consolidated into compacts using the P2C method at
11231223 K at a pressure range of 80100 MPa [581]. Based on
consolidation conditions, specimens exhibited nal densities in
the range 7991%. The obtained sensors showed metallic behavior
and strong positive temperature coefcient of resistivity.
ZnO, ZrO2/3 wt.% Y2O3, and Al2O3 were compacted by SPS at
50 MPa at a heating rate of 200 8C/min up to 850, 1100 and 1250 8C,
respectively [582]. Very homogeneous microstructure was
obtained with average grain size around 500 nm for alumina
and less than 100 nm for zirconia.
SPS was also used to prepare Al2O350BaSO420Ag, Al2O3
50BaSO410SiO2, Al2O350SrSO4, Al2O350PbSO45SiO2, Al2O3
50BaSO4 and Al2O350BaCrO4 (mass%) composites under a
pressure of 40 MPa for 0.3 ks [583]. It was found that the relative
density of Al2O350BaSO4 (about 90%) sintered at 1273 K
decreased by adding 10 mass% SiO2 (80%). On the other hand
density strongly increased up to theoretical value by adding
20 mass% Ag at lower temperature (1173 K). When sintering
Al2O350SrSO4 and Al2O350PbSO45SiO2 at 1273 and 1073 K,
respectively, relative densities were below 90%. In addition, Al2O3
50BaSO420Ag showed the lowest friction coefcient in the
temperature range 4731073 K.
Ultra-ne powders of b-Ca3(PO4)2 (b-TCP) powders (100 nm
average size) obtained by precipitation method, were processed by
SPS at 875 8C (heating rate 150 8C/min) for 2 min under 40 MPa.
Transparent b-TCP with relative density over 99.7% and average
grain size of 250 nm was obtained [584].
PECS method was applied for the fabrication of Linde type-A
zeolite (LTA) with HA thin layers and uoroapatite (FAp) sintered
bodies that may represent long-term materials for radioactive
waste disposal [585]. LTA powders, synthesized by hydrothermal
sintering, and spray dried FAp powders made by reacting
orthophosphoric acid with calcium hydroxide, were mixed at a
weight ratio of 3/7 and subsequently sintered by PECS (SPS-1030,
Sumitomo Coal Mining Co.) at 50 MPa. Temperature was increased
to 900 8C at a rate of 50 8C/min and, after holding at 900 8C for
10 min, samples were slowly cooled to 600 8C at a rate of 5 8C/min.
XRD analysis performed after sintering identied only FAp phase
which was an indication of the LTA amorphization induced by PECS
method. The amorphous LTA in the sintered bodies was covered
with HA crystals and the HA layer completely coupled with FAp
grains. Mechanical properties were also measured. The micro-
hardness of the amorphous LTA and the interface LTA/FAp were
lower than that of FAp. Bending strength showed that the LTA/FAp
interface is weak.
Ceramic samples of Zn1xLixO were prepared using SPS starting
from stoichiometric amounts of ZnO and Li2O. Sintering was
performed at 800 K under the pressure of 450 kg/cm2 for 5 min.
Subsequently dense products were annealed at 1070 K for 3 min
[586].
The new B10Mo3O24 phase, belonging to the Bi2O3:MoO3
system, was synthesized by wet chemistry method and then
sintered by SPS in 5 min at 650 8C under a pressure of 75 MPa
[587]. The compound was found to exhibit good ionic conductor
properties in the whole temperature range of stability.
2.8. Sialon
Dual cation (Yb + Y)-stabilized a-sialon ceramics, with either
stoichiometric composition or non-stoichiometric composition
193
that yield less than 3 vol.% of an additional intergranular liquid/
glass phase, were consolidated by SPS [588]. Below a temperature
threshold, full densication and complete a-sialon formation were
accompanied by very limited grain growth. Direct annealing by SPS
process yielded in situ reinforced microstructures which were
generated via a dynamic ripening mechanism. This provided an
efcient means of developing in situ reinforced microstructure in
a-sialon ceramics with improved mechanical properties.
It was also found [588,589] that single-phase a-sialon ceramics
with in situ reinforced bimodal microstructure (i.e. large elongated
grains embedded in a matrix consisting of small equiaxed grains)
were obtained above 1750 8C in all systems compacted by SPS
from a-Si3N4 as precursor powder and Y, Nd, Sm, Dy, and Yb as
stabilizers.
Using SPS above 1200 8C, it has been shown by Shen and Nygren
[590] that a-SiAlON phases were initially formed in Ce-, La-, Eu-
and Sr-doped sialon systems, and that subsequent in situ and ex situ
post-heat-treatment results in a decomposition of the a-sialon
phase. These observations showed that cations with a radius larger
than 1 Angstrom were able to stabilize the a-sialon phase, in
contrast with previous ndings. Cerium-doped a prime-SiAlON
material was prepared by SPS at 1750 8C under 30 MPa pressure for
10 min. Yttrium a prime-SiAlON seeds (1 wt.%) were added to the
starting powder mixture [591]. The structural analyses revealed a
high density of domain boundaries, within which larger amounts
of cerium ions were segregated in the matrix. The density of the
domain boundaries was proportional to the amount of incorpo-
rated cerium ions. These structural defects eventually dominated
the growth habits of the a prime-SiAlON crystals, by modifying the
structure of the interstices at the boundary sites.
SPS has been used to consolidate a lithium-doped duplex ab-
sialon with the overall composition Li0.5Si9.5Al2.5O2.0N14 [592]. The
kinetics of densication has been studied, and the phase transfor-
mation, reactions and grain growth occurring in the dense compacts
upon further heat treatment have been investigated. Two sources of
Si3N4 powders were used, namely a- and b-Si3N4. Green bodies
heated at a rate of 100 8C/min yielded full dense compacts at 1450 8C
(a-Si3N4) and 1500 8C (b-Si3N4) without holding, and these
compacts consisted mainly of a locally formed liquid and precursor
Si3N4 particles. Upon further heating it was observed that a-sialon is
formed initially, irrespectively of whether a-Si3N4 or b-Si3N4
powder was used as Si3N4 source. When a-Si3N 4 was used as
starting powder, almost monophasic a-sialon compacts were
formed before any transformation to b-sialon takes place on further
heating. When b-Si3N4 was used as starting powder the formation
of b-sialon was kinetically promoted, and compacts containing a-
sialon, b-sialon and b-Si3N4 were obtained before the equilibrium
phase assemblage was reached (i.e. a lithium-doped duplex
ab-sialon ceramic). These observations can be interpreted in
terms of the Ostwald step rule. Grain growth does not occur until the
equilibrium phase assemblage has been established. The separation
of grain growth from densication and phase transformation has
implications for preparing Si3N4-based nanoceramics and permits to
further study the kinetics of grain growth in Si3N4-based ceramics.
Isothermal deformation by SPS-pre-prepared, fully densied
ceramics performed at temperatures greater than or equal to
1450 8C yielded strain rates in the order of 102 s2 [593]. It was
suggested that a high heating rate promotes material transport via
formation of a non-equilibrated oxygen-rich liquid of low viscosity.
a-Sialon solid solutions with formula MxSi12(m+n)Alm+nOnN16n
(M = Ce, La, Sr and Eu) have been fully densied at 1500 8C (200 8C/
min heating rate) at 50 MPa [582]. Prolonged heat treatment at
1700 8C or above made a-sialon decompose into b-sialon and
various nitrogen rich phases. Ce3Si8xAlxN11xO4x with x = 1.75 and
Ba2AlxSi12xN16xO2x with x = 2.0 were prepared by SPS starting
194 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
from appropriate powder mixture of Si3N4, AlN, Al2O3 and
Ce2(CO3)3/BaCO3. SPS process was conducted at 14001600 8C
(200 8C/min heating rate) under a pressure of 50 MPa. Full dense
compacts were obtained, and the main part of Si3N4 and AlN was
retained after sintering. Oxide reactants formed an homogeneously
distributed liquid/glassy phase.
New types of tough a-SiAlON ceramics have been produced by
SPS, and their wear properties assessed through block on ring wear
tests under dry conditions [594]. The microstructures of the
samples, tailored by adjusting chemical compositions and/or
exploiting grain growth kinetics, ranged from equiaxed to coarse
elongated a grains. It is also shown that the coarse-grained
elongated a material showed good wear properties over a wide
range of loads.
By SPS and post-sintering thermal treatment at 1700 8C for 7
and 17 h, respectively, the infrared transmissions of Dy-a-sialon
(with three compositions, Dy0.33Si9.3Al2.7O1.7N14.3, Dy0.4Si10.2A-
l1.8O0.6N15.4 and Dy0.67Si9Al3O1N15), in 15004000 cm1 wave
number (6.62.5 mm) regions were investigated by Su et al. [595].
Results showed that the second crystallized phase, the sizes of a-
sialon grains, the distribution of cations in the grains, and the
existence of holes on the surface of ceramics mainly affected
infrared transmittance of Dy-a-sialon.
A single-phase b-sialon nanoceramic, Si5AlON7, has been
prepared by high-energy mechanical milling, followed by SPS
[596]. After milling, the starting powder mixture (Si3N4, AlN,
Al2O3) was mostly transformed into an amorphous phase that
contains a large number of well-dispersed nanocrystalline b-Si3N4
particles. Milling improved the sintering ability of the starting
powders, so that the densication temperature was lowered of
about 100 8C, compared with that for as-received powders. Particle
rearrangement was the main densication mechanism for the
milled powders. An homogeneous microstructure composed of
equiaxed b-sialon grains with a diameter of about 50 nm was
obtained after sintering at 1550 8C for 5 min.
By applying SPS technique, new Yb a-SiAlON ceramics in situ
toughened by rod-like grains were prepared at a relatively low
temperature of 1600 8C, with addition of combustion synthesized
seed crystals [597]. It was shown that Yb a-SiAlON ceramics could
be almost fully densied quickly by SPS, and the fast heating rate
was helpful to reduce the amount of intermediate phases. It was
also demonstrated that the added seed crystals played an
important role in enhancing the phase transformation and
facilitating the growth of rod-like grains.
a-sialon (m = 1.35, n = 0.675) ceramics were prepared by high-
energy mechanical milling followed by SPS [598]. The milling
promoted not only liquid-phase sintering, but also phase
transformation from b-Si3N4 to a-sialon. Under the same holding
time of 5 min, milled powder could be completely densied at
1500 8C, which is about 250 8C lower than that required for as-
received powder. The temperature where the phase transforma-
tion nished was 1600 and 1750 8C for milled and as-received
powder, respectively. Nano-sized dense ceramics have been
obtained by sintering the milled powder at 1500 8C for 5 min.
a-Sialons, with varied chemical compositions and starting
precursors, were sintered in SPS furnace by Salamon et al. [599]
to verify the inuence of electrical conduction, mechanical
pressure and heat transfer efciency.
b-SiAlON nanoceramics were fabricated from b-SiAlON nano-
powder using SPS [600]. The heating rate for SPS was 50 8C/min.
The b-SiAlON nanoceramics had high strength (500 MPa). TEM
observation showed that the intergranular glassy phase was
scarcely present at the grain boundary of the b-SiAlON nano-
ceramics. It was found that b-SiAlON nanoceramics have much
higher corrosion resistance than commercialized silicon nitride
ceramics in acid solutions. Commercialized Si3N4 ceramics have an
intergranular glassy phase created as a result of the sintering aids
in them. Thus, they were easily corroded by acid solutions because
the intergranular glassy phase is easily corroded under such
conditions on the contrary, the excellent corrosion resistance of the
b-SiAlON nanoceramics stems from their glass-free grain bound-
aries. b-SiAlON nanoceramics were produced without using a
sintering aid.
SPS of TiN/Y-a-sialon particles produced composite ceramics
with continuous TiN networks at 1400 8C, but with TiN grains
isolated in elongated b-sialon grains at 1600 8C [601]. The
electrical resistivity range from 104 to 100 V cm for the ceramics
sintered at 1400 8C, but increased to 101 and 105 V cm at
sintering temperatures 1500 8C. It was found that the complete
transition to b-sialon increased the resistivity to 103 to 105 V cm,
due to the breaking up of the continuous TiN layers by elongated b-
sialon grains.
Powder samples of sialon Ba S-phases Ba2AlxSi12xN16xO2+x (x
approximately equals to 0 and 2) and an S-phase with 10% of the Ba
atoms substituted by Eu atoms (x approximately equals to 2) were
prepared by SPS and post-heat treatment at 1600 8C for 15 h [602].
The S-phases were studied by 29Si and 27Al magic-angle spinning
NMR and the results were discussed in relation to proposed
distributions of Si/Al and O/N atoms in the structure.
Monophase magnesium aluminum oxynitride (MgAlON) with-
out pores was easily obtained (from MgO, alumina and AlN at
molar proportions 4:13:3, respectively) by SPS at 1700 8C under a
pressure of 30 MPa [603]. By performing specic oxidation tests of
the MgAlON plates prepared by SPS, it was found that a detectable
mass gain of the plates could not be obtained below 1200 8C,
because the oxidation was very low and occurred only on the
surface.
2.9. Ceramicmetal and ceramicintermetallic composites
2.9.1. Cemented carbides
Due to their practical importance, cemented carbides based on
WCCo with different binder content and with micro- or
nanograined WC are among the most investigated systems by
electric current activated sintering.
The direct resistance method using a pulse current process was
for instance adopted by Moriguchi et al. [604] for the sintering of
WCCo with ne grain size. It was observed that through this
method the addition of VC as grain growth inhibitor, often
employed in conventional sintering, can be avoided thus
improving mechanical properties such as transverse rupture
strength.
Using a pulsed current activated sintering system (Eltek Co.,
Republic of Korea), the densication of WCx wt.%Co (x = 0, 8, 10,
12) hard materials was obtained starting from ultra-ne powder of
WC and WCCo (grain size equal or less than 0.4 mm) [605]. Nearly
full dense products (relative density up to 99.2%) were obtained
with simultaneous application of 60 MPa and 2800 A DC within
2 min, without signicant change in grain size.
The synthesis and simultaneous consolidation of WCx vol.%Co
(5  x  20) composites, with WC grain size less than 1 mm, was
performed by FAPACS starting from elemental powders [606]. The
operating processing parameters used during the FAPACS process
were an electric current of 3000 A, a voltage of 18 V, 1200 8C/min
heating rate, 600 8C/min cooling rate, 34 min duration. The
density of the nal product depending on the Co content was
always higher than 98% of the theoretical value. The single-step
synthesis and densication of the WC6 wt.%Co cemented carbide
starting from elemental powders was carried out by the SPS
technique [607]. A systematic study regarding the effect of the
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 72. Relative amount of the different phases detected in the WC-Co SPS products
as a function of the time interval during which the pulsed electric current is applied
(I = 800 A, P = 40 MPa). Adapted from Locci et al. [607].
electric current level (600900 A) and the processing time (0
10 min) on the synthesis/consolidation process and product
characteristics was performed. Consequently, the operating con-
ditions, which guarantee the complete conversion of the reactants
to the desired full-dense material, were identied. Specically,
under the application of 800 A and a mechanical pressure of
40 MPa for about 200 s, a product with relative density higher than
99%, hardness of 14.97  0.35 GPa, and 12.5  1.0 MPa m0.5 fracture
toughness, was obtained. A kinetic investigation of the SPS process
was also performed. Quantitative insights on the evolution of the
reaction synthesis during SPS can be gained by examining the results
shown in Fig. 72, where the relative amount of each phase involved
in the process is reported as a function of the time interval during
which the pulsed electric current is applied. It is apparent that an
intermediate phase, i.e. W2C, is the rst carbide formed during the
carburization process.
It was also observed that the synthesis and sintering stages take
place simultaneously, as it may be seen in Fig. 73 where the
evolution of densication phenomena during the synthesis process
by SPS is reported. It was also found that as the applied pulsed
current intensity was augmented, the required synthesis/sintering
time decreased signicantly when operating at low current levels.
Fig. 73. Densities of WC-Co end-products obtained by SPS as a function of the time
interval during which the pulsed electric current is applied (I = 800 A, P = 40 MPa).
Adapted from Locci et al. [607].
195
Table 3
Properties of WC6.29Co cemented carbide prepared by different processes.
Adapted from Shi et al. [608].
SPS SPS with HIP Vacuum Vacuum
with HIP
Theoretical density (%) 99.1 99.0 97.7 98.8
Average grain size (nm) 350 400 700 800
TRS (MPa) 1220 2740 1800 2260
Rockwell A hardness (HRA) 94 93.8 93.2 93.1
Saturation induction (%) 75 90 83 94
Magnetic coercivity (kA/m) 47.2 44.4 43.8 41.5
The fabrication of dense WC6.29Co nanocrystalline composite
by SPS, employed either alone or in combination with HIP, was
investigated using powder prepared by spray thermal decom-
position-continuous reduction and carburization technology
[608]. For the sake of comparison, the same powders were also
processed by vacuum sintering coupled with HIP. SPS experiments
were conducted at 1100 8C and 50 MPa for 10 min, while vacuum
sintering was performed at 1380 8C for 60 min. Both sintering
processes were followed by HIP at 1320 8C for 60 min. The best
results were obtained by SPS with HIP (cf. Table 3). Specically, in
this case a cemented carbide with 99.0% relative density, grain size
of about 400 nm, and characterized by relatively improved
mechanical properties, was achieved.
WC8Co nano-grained cemented carbide was sintered by SPS
[609]. Complete densication was obtained at 1150 8C, under
4.5 kN for 5 min. Final products were characterized by 200 nm WC
grains and 94.2 HRA hardness. For the sake of comparison, the
same powders were also processed by a normal vacuum sintering
process. In this case, sintering was carried out at 1400 8C for
30 min, and the resulting product had 300400 nm WC grains and
93 HRA hardness.
Various current activated sintering techniques were exploited
for the preparation of WC10Co cermets. For instance, the EDC
technique was used for the fabrication of WC10Co cemented
carbides with grain size as small as 120 nm, starting from powders
obtained by spray conversion process consisting of WC, Co and
Co3W3C and characterized by a an average grain size of about
50 nm [22,610]. The initial powders were subjected to an external
pressure up to 300 MPa and then discharged from a 360 mF
capacitor with an input energy of 3 kJ/g. The nal sample had a
density of approximately 95% and consisted of WC and Co only,
being the disappearance of the Co3W3C attributed to its
carburization with free carbon at the high temperature conditions
encountered during EDC.
WC-10Co was also manufactured by SPS using WC nanocrystal-
line powders (50120 nm), prepared by a combination of spray
drying and mechano-chemical processes, after mixing with Co
binder [611]. The consolidation by SPS was investigated at dwell
temperatures in the range 9001100 8C, heating rate of 100 8C/
min, holding time of 10 min, and under a pressure of 50100 MPa.
Full densication was obtained at 9501000 8C and the nal
product obtained under optimum consolidation conditions had a
grain size of about 300 nm (cf. Fig. 74).
The FAPACS technique was adopted for the preparation of WC
10Co cermet composites from reactants mixtures made of W, Co
and different carbon sources [612]. Experiments were conducted
using a 27 V, 3000 A DC system, under a uniaxial pressure of
60 MPa and had few minutes duration. The obtained product
consisted of WC and Co only and had a relative density higher than
99% of theoretical.
The addition of VC in WCCo cemented carbides was
investigated for the preparation of WC10 wt.%Co0.8 wt.%VC
starting from powders synthesized by mechanical alloying and
196 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 74. The variation of (a) relative density and (b) WC grain size in sintered
nanocrystalline and conventional WC-10Co powders when varying the SPS
temperature. Adapted from Cha et al. [611].
sintered by SPS at 1200 and 1300 8C under a mechanical pressure
of 30 MPa [613]. It was found that a nal product with 95.1% of the
theoretical density can be obtained at 1200 8C in 5 min, while
sample density is increased (97.7%) at 1300 8C for 3 min. For the
sake of comparison, the same powders were also subjected to
sintering in a conventional vacuum furnace at 1300 8C for 30 min
and the resulting density was only 92.8%. Moreover, the sample
prepared by SPS possessed higher hardness but lower fracture
toughness as compared to that consolidated in the vacuum
furnace.
The WC11Co cermet composite was fabricated by SPS starting
from nanopowders of WC (80 nm) and Co (60 nm) prepared by
Atomization Fabrication Techniques [614]. Sintering was per-
formed at different temperatures in the range 9001100 8C, while
maintaining heating rate (200 8C/min), heating time (5 min) and
mechanical pressure (25 MPa) constant. Full densication was
achieved at 1100 8C and the resulting product exhibited a WC grain
size of about 0.77 mm.
Nanocrystalline WC12 wt.%Co powders with WC grain size
within the range 4080 nm were consolidated by the pulse plasma
sintering method [46]. Sintering was performed at various
temperatures in the range 9001200 8C for 5 min under a pressure
of 60 MPa.
The samples sintered at 1100 8C had a relative density of about
98%, hardness of 2250 HV30, KIC = 15.3 MPa m1/2, and WC
crystallite size of about 50 nm. An augmentation of the sintering
temperature to 1200 8C results in the increase of the WC crystallite
Fig. 75. Average WC grain size in the PECS and pressureless sintered (CS) cemented
carbide grades. Adapted from Huang et al. [615].
size to about 110 nm, the hardness and KIC being decreased to 2200
HV30 and 11.9 MPa1/2, respectively.
An equipment (Type HP D 25/1, FCT Systeme, Rauenstein,
Germany) based on PECS method was employed for the
consolidation of WC12 wt.%Co cemented carbides doped with
0.9 wt.% VC, NbC or Cr3C2 as grain growth inhibitors [615]. Nearly
fully densied cemented carbides either undoped or doped were
obtained at 1240 8C for 2 min, while the process was governed by a
solid-state mechanism. The microstructure and properties of the
PECS material were compared with those of liquid phase sintered
at 1420 8C for 1 h. It was found that the PECS technique is very
efcient to limit grain growth of undoped WCCo cermets when
compared to conventional liquid phase sintering (cf. Fig. 75).
Ball milled WC12Co powders with a grain size of 40250 nm
and different content of VC and (VC + Cr3C2) were densied by SPS
[616]. SPS consolidation (Dr. Sinter 1050) was performed in the
temperature range 10001100 8C for 310 min, heating rate of
about 150 8C/min, under a pressure of 50 MPa. Liquid phase
sintering consisting of heating to 900 8C at 10 8C/min, holding for
30 min, heating to 1300 8C at 5 8C/min, followed by heating at a
rate of 20 8C/min to nal sintering temperature (1400 and 1450 8C)
which was maintained for 3045 min, was also carried out. Full
dense samples were obtained in 10 min by SPS at a temperature of
1100 8C. In contrast, a high sintering temperature of 1450 8C
(45 min) was necessary to obtain similar density via liquid phase
sintering. Grain size was comparable in the two cases. Cobalt
distribution was found to be more uniform using SPS than in liquid
phase sintering. Correspondingly, higher hardness but lower
fracture toughness was obtained in SPS (cf. Fig. 76).
The current activated sintering equipment was also used for
some other peculiar applications dealing with the WCCo system.
For instance, SPS was applied as a post-spray heat treatment to
reinstate the WC phase in plasma spray WC/Co coatings, since
decarburization of WCCo is a phenomenon commonly observed
during spraying deposition [617,618]. The SPS post-spray treat-
ment, which is schematically represented in Fig. 77, was carried
out at 800 8C for 5 min. Specically, results showed that treatment
by SPS (model 1050), with the graphite punch directly in contact
with the coating surface, was capable to restore the WC phase to
approximately 52.3 wt.% of the overall phases in the coating. This
values is close to the amount of WC found in the original WCCo
feedstock used in the coating [617].
The SPS technique was also used to prepare diamond-enhanced
ultra-ne WC10Co cemented carbide composites, which combine
high abrasion resistance and hardness of the former one with good
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 76. Comparison of (a) hardness (HV30) and (b) fracture toughness (KIC) as a
function of VC addition in WC-Co products obtained by SPS and conventional
sintering (CS). Adapted from Sivaprahasam et al. [616].
toughness of WCCo [619,620]. The starting powders, produced by
spray pyrolysis-continuous reduction and carbonization technol-
ogy and diamond coated with tungsten by vacuum vapor
deposition and uncoated diamond, were consolidated by SPS
3.20 model for 3 min at 1000, 1100, and 1280 8C, under a pressure
of 30 MPa. It was found that the SPS product consisted of well
chemically bonded phases and there were almost no gaps between
diamond and matrix. However, the temperature of 1280 8C was too
high since the diamond was thermally damaged, thus deteriorating
the properties of the diamond-enhanced WCCo material ser-
iously.
The inuence of the incorporation of carbon nanotubes (CNTs)
in cemented carbides was also studied during the consolidation by
Fig. 77. Preparation of the sample-die set for the SPS post-spray treatment. Adapted from Yu et al. [617].
197
SPS of WC10Co0.5 wt.%CNTs composites [621]. It was found that
CNTs could preserve their tubular structures under the experi-
mental conditions encountered in the SPS equipment, have a
retardation effect on WC grain growth, and lead to a composite
product with superior hardness to toughness combination as
compared to pure WC10Co cermets.
The SPS apparatus (model 1050) was also employed for the
sintering of WCCo/TiCAl2O3 composites using coated particles
obtained by high speed rotational impact blending machine,
starting from WC coarse particles, Co as binding phase, and TiC and
Al2O3 as ne coating particles [622]. Consolidation experiments
were performed at different sintering temperatures in the range
13801680 8C for 5 min, under a pressure of 50 MPa. The
microstructure of the obtained products was deeply investigated.
Specically, it was found that a more uniform dispersions of WC
and Al2O3 grains were obtained at low sintering temperature to
yield higher strength, while the TiCWC phase was dispersed
uniformly at the high temperature to yield higher hardness.
The preparation of the WCNi cermet composite, among the
most interesting cemented carbides, was widely investigated using
the FAPACS technique [612,623,624].
Mixtures of W, carbon black and Ni were subjected to FAPACS
using high DC current and mechanical pressure (3060 MPa) for
the fabrication of dense WC10Ni composite [623]. In some
experiments, a pulsed current (30 V, 750 A, onoff duration of
30 ms, total duration 30900 s) was rst applied, followed by the
imposition of a second high current in the continuous mode (18 V,
20003000A, duration 1.530 min, heating rate 8001200 8C/min,
maximum temperature 1200 8C). Under these conditions, a
reaction is initiated by eld activation and completed within a
short period of time. For sample with too short duration of pulse
current, the nal density was smaller than that without pulse
stage. However, product density with the imposition of a pulsed
current was increased as the pulsing time was augmented (cf.
Fig. 78). Increasing the pressure from 30 to 60 MPa resulted in a
large increase of nal density. At last a 99.2% dense WC10Ni
composite with fracture toughness and hardness of 5.9 MPa m1/2
and 1424 kg/mm2, respectively, was obtained. The same authors
replaced the black carbon used in the previous investigation with
activated carbon [612] and the obtained product exhibited a
fracture toughness and hardness of 7.8 MPa m1/2 and 1287 kg/
mm2, respectively. The same process was utilized to produce WC
CoNi composites from reactant mixtures of W, C, Co and Ni [625].
The synthesis/consolidation process was performed using high
current (18 V, 3000 A, duration 3 min, heating rate 1200 8C/min,
maximum temperature 1250 8C) and pressure (60 MPa) and led to
a product with relative densities ranged from 97.7 to 99.3% and
Vickers microhardness measurement (at 50 kg force) from 15.28 to
18.99 GPa.
Using a pulsed current activated sintering apparatus (Eltek Co.,
Republic of Korea), the densication of WCxNi (x = 0, 8, 10,
12 wt.%) hard materials was accomplished starting from ultra-ne
198 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 78. Effect of different duration of pulse current on the relative densities of the
WC-Ni samples obtained by FAPACS. Adapted from Jiang et al. [623].
powder of Ni (6080 nm) and WC (0.4 mm) [55]. Products with a
relative density of up to 97.6% were obtained with the
simultaneous application of 60 MPa pressure and electric pulsed
current (2800 A, 18 V, heating rate of about 1400 8C/min) within
2 min without a signicant change in WC grain size (350 nm). The
comparison of mechanical of WCNi sintered in this study with
previously reported values related to conventional techniques
showed that those obtained by the current activated method were
relatively higher.
Another promising cemented carbide system, the NbCCo, was
recently investigated taking advantage of a pulsed electric current
activated equipment (Type HP D25/1, FCT Systems, Rauenstein,
Germany) [626]. NbCxCo (x = 8, 12, 18, 24.5 wt.%) powder
mixtures with particles size of 1.18 and 0.5 mm for NbC and Co,
respectively, were consolidated in 2 min at 12001280 8C and 30
60 MPa. Specically, the NbC12 wt.%Co powders were fully
consolidated (relative density of about 99.1%) in 2 min at
1280 8C under a pressure of 60 MPa with limited NbC grain
growth (cf. Fig. 79).
Another very promising application of electric current activated
devices in the eld of cemented carbides is represented by the
fabrication of dense diamond/cemented carbide, capable to
combine the performance and properties similar to those of
diamond and the low cost of cemented carbides. A PECS equipment
Fig. 79. Microstructure of the NbC12Co cermet grade; powder compact (a) and sintered at 1200 8C (b); 1240 8C (c) and 1280 8C (d). Adapted from Huang et al. [626].
was recently employed to this aim by Moriguchi et al. [627]. In
particular, to prevent the graphitization of diamond, diamond
particles were rst coated with SiC, mixed with WC and Co
powders, with a ratio of WC10 wt.%Co, and then sintered by PECS
(maximum temperature 1300 8C, heating rate 6 8C/min, holding
time 3 min, and mechanical pressure 41 MPa). The diamond
content was 20 vol.%. After sintering, no graphitization of diamond
was conrmed by microstructure observation and Raman
scattering analysis. These obtained material was composed of
diamond and cemented carbide, and exhibited a 50% larger
fracture toughness and 10 times better wear resistance compared
with conventional cemented carbides, as well as ve times better
machinability compared with diamond compacts (cf. Fig. 80).
2.9.2. Other carbides, nitrides and boridesmetal/intermetallic
composites
TiC20 mass%Ni cermet composites containing ultra-ne TiC
particles were obtained by pulsed-current sintering [628]. Mechani-
cally alloyed Ti, graphite, Ni composite powders were consolidated
at 1223 K under 70 MPa pressure. The sintered compact consisted of
TiC and Ni with average grain size of TiC particles of about 0.80 mm.
The relative density and Vickers hardness of the sintered compact
were about 92% and 2260 HV, respectively.
TiC reinforced Fe28 at.%Al intermetallic composites were
manufactured in situ by pulse discharge sintering starting from
mechanical alloyed Fe, Al, Ti and graphite powders [629]. Pulse
discharge synthesis/consolidation was carried out at 1273, 1373
and 1473 K, under an applied pressure of 55 MPa, 20 K/min heating
rate and 10 min holding time. During sintering, Fe3Al and TiC
precipitated from the supersaturated Fe solid solution containing
Al, Ti and C. Microstructure of the sintered product obtained using
powder milled for 200 h consisted of three regions, that is, large TiC
particles of about 5 mm in size, Fe3Al matrix with TiC particles of
submicron size and particle-free Fe3Al region. For the sintered
body after milling of 400 h, however, the large TiC particles dis-
appeared due to the complete solid solution during mechanical
alloying. Sintering of the powders milled for the period shorter
than 50 h formed intermediate phases, such as Al5Fe2, Al3Ti and
Fe3AlCx, by heat treatment up to 1273 K, while that of the powder
milled for 400 h showed direct precipitation of Fe3Al and TiC from
the supersaturated Fe solid solution.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 80. Wear resistance and machinability of a conventional cemented carbide, a
diamond compact and a diamond/cemented carbide with 816 mm SiC-coated
diamond particles sintered by PECS. Adapted from Moriguchi et al. [627].
TiC/Ti and TiC/Ti15Mo cermet composites were prepared by
SPS for the bearings of joint prostheses [630]. It was found that,
when the volume fraction of the metal phase was increased, the
fracture toughness and the bending strength increased for both
systems. The TiC/Ti and the TiC/Ti15Mo cermets showed high
biocompatibility and corrosion resistance.
TiB particle reinforced titanium metal matrix composites were
synthesized in situ and simultaneously consolidated by SPS using
mechanically alloyed Ti, and TiB2 powders [631633]. One step
reaction and densication was performed using the SPS-2050
system apparatus at various temperatures in the range 800
1200 8C, under an applied pressure of 20 MPa, 5 min holding time,
Fig. 81. SEM micrographs of the TiTiB composite sintered at: (a) 600 8C; (b) 800 8C; (c) 1000 8C and (d) 1200 8C. Adapted from Feng et al. [633].
199
and with a heating rate of 50 8C/min. The obtained SPS product
consisted of TiB whiskers uniformly dispersed in the titanium
matrix (cf. Fig. 81).
The composite sintered at 1000 8C had the maximum value of
relative density (99.6%), and good mechanical properties with a
exural strength of 1007 MPa, Youngs modulus of 146 GPa and
fracture toughness of 8.64 MPa m1/2, respectively (cf. Fig. 82).
Analogously to the procedure reported above, the same authors
investigated the in situ fabrication of TiB/Ti4.0Fe7.3Mo compo-
sites via SPS technique using mechanical alloyed Ti, Fe65Mo and B
powder [634]. A systematic study of the effect of sintering
temperature in the range 6001200 8C on densication of the
composites and microstructure of the in situ synthesized TiB was
investigated. The mechanical pressure and holding time were kept
constant to 20 MPa and 5 min, respectively. An in situ TiB
reinforced Ti4.0Fe7.3Mo composite with relative density
exceeding 99% was obtained after sintering at 1000 8C for 5 min.
The matrix of the composite consisted of both a-Ti and b-Ti
phases. The size of the synthesized TiB grains rapidly increased
when the sintering temperature was increased.
A TiB25 vol.%Ni composite was fabricated using pulsed plasma
sintering by processing Ti, B and Ni powders [41]. The samples
were rst heated in a pulsed way at 600 8C for 3 min and then
sintered at three different temperatures: 1300, 1250 and 1150 8C,
under a load of 60 MPa for 10 min. The electric pulses, dissipating
the energy E = 8.1 kJ in each cycle, were applied at every second
during the whole sintering process. An SHS reaction was observed
to occur during the process. The material obtained was a composite
99.8% dense that contained the desired TiB2 and Ni phases.
Microscopic examinations have shown that nickel occurs at the
boundaries of the TiB2 grains, where it forms a thin lm, and also
appears in the form of small agglomerates (cf. Fig. 83). The
hardness of the composites was about 2500 HV1.
The SPS apparatus was also used for consolidating nanocom-
posite CuxTiB2 (2.5  x  60 wt.%) powders (TiB2 particles
smaller than 250 nm) obtained by SHS using mechanically
200 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 82. Variation of relative densities and mechanical properties of the TiB particle
reinforced titanium metal matrix composites with sintering temperature. Adapted
from Feng et al. [633].
activated Ti, B, and Cu powders eventually diluted with Cu to
obtain the desired compositions [635,636].
The applied pressure and temperature during SPS experiments
were 5070 MPa and 500950 8C, respectively, while the holding
time at the nal temperature was varied in the range 030 min.
Product density and Vickers hardness values were found to
increase as temperature, holding time and SPS pressure were
augmented. In particular, for the case of the Cu60 wt.%TiB2 the
maximum values obtained, i.e. 93.9% density and 673 HV,
corresponded to 950 8C, 70 MPa, and 30 min. The resulting
product consisted of a ne-grained skeleton of TiB2 interpene-
trating the Cu matrix.
Intermetallic matrix composites of Fe28 at.%Al containing 0, 5,
15, and 25% volume of TiB2 particles were fabricated in situ by a
PDS process starting from Al, Ti, and B mechanically alloyed
Fig. 83. SEM micrograph of TiB2/Ni composites. Adapted from Jaroszewicz and
Michalski [41].
powders [637]. Sintering was performed at 1100 8C for 10 min
under a continuous pressure of 30 MPa. During the PDS process, a
Fe3Al matrix and TiB2 particles were successfully synthesized in
situ. A nearly homogeneous particle distribution was achieved
through the PDS process. The tensile properties of the composite
had improved tensile strength.
Pulsed-current sintering was employed for the synthesis of
TiB2FeAl cermet composites consisting of titanium boride and
iron aluminide intermetallic compound [638]. The starting
mixture was obtained by mechanically alloying TiB2 and Fe
powders, and subsequently mixing Al to satisfy the nominal
compositions TiB220 mass%Fe3Al and TiB224 mass%FeAl. Sev-
eral iron aluminide intermetallic compounds were generated
during sintering in the TiB220 mass%Fe3Al. Therefore, the TiB2
20 mass%Fe3Al compact was hard and brittle. However, the TiB2
24 mass%FeAl sintered sample consisted only of TiB2 and FeAl, and
shows better ductility.
A bulk nanocomposite in the TiAlB system was produced after
consolidation by SPS of nanopowders obtained through mechanical
activation of elemental powders [639]. Three different Ti/B/Al
compositions, i.e. 0.9:0.1:2.0, 0.7:0.3:2.0, and 0.5:0.5:2.0, were
considered. SPS was performed at 1400 8C under 60 MPa in vacuum
for 4 min. SPS products consisted of TiB2 particles with 1030 nm
grain size with an amorphous phase of Al and unreacted Ti and B
localized at the grain boundaries. The sample obtained using the
(0.7:0.3:2.0) composition had the highest relative density (98%) and
bending strength (846.9 MPa), while the highest hardness
(19.6 GPa) was obtained with the (0.9:0.1:2.0) composition.
AlNxCu powder composites (x = 40, 60, 80 vol.%) obtained by
mechanically alloying of Cu and AlN were recently consolidated
using a PECS equipment (Izumi Tech, Japan) [640]. Sintering was
carried out at 50 MPa, 200 K/s heating rate, 900 8C of sintering
temperature, 5 min sintering time. The obtained products were
characterized in terms of thermo-mechanical properties, i.e.
coefcients of thermal expansion (CTE) and thermal conductivity
(TC), in view of possible applications as heat sink material. It was
found that CTEs exhibited good consistency with Turners model
when the volume fraction of Cu was less than 60%, even in presence
of a certain amount of pores. On the other hand, when Cu content
was more than 60%, the values of thermal expansion were in
agreement with the rule of mixtures. The porosity compensated
TCs of AlN-40, 60, and 80 vol.% Cu measured at 200 8C were 62.7,
82.2, and 95.1 W/(m K), respectively.
Ultra-ne dense Ti(C,N)-based cermet with designed chemical
composition of TiC23TiN11.28Mo0.72C12Ni (wt.%) was pre-
pared by SPS [641]. SPS was conducted using a Dr. Sinter 1050 SPS
system at a temperature in the range 10501430 8C, 8 min
dwelling time, 200 8C/min heating rate and under an applied
pressure of 30 MPa. It was found that SPS, in comparison with
conventional vacuum sintering, remarkably accelerated phase
transformation and decreased the end temperature of some phase
transformations.
A comparison between SPS and conventional vacuum sintering
(VS) to fabricate ultra-ne Ti(C,N)-based cermets was analyzed by
these authors [642]. SPS was carried out in vacuum (5 Pa) using a
Dr. Sinter 1050 SPS apparatus, the heating rate was maintained at
200 8C/min, a pressure of approximately 30 MPa was applied, and
the sample was heated to the maximum sintering temperature
(12501350 8C) for 8 min. It was observed that the shrinkage
process occurred mainly in the range of 10001300 8C during the
VS process, and only a 0.2% linear shrinkage ratio appeared below
800 8C, while during the SPS one, a 60% dimensional change
occurred below 800 8C.
More recently, other Ti(C,N)-based cermets, specically the
33TiC23TiN32Ni16Mo6.9WC1.5C0.6Cr3C2 (wt.%) with TiN
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 201

and TiC, either micro- or nano-sized, additions, were investigated

using the SPS by the same authors [643]. Sintering was performed
at 1623 K, 3 min holding time, 300 K/min heating rate, and 20 MPa
pressure. It was found that the SPS samples contained many grains
with the typical corerim structures, which were believed to be
formed by Ostwald ripening mechanism. The grain size was found
to reduce with increasing nanoscale-sized additions. The cermet
with all the ceramic powders being nanoscale-sized structure
contained several small grains, the sizes of which were less than
100 nm, besides some larger grains with about 200300 nm size.
Moreover, when the cermets were sintered by SPS, the addition of
nanopowders could considerably improve the mechanical proper-
ties of the cermets.
The consolidation of Ti(C,N)-based cermet by electric current
activated sintering was also obtained from Ti(C0.5,N0.5)Mo2CNi
and Ti(C0.5,N0.5)Mo2CNiTiAl3 powder mixtures [644]. Sintering
(HPD 200/180, FCT) was performed under a maximum pressure of
100 MPa, 100 8C/min heating rate, sintering temperature ranging
from 1250 to 1400 8C. Typical electric current values, which was
applied in the form of pulses with duration of 10 ms and pauses of
5 ms between them, were from 3500 to 4000 A. Sample porosity was
found to decrease as the temperature was augmented reaching a
minimum value of 0.5 vol.% at 1370 8C. The Ti(C0.5,N0.5)Mo2CNi
alloy presented signicant exudation of the liquid phase through the
clearance between SPS punches and die. However, this phenomenon
was almost negligible when adding TiAl3. The presence of ultra-ne
Ti(C,N) grains along with the relatively tough behavior of the binder
phase led to a combination of hardness and toughness (HV10 over
18 GPa and KICS around 7.5 MPa m1/2) close to the range covered by
ultra-ne WCCo hard metals with similar binder content.
TiB2- and ZrB2-based cermets were sintered by SPS with 6 wt.%
Cu [645]. SPS experiments were carried out in the temperature
range 12001500 8C, with a heating rate of 500 K/min and holding
time ranging from 10 to 15 min. Maximum relative densities of
about 95% and 99% were obtained for ZrB2/Cu and TiB2/Cu,
respectively, when operating at 1500 8C for 15 min (cf. Fig. 84). Fig. 84. Plot of relative density vs. SPS temperature of TiB26 wt.% Cu (a) and ZrB2
While the optimized TiB2/Cu cermet displayed hardness and 6 wt.% Cu (b) cermets for various holding time at peak sintering temperature.
Adapted from Venkateswaran et al. [645].
fracture toughness of approximately 17 GPa and 11 MPa m1/2, the
ZrB2/Cu cermet had higher hardness of 19 GPa and fracture
toughness of about 7.5 MPa m1/2. High electrical conductivity of tively, the heating rate was set equal to 100 8C/min with 10 min
0.20 MV1/cm (TiB2/Cu) and 0.15 MV1/cm (ZrB2/Cu) were also holding time. In absence of bers, the Ti alloy was fully
obtained with the optimally sintered cermets. consolidated at 900 8C/60 MPa or 1000 8C/30 MPa. The titanium
Fine-grained, particle-dispersed Mo alloys were fabricated by matrix composite (TMC) material consolidated at 900 8C/60 MPa
SPS of mechanically alloyed powders of Mo and 0.8 mol% ZrC or exhibited the maximum tensile strength. The latter one increased
TaC [646648]. The fabricated Mo alloys displayed no signicant with SiC bers volume fraction up to 26%.
grain growth even after annealing at 2470 K for 3.6 ks due to the Mechanically alloyed and simply blended Nb and AlN powder
pinning effect of the particles against grain boundary migration. mixtures with global composition Nb8Al8N, Nb10Al10N, Nb
The ductile-to-brittle transition temperatures assessed by impact 12Al12N, Nb16Al16N, Nb22Al22N and Nb36Al36N (at.%),
bending were lower and the tensile strengths up to 1770 K were were sintered by the SPS process [216]. SPS runs were carried out
higher for the fabricated alloys than for recrystallized pure Mo. in a SPS-2050 apparatus at temperatures between 1623 and
Specically, for the fabrication of the molybdenum alloy dispersed 1973 K, under a pressure of 49 MPa for 5 min. All the NbAlN
with 0.8 mol% ZrC particles (2 mm), powders were pressed under dense compacts consisted of phases of the NbAl system in which
74 MPa, heated from room temperature to 2070 K (heating rate the Nb2N phase was dispersed.
2 K/s) and then maintained at this temperature for 10 min TiAl/Ti2AlC composites were produced by SPS technology from
[646,647]. The obtained SPS product exhibited much higher mixed powders of Ti, Al with 0, 7, 15 and 30 vol.% TiC [650]. SPS was
strength at room temperature (1.8 times larger) than pure Mo, performed at various temperatures in the range 8731423 K for
and showed a large elongation of 180% at 1970 K. The high 6 min and under a pressure of 30 MPa. The sintered products
toughness was attained for the Mo alloy fabricated by sintering mainly consisted of TiAl and Ti2AlC phases as a consequence of the
without additional hot working. These excellent properties of the reaction Ti + Al + TiC ! TiAl + Ti2AlC, which took place above the
particle-dispersed Mo are attributed to a very small grain size of melting point of Al and was completed between 1173 and 1423 K.
about 3 mm, and the uniform distribution of ZrC particles. Different microstructures, depending on the starting mixture
The consolidation process by SPS of a titanium alloy (Ti15V composition, were obtained. Specically, when 7 vol.%TiC was
3Cr3Sn3Al, wt.%) reinforced with SiC bers (up to about mixed in the starting powders, the produced Ti2AlC particles were
35 vol.%) was recently investigated [649]. The sintering tempera- uniformly dispersed in the TiAl matrix with the partial lamellar
tures and pressure were 8001000 8C and 3060 MPa, respec- structure containing g and lamellar phases (duplex structure).
202 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Conversely, while 15 vol.%TiC was added, the composites consisted
of interpenetrating networks of Ti2AlC and TiAl phases.
2.9.3. Ceramic particles reinforced metal matrix
One of the most investigated ceramic particles/metal system by
electric current activated sintering method is represented by the
SiCp/Al. In this context, mechanically alloyed Al and b-SiC particles
(0.385 mm average size) were consolidated by resistance sinter-
ing for the preparation of the AlxSiC (x = 1030 vol.%) composite
[651653]. In these studies the current was kept constant at
4000 A, the sintering pressure was varied in the range 67.5
337.5 MPa and the sintering time was varied from 1 to 25 AC
cycles, corresponding to (1/6025/60 s). The voltage across the
sample was found to be approximately constant during the
sintering process and the estimated specic energy input resulted
in the range 0.53.6 kJ/g. The effect of the sintering time was
investigated for the case of the Al30 vol.%SiC and when
P = 200 MPa. It was observed that the compact density increases
with increasing sintering time up to 1015 cycles (1/61/4 s) thus
reaching about 95% of the theoretical density and then decreases.
Both the compressive yield stress and the ultimate compressive
strength increases with sintering time, while fracture strain
exhibited a maximum at 15 cycles (1/4 s). Regarding sintering
pressure, it was found that both sintered density and fracture
strain increase with pressure but this effect decreases above
135 MPa. In contrast, this parameter has a little effect on
compressive strength. In general, a nearly fully dense product
with excellent compressive properties (i.e. 500700 MPa yield
stress, 600800 MPa ultimate strength, and 35% fracture strain)
was obtained by resistance sintering. Moreover, the composites
made from mechanically alloyed AlSiC powders exhibited good
thermal stability even after heating at 873 K for 120 h.
SiCp/Al composites with different SiC content (1030 wt.%) and
particle size (25, 1525, and 7085 mm), were fabricated by
combining mechanical alloying and spark sintering processes
[654]. Spark sintering was performed for a duration of 2 s with an
applied voltage of 4 V and a current of 3000 A. Fairly dense
structures (96.8  1.6% of theoretical values) were obtained by spark
sintering. The obtained SiCp-reinforced composites resulted more
wear resistant than the unreinforced Al sample. In addition, for a xed
size of SiC particles, wear resistance was found to increase with the
SiC content. On the other hand, for a xed content of SiC particles,
samples containing coarser particles were more wear resistant.
Along these lines, various volume fractions (3363 vol.%) of SiC
particles reinforced Al matrix composites were prepared by SPS
from a-SiC and Al [655,656]. The mixture was sintered using a SPS-
1050 system at temperatures in the range 550600 8C, heating rate
of 100 8C/min and 2050 MPa for 5 min. SiC particles resulted
Fig. 85. Microstructure of 46 vol.% SiCp/Al composite fabricated by SPS: (a) 200 and (b) 1000. Adapted from Yang et al. [656].
distributed homogeneously in the Al matrix (cf. Fig. 85). The
maximum densities of the obtained product was 99.7% and, as long
as the relative density was higher than 94%, the measured thermal
conductivities were all higher than 190 W/m K. A SiC particles
reinforced Al matrix composite, i.e. the 60 vol.%SiC30 vol.%Al
10 vol.%Si system, was also fabricated by SPS using a-SiC,
aluminum and silicon powders [657659]. A SPS-1050 system
was employed for sintering and the experimental conditions
adopted during sintering were characterized by a maximum
temperature of 550 8C, 50 MPa mechanical pressure and duration
of about 20 min. The maximum relative density achieved for
sintered compacts was 97.2%. The thermophysical properties, such
as TC and CTE of the obtained SPS samples were evaluated. In
particular, the measured TCs of the SiCp/Al composites fabricated
by SPS resulted higher than 195 W/m K.
Another interesting ceramic reinforced metal matrix system is
the Cu/SiCp. More specically, Cu25 vol.%SiC bulk composites
were obtained by SPS from Cu-coated b-SiC particles prepared
using an electroless coating process [660,661]. The average
diameter of b-SiC, copper, and coated particles were about 100,
47, and 270 nm, respectively. A SPS-2040 system was employed for
consolidation, using sintering temperatures in the range 450
800 8C, heating rate equal to 70 8C/min, the uniaxial pressure equal
to 50 MPa and holding time set to 5 min. During the SPS process,
the Cu2O, initially present in the coated particles along with Cu and
SiC (as a consequence of the instantaneous oxidation of Cu during
the coating process), rst reacted with the entrapped oxygen to
form CuO. Subsequently, the latter one decomposed at about
500 8C, i.e. 350 8C lower than conventional heating. It was found
that the optimal sintering temperature for improved hardness and
microstructure homogeneity was 730 8C. In particular, Vickers
hardness of the optimized product was about 1.4 GPa, i.e. much
higher than that of pure Cu (about 0.5 GPa).
A specic investigation was performed by the same authors to
investigate the role played by Cu2O on the interface behavior in
CuSiC composite obtained by SPS [661]. It was found that Cu2O
facilitates the physical wetting at the interface through the
formation of an amorphous intergranular phase and limits the
reaction between SiC and Cu, which leads to the degradation of SiC
reinforcements and the decrease in hardness of the composites.
Moreover, the fabrication of TiAl-containing dispersed particles
of SiC in 5, 10, and 15 mass% has been performed by SPS starting
from mechanically alloyed powders [662]. The obtained product
was characterized in terms of high temperature oxidation. It was
found that SiC additions decreased the oxidation rate and exhibited
a most pronounced effect for TiAl10 and 15 mass%SiC composites.
The inuence of SiC particles in protecting the intermetallic matrix
was deeply investigated. The obtained TiAl/SiCp composites were
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
considered to be one of the most oxidation-resistant TiAl alloys
developed.
2.9.4. Metalintermetallics and metalalloys composites
Various AlAl3Ti composites were fabricated by the PDS
starting from Al and Ti (0, 6.25, 9.40 and 12.5 mol%) powders
[663]. The PDS process was performed in vacuum under an applied
maximum pressure of 38 MPa. The powder compact was rst
subjected to a pulse current of 800 A for 30 s and, subsequently, a
direct current with superimposed pulse wave and load were
applied. It was found that a sintering temperature and time of
903 K and 1200 s, respectively, were sufcient to produce fully
dense composite with low Ti content while for the Al12.5Ti
composite longer sintering time was required. When Ti content
9.4 mol%, the resulting composite exhibited a Youngs modulus of
about 110 GPa and a reasonable ductility was maintained.
Composites consisting of Ti and Ti aluminides were fabricated
via SPS technique (Dr. Sinter SPS-1020 machine) by utilizing a
combustion synthesis reaction occurring at the interface between
Ti and Al foils [664,665]. The fabrication process involved two
processing steps. As schematically shown in Fig. 86, during the rst
one, stacking of foils consisting of 21 layers were heated to 1173 K
at a heating rate of 1.7 K/s, under a low mechanical pressure (about
2 MPa), to avoid the spillage of molten Al, followed by cooling to
ambient temperature. A combustion synthesis reaction took place
and a Ti-matrix composite containing porous Ti-aluminides was
obtained. In the second processing step, the composites were
heated again to 1173 K (1.7 K/s heating rate) under a pressure of
3 MPa. A soon as the temperature of 1173 K was reached, the
Fig. 86. Processing of composites consisting of Ti and Ti-aluminides using SPS process. Adapted from Mizuuchi et al. [664].
203
pressure was increased to 32 MPa and held for 10 min to let the
composite to be densied. The global process nally led to the
formation of multilayered Ti-aluminides between Ti foils, being
these Ti and Ti-aluminides densied and bonded to each other (cf.
Fig. 87). When the thickness of Al foils was increased, the layer of
Al3Ti formed in Ti-aluminides became thicker. The obtained
composite products resulted strong in tensile strength at room
temperature. Specically, the tensile strength and the elongation
of a composite produced using 0.04 mm thick Ti and 0.012 mm
thick Al foils was about 700 MPa and 3.5%, respectively, while they
were about 420 MPa and 2.6% when starting from 0.04 mm thick Ti
and 0.024 mm thick Al foils. This good ductility properties were
considered to avoid the propagation of numerous cracks emanat-
ing from the Ti-aluminides when reaching Ti layers.
Laminate type Ni-matrix composites containing Ni-aluminides
were fabricated by a SPS process starting from Ni and aluminum
foils alternatively stacked [666]. A SPS Dr. Sinter 1020 apparatus
was employed in the processing route, which involves more stages.
Firstly, the stack of foils were heated up to a given temperature in
the range 10731373 K with a heating rate of 1.7 K/s, and under a
mechanical pressure of 2.7 MPa, to give a Ni-matrix composite
containing porous Ni aluminides. Subsequently, the pressure was
increased to 32 MPa and the sample held for 600 s.
The composites possessed laminated structure composed of Ni
and reacted layers containing Ni-aluminides (cf. Fig. 88). The
composition of the reacted layers was dependent on the reaction
temperature employed. Results obtained in tensile testing at room
temperature revealed that the reaction temperature affects
effectively the mechanical properties of the SPS composites,
204 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 87. SEM micrographs and X-ray dot mappings of Al and Ti elements taken from SPS-processed composites fabricated from 0.04 mm thick Ti foils with 0.012 (COMP12) (a
c) and 0.024 mm (COMP24) (df) thick aluminum foils. Adapted from Mizuuchi et al. [664].

Fig. 88. Microstructures of composites fabricated from 0.05 mm thick Ni foils with 0.012 mm thick aluminum foils at various temperatures by SPS process: (ad) low
magnication and (eh) high magnications at and near Ni-aluminides. Adapted from Mizuuchi et al. [666].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
including tensile strength, elongation and fracture mode. Speci-
cally, the tensile strength and elongation of composites fabricated
at 1373 K from 0.05-mm-thick Ni and 0.012-mm-thick Al foils
were 500 MPa and 3.8%, respectively.
The SPS equipment was recently employed to develop a
multiferroic type composite actuator, which combined the
magnetostriction properties of Ni matrix and the superelastic
characteristics of TiNi alloy ber llers [667]. As a matrix and
ller starting materials Ni powders and Ti51.2 at.%Ni wires
were utilized, respectively. SPS experiments were conducted
under a pressure of 300 MPa, 773 K sintering temperature,
20 min sintering time. The amplication effect of about a
maximum of 1.5 times magnetostriction was veried in the
fabricated composite actuator.
SmCo5 + xFe (x = 0, 5 and 10 wt.%) nanocomposite powders
obtained by mechanical milling (1520 nm sized of the crystallites
estimated from XRD) were densied by means of the SPS technique
[668]. A magnetic eld of 2 T was applied to orient the milled
powders prior to SPS process. Consolidation was performed at
700740 8C sintering temperature, 5560 MPa mechanical pres-
sure, 5 min sintering time. The relative densities of samples
consolidated at 700 and 740 8C were less than 85 and higher than
95%, respectively. A typical TEM microstructure shown in Fig. 89
reveals that the sample consists of randomly oriented nanograins,
with an average grain size of 20 nm. Thus, the samples obtained
under the latter conditions were further characterized in terms of
magnetic properties. A maximum coercivity of 8.9 kOe was
achieved in SPS SmCo5 + 5 wt.% Fe sample. The exchange spring
interaction between the hard and soft magnetic phases was
evaluated and it was found that the sample containing 5 wt.% Fe
had a stronger exchange coupling between the magnetic phases
than that of the sample with 10 wt.% Fe.
TiNi SMA bers reinforced Mg alloy composites were fabricated
by SPS using Ti50.3 at.%Ni bers, as reinforcement, sandwiched
with AZ31 magnesium plates, as a matrix material [669]. As
schematically represented in Fig. 90, two Mg alloy plates with
20 vol.% of the TiNi bers were subjected to the SPS process under a
pressure of 32 MPa, 773 holding temperature, 1.7 K/s heating rate,
and 300 s total processing time. The corresponding maximum
pulsed current was about 1900 A. During the SPS process, the
thickness of the preform composed of Mg plates and TiNi bers
decreased rapidly at the temperature range 400650 K, resulting in
the bonding between the bers and the matrix plates. A reaction
occurred at the interface between Mg alloy plates and TiNi ber.
Reinforcement by TiNi ber was found to improve yield stress of
the AZ31 Mg alloy of about 55% at 373 K and 105% at 423 K.
Fig. 89. TEM micrograph of spark plasma sintered SmCo5. The inset shows
nanobeam diffraction pattern of the SmCo5 phase. Adapted from Rama Rao et al.
[668].
205
Fig. 90. Processing of TiNi shape memory alloy ber reinforced AZ31 Mg alloy
matrix composite by SPS. Adapted from Mizuuchi et al. [669].
An attempt to form Mg2Ni/LaNi5 composites by pulse-electric-
current-sintering using mechanical alloyed was made for utiliza-
tion of synergy effect to acquire both high hydrogenation capacity
(Mg2Ni) and ability to absorb/desorb (LaNi5) protium at relatively
low temperatures [670].
Amorphous Cu54Ni6Zr22Ti18/xNi composites (x = 0, 15, 35 vol.%)
produced by electroless coating of nickel on the amorphous
powder of Cu54Ni6Zr22Ti18 were subjected to spark plasma
sintering [671]. No specic details of the SPS conditions adopted
are reported. Main attention was focused on the deformation
behavior of the obtained composites, which was investigated at
temperatures in the supercooled liquid region.
2.9.5. Metalsilicides composites
Composite materials of a-Fe0.91Mn0.09Si2.5xCu (0  x
 2 mass%) with thermoelectric properties were produced by
SPS using commercially available Fe0.91Mn0.09Si2.5 and Cu as
starting powders [672]. The sintering process was performed
under 25 MPa and involved 4 thermal stages. In the rst one (600 s
duration) the sample was heated up to 1173 K and was maintained
for 60 s at this temperature (II stage). Then the temperature was
decreased down to 943 K in 180 s (stage III) and, nally, the sample
was annealed at 943 K for different holding times in the range 3.6
14.4 ks (stage IV). The thermoelectric properties of the obtained
products were investigated. Specically, it was found that the
optimal annealing conditions were at 943 for 3.6 ks when x = 0.5
mass% Cu.
Nbss/Nb5Si3 composites were synthesized by reactive spark
plasma sintering (RSPS) using mechanically alloyed Nb and Si
powders with average composition Nb16 mol%Si and average
particle size of 30 mm [673]. SPS experiments were performed at
different sintering temperatures in the range 14731973 K, under
a mechanical pressure of about 35 MPa, holding time to the
sintering temperature equal to 30 min, while non-isothermal
heating was performed in 2025 min. The sintered compacts
consisted of Nbss and Nb5Si3 and was characterized by equiaxed
grain microstructures and a nearly full density, when RSPS was
carried out above the melting point of silicon (about 1680 K). The
in situ composites obtained by RSPS exhibited large compressive
ductility at room temperature and considerably high strength at
elevated temperatures.
206 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 91. Microstructures of the Nb18 at.%Si alloy as fabricated by (a) HP at 1873 K
under 50 MPa for 4 h and (b) SPS at 1600 K under 30 MPa for 0.6 ks. Adapted from
Kimura et al. [674].
Dense Nb5Si3xNb composites (x = 090 mol%) were also
obtained by reactive sintering starting from a mixture of Nb and
Si and taking advantage of either the SPS or FAPAS apparatuses
[90]. Two types of samples, i.e. disks of 45 mm in diameter using
the more powerful SPS and smaller disks of 19 mm in diameter
employing FAPAS, were produced under different experimental
conditions. SPS experiments were performed under an applied
pressure of 26.4 MPa, sintering temperature of 1400 8C, heating
rate of 25 8C/min, holding time equal to 20 min. FAPAS samples,
subjected to a mechanical pressure of 78.6 MPa, were heated at
100 A/min to 1700 A, then held for a total time of 25 min before
natural cooling. A complete reaction with full densication was
obtained and densities as high as 99.9% were achieved.
The SPS technology was recently employed for the fabrication
of the NbNb5Si3 two-phases alloy (Nb-18 at.%Si) using Nb and
Fig. 92. Effect of sintering temperatures on microstructure of Nb/Nb5Si3 in situ composites obtained by SPS: (a) 1300 8C; (b) 1500 8C and (c) 1600 8C. Adapted from Chen and
Yan [675].
prefabricated Nb5Si3 powders [674]. Experiments were conducted
using the SPS-510A equipment at a sintering temperature of
1673 K for 0.6 ks, under 3050 MPa mechanical pressure. A
product with relative density of around 95% was obtained. By
considering samples obtained by HP (1873 K, 50 MPa, 4 h) when
starting from the same powders, it is shown that the SPS products
are characterized by more uniform two-phase microstructure with
respect to the alloy fabricated through HP (cf. Fig. 91), which tends
to provide higher elevated temperature strength.
Nb/Nb5Si3 in situ composites were successfully fabricated by
SPS using Nb and Si elemental powders as raw materials [675]. The
inuence of sintering temperatures on the microstructures of the
synthesized composites was investigated in the range 1300
1650 8C, by adopting a xed holding time of 10 min and an applied
pressure of about 35 MPa. The results showed that a critical
sintering temperature Tc (1400 8C) was identied during the
synthesis of Nb/Nb5Si3 composites by SPS. When sintering
temperature is lower than Tc, an intermediate Nb3Si phase is
produced, and the relative density of the samples is relatively low.
Only if the sintering temperature is higher than Tc, the
intermediate Nb3Si phase is eliminated, the Nb particles size
becomes ner (cf. Fig. 92) and desired Nb/Nb5Si3 composites up to
99.59% theoretic density is obtained.
A Ti matrix composite reinforced with dispersed Ti5Si3 particles
was obtained by SPS starting from Ti and SiO2 according to a
reaction Ti + SiO2 = Ti(O) + Ti5Si3 [676]. The effect of sintering
temperature in the range 8001200 8C on microstructure, bulk
density, fraction of spatial occupation and Vickers hardness was
studied systematically. At low sintering temperature, the synthesis
reaction resulted incomplete. Vickers hardness of the Ti5Si3/Ti
composite was found to increase with increase sintering tem-
perature, and it is remarkably larger than that of commercial pure
Ti. The bulk density and fraction of spatial occupation also
increases when temperature is augmented.
2.9.6. Oxides/metal or oxides/intermetallic composites
With the aim of improving mechanical properties of Al2O3, the
fabrication of dense composite where nano-sized metal particles
are incorporated into an Al2O3 matrix was also investigated by
taking advantage of electric current sintering apparatuses. Along
these lines, Al2O3/xCu nanocomposites (x = 510 vol.%) were
sintered by SPS (Model SPS-2040) at 11001400 8C for 5 min
under 50 MPa [677,678]. Starting mixtures to be processed by SPS
were obtained by rst ball milling Al2O3 and CuO powders and
then heat treating them in H2 to reduce CuO to Cu. The other SPS
parameters used during the sintering process were a pulse
frequency of 14 ms, 6:1 pulse onoff ratio, soaking temperature/
time 900 8C/5 min and heating rate of 100 8C/min. A nearly fully
dense composite (>97%) with nano-sized Cu particles uniformly
distributed and located on the grain boundary of Al2O3 matrix was
obtained (cf. Fig. 93). Moreover, enhanced fracture toughness
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 93. Typical TEM microstructure for Al2O3/5 vol.% Cu nanocomposite, sintered at
1250 8C. Adapted from Kim et al. [677].
(4.9 MPa m1/2, i.e. 1.3 times larger than that of monolithic Al2O3)
was produced by SPS at a temperature above 1250 8C, while a
sintering temperature above 1450 8C was required by hot pressing.
Following the approach above, high-density Al2O3/NiCo
composites were prepared [679,680]. Final products with ne
microstructure of NiCo dispersion with the average size of 90 nm
and high strength of over 1 GPa and hardness of 19 GPa were
obtained.
Al2O3/5 vol.%Ni nanocomposite materials were fabricated by
SPS (SPS-3.20 MK-IV) using a composite powder mixture prepared
by a solution chemistry route [681,682]. Sintering temperature
was investigated in the range 10001450 8C, while holding time
and applied pressure were maintained constant to 10 min and
30 MPa, respectively. The SPS product achieved 91% of the
theoretical density at 1300 8C while nearly full densication was
obtained at 1450 8C. Various microstructures (cf. Fig. 94) were
accomplished by properly controlling SPS temperatures and well
balanced mechanical and magnetic properties can be obtained.
The inuence of sintering temperature and holding time on the
properties of Al2O3/5 vol.%Ni composites prepared by SPS was also
recently investigated starting from ne composite powders
synthesized by a thermalchemical method [683]. Sintering
(SPS-2040) was performed under 15 MPa mechanical pressure
by heating the powder compact to 10001270 8C at a heating rate
of about 200 8C/min with 020 min holding time. The results
showed that the nickel phase was uniformly dispersed in an
alumina matrix. Alumina grain sizes were observed to augment
with increasing sintering temperature and holding time. The
relative density of the samples showed that, without holding time,
the composites fabricated by SPS could not be consolidated to
full density and 85.5% was the maximum value achieved. The
Fig. 94. Fracture surfaces of post-SPS Al2O3/5 vol.% Ni nanocomposite obtained at (a) 1300 8C and (b) 1450 8C. Adapted from Kim et al. [681].
207
Fig. 95. TEM image of Al2O3/5 vol.% Ni composite sintered by SPS at 1170 8C for
10 min. Adapted from Yao et al. [683].
composites were consolidated to 99.6% relative density at 1170 8C
for 10 min holding time, and grain size of Al2O3 was 0.51.0 mm (cf.
Fig. 95). The fracture toughness of dense composites was
3.84 MPa m1/2, higher than that of monolithic Al2O3 ceramics.
Nano-sized nickel dispersed Al2O3 composites obtained by a
soaking technique followed by a H2 reduction were subjected to a
sintering process by PECS also in presence of a-Al2O3 seeding
[684686]. Consolidation of the resulting composite (Al2O3/
3 vol.%Ni) was performed under 30 MPa in vacuum, in the sintering
temperature range of 13501550 8C with soaking time of 5 and
60 min. A nearly full consolidation was obtained at 1450 8C after
60 min soaking time or, when the temperature was increased to
1550 8C, the holding time required to be decreased to 5 min (cf.
Fig. 96). In addition, specimens with a-Al2O3 seeding or with
sintering additives improved their density. The maximum
strength was 984 MPa for samples sintered at 1450 8C and the
maximum fracture toughness was 5.5 MPa m1/2 for specimens
sintered at 1350 8C.
Dense Al2O3/0.6 vol.%Ni and Al2O3/(5.2 vol.%ZrO2 + 1.2 vol.%Ni)
nanocomposites were produced by SPS from composite mixtures
where nanometer-sized Ni particles (about 10 nm) were intro-
duced into the (Al2O3 + ZrO2) powders by using a coating
technique [687]. A Dr. Sinter 1050 SPS equipment was used for
208 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 96. Relative densities with sintering temperatures of aluminanickel
nanocomposites. Adapted from Leela-Adisorn et al. [685].
consolidation purposes under the following experimental condi-
tions: 12:2 pulse sequence, 30 MPa external pressure, 1350 8C
peak temperature, 130 8C/min heating rate, holding time in the
range 15 min. It was found that the density of the SPS Al2O3/
(ZrO2 + Ni) specimen increased from 96.5 to 99% as the processing
time was augmented from 1 to 5 min. The density of the Al2O3/Ni
product was also higher than 99%. It was observed that the
presence of Ni particles enhanced the grain growth of the
composites, while, as long as both Ni and ZrO2 were incorporated
simultaneously into the Al2O3 matrix, the coarsening of matrix
grains is constrained (cf. Fig. 97). It was also found that the strength
of the obtained Al2O3/(ZrO2 + Ni) nanocomposite was about 40%
higher than that of Al2O3 alone.
Additional experiments were conducted consisting of proces-
sing the powder mixtures mentioned above by SPS at 1350 8C for
5 min with a heating rate of 130 8C/min and 1300 8C for 5 min with
a heating rate of 200 8C/min [688,689]. From microstructural
observations, it was found that when the heating rate was set to
200 8C/min, the temperature at the edge of the sample was higher
than that at the center. The temperature difference was smaller for
the specimen prepared by the heating rate of 130 8C/min. Large
ZrO2Ni agglomerates were formed within the Al2O3 matrix after
sintering. Depending on the heating rate, these agglomerates
formed networks within the matrix. The networks were hetero-
geneously distributed in the specimens prepared by the heating
rate of 200 8C/min but homogeneously in the specimens prepared
by the heating rate of 130 8C/min. The small ZrO2 particles tend to
associate with nickel melt to form ZrO2Ni agglomerates. Then the
ZrO2Ni agglomerates were reported to migrate by magnetic eld
induced by the pulse electric current.
High-energy attrition-milled Cr50 vol.%Al2O3 and Nb
50 vol.%Al2O3 powder composites were used as starting material
for SPS consolidation [690]. A SPS-1020 apparatus was used by
setting the on/off pulse current mode to 12/2, the average
maximum current and voltage were about 2000 A and 5 V,
respectively, the sintering temperature/time conditions were
1310 8C/4 min or 1440 8C/5 min, and the entire sintering cycle
lasted no more than 10 min. The obtained results revealed that in
both systems the composites sintered at 1310 8C/4 min showed
better corrosion resistance as compared with those found when
Fig. 97. TEM micrographs of Al2O3/(ZrO2 + Ni) composites after SPS at 1350 8C for
(a) 1 min and (b) 5 min. Adapted from Tuan et al. [687].
adopting 1440 8C/5 min. For the former composite, a protective
Cr2O3 layer immediately forms upon heating, whereas for the latter
one pest disintegration was noted. Thus, under the same SPS
conditions, the NbAl2O3 composites showed the highest weight
gains.
Various alumina composites containing nano-sized metallic
dispersions, i.e. Cu, Ni, Co, and W, solgel derived, have been
recently pulse electric current sintered [691]. Two different
sintering conditions were considered, i.e. at low temperature
and short sintering time (1250 8C for 5 min) or high temperature
and longer dwell time (1450 8C for 30 min), and the properties of
resulting products were evaluated.
Among the Al2O3/intermetallic systems, dense NiAlAl2O3
composites were obtained by resistance sintering or pulse electric
discharge method using the powder mixture (crystallite size of
about 20 nm) prepared by reactive milling of NiO + Al (NiO/Al = 3/5
molar ratio) [692]. During the resistance sintering process the
current was kept at about 800 A, sintering time in the range 1
3 min and the applied pressure was 30 MPa. Surprisingly, the
temperature was also kept constant to 1200 8C. In the pulse electric
discharge method, a 200 mF capacitor battery was used and a
maximum voltage of 10 kV was applied. The current impulses
generated had the duration of few ms and magnitude of hundreds
of kA. In both cases there are no phases transformations due to the
consolidation and sample densities of about 90% of the theoretical
value were achieved. However, a signicant increase in average
NiAl crystallite size up to hundreds of nm was observed.
NiAlxAl2O3 composites (x = 13, 38 and 55 vol.%) were pro-
duced from mixtures of Ni, Al and Al2O3 powders in a single step
using the PPS method [42]. The process was performed in two
thermal stages. In the rst one (2.5 kJ discharge energy, 1 Hz
frequency, 5000 V), powder compact was heated to 600 8C (heating
rate of 10 8C/s) and was maintained at this temperature for about
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
5 min. Then (8.1 kJ discharge energy, 1 Hz frequency, 9000 V) the
temperature was increased up to 1100 8C (heating rate 7 8C/s) and
maintained at this level for about 10 min. The composite was
synthesized and simultaneously consolidated under the applied
pressure of 60 MPa. The obtained NiAlAl2O3 composites had a
hardness ranging from 480 HV10 (13% Al2O3) to 680 HV10 (55%
Al2O3). The fracture toughness of the sintered materials depended
on the amount of the dispersed Al2O3 phase. When examined with
a Vickers indenter under a load of 10 kg, the composite containing
13% of Al2O3 showed no cracking. For the composites with 38%
Al2O3 and 55% Al2O3 contents, the values of KIC were 9.1 and
8.2 MPa m1/2, respectively.
The Al90Mn9Ce1/Al2O3 bulk metal/ceramic composite material
with a honeycomb-like microcell structure was recently obtained
by sintering spherical Al90Mn9Ce1 alloy powders clad by Al2O3
nanopowder with the SPS technique (cf. Fig. 98) [693]. The as-
prepared material consisted of Al90Mn9Ce1 alloy cell and closed
Al2O3 ceramic cell wall. The diameter of the cells was approxi-
mately 2040 mm, while the thickness of the cell wall was about
12 mm. The ultimate compressive strength of the as-sintered
materials was about 514 MPa, while its fracture strain was up to
about 0.65%. The result showed that the Al90Mn9Ce1/Al2O3
composite powders can be sintered by SPS technique despite
the large difference in their sintering temperature.
A metal ceramic composite was fabricated by SPS using alumina
sludge (91.2 mass% Al2O3) and Al powders [694]. The sludge
content was varied in the range of 06 vol.%. Consolidation was
carried out using a Dr Sinter SPS-2050 apparatus under 1040 MPa
mechanical pressure while the temperature was set not above
Fig. 98. SEM images of the Al90Mn9Ce1/Al2O3 composite powders before sintering
(a) and the microstructure of the specimen sintered with SPS method (b). Adapted
from Zhao et al. [693].
209
773 K, to avoid Al melting. It was found that the bending strength is
strongly affected by the sludge content and the maximum value
was obtained at 2%.
CoAl powder prepared via SHS were processed, along with
ZrO2(3Y) (0.1 mm) and Al2O3 (0.3 mm), by SPS to produce dense
particle dispersed-CoAl materials [695,696]. Six compositions, i.e.
80 mol% CoAl, 1420 mol% ZrO2(3Y), 06 mol% Al2O3, were inves-
tigated. Starting powders were sintered for 10 min at 1300 8C,
100 8C/min heating rate, under a pressure of 30 MPa. A nearly full
densication (higher than 99.6% of theoretical) was achieved for all
compositions considered. SPS products consists of tetragonal
ZrO2 (0.3 mm) and Al2O3 (0.5 mm) particles located at the grain
boundaries of the CoAl (8.5 mm) matrix. Improved mechanical
properties, especially the fracture toughness (3.87 MPa m1/2) and
the bending strength (1080 MPa) of the materials with ZrO2(3Y)/
Al2O3 = 16/4 mol%, were obtained.
Dense Cr2O3xW (x = 10 vol.%) composites were successfully
obtained by SPS starting from solgel prepared Cr2O3 and W
obtained after reduction with H2 of commercially available WO3
powders [697]. SPS was carried out at 1300 8C for 10 min, 100 8C/
min heating rate, and 30 MPa mechanical pressure. The resulting
sample was 99.8% dense and consisted of Cr2O3 and W only. It was
found that the mechanical properties of the obtained composites
(bending strength and fracture toughness) were improved, as
compared to pure Cr2O3, by the addition of W.
WLa2O3 materials were processed by SPS using nanocompo-
site (W2.2 wt.%La2O3) powders obtained by a liquidliquid
mixing, freeze-drying and reduction process [698]. No experi-
mental details on the SPS process were reported in the paper. A
uniform distribution of lanthanum is found in the obtained
nanocomposite WLa2O3 material (cf. Fig. 99). The latter one
exhibited good electron emission performance: a saturated
emission current density of 1.46 A/cm2 can be reached at
1673 K with a corresponding work function of 2.79 eV. The surface
analysis results showed that the good emission capability might be
related to an about 10 nm surface layer contained excess La caused
by diffusion of La from bulk material to the surface.
Pulse electric current sintering of mullitexMo (x = 0100 vol.%)
composites was performed by SPS (SPS-515S) using mullite, Mo
and MgO, as sintering aid [699701]. Experiments were carried out
at temperatures of 1500 8C, heating rate of 150 8C/min, 10 min
holding time at the maximum temperature, with an applied
pressures of 20 MPa. For all the compositions investigated, no
oxides of Mo were formed during sintering, and the densities of the
obtained composites were more than 98% of the theoretical values.
Fig. 99. Back scattered emission micrographs of SEM for WLa2O3 material: the
dark gray phase is La-rich and the light gray one is W. Adapted from Xi et al. [698].
210 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Microstructural observations revealed that Mo particles were

dispersed uniformly at lower Mo contents and exhibited aky and
elongated structure at higher content. Simultaneous increase of
fracture strength and toughness occurred with increase in Mo
content. It attained a maximum of 1.1 GPa and 9.2 MPa m1/2,
respectively, for 90 vol.% Mo composites.
Oxide-dispersion-strengthened Ni3Al composites were fabri-
cated by reacting Ni, Al and B co-milled powders in a SPS-1050
apparatus [702]. Element O was incorporated during mechanical
alloying. The sintering temperature was 1150 8C with a holding
time of 5 min by heating rate of 100 8C/min and under a pressure of
40 MPa. The resulting composites had a nearly full density and
contained about 3 vol.% oxides disperse in the matrix uniformly.
The average size of oxide was about 50 nm. The produced oxide-
dispersion-strengthened Ni3Al composites showed high bending
strength (about 2450 MPa) and large strain.
Well densied NiAl/10-mol%ZrO2(3Y) composites were fabri-
cated via SPS starting from NiAl, prepared by SHS and containing
traces of a-Al2O3, and ZrO2(3Y) [703]. SPS experiments were
carried out at 1300 8C for 10 min, heating rate of 100 8C/min, and
30 MPa. The product microstructures consisted of tetragonal ZrO2
(0.2 mm grain sized) and Al2O3 (0.5 mm grain sized) particles
located at the grain boundaries of the NiAl (46 mm grain sized)
matrix. Improved mechanical properties are obtained: the
fracture toughness and bending strength are 8.8 MPa m1/2 and
1045 MPa, respectively, and high strength (>800 MPa) can be
retained up to 800 8C.
SPS was recently used for the manufacturing of rare earth
oxidemolybdenum (Y2O3, La2O3Mo) cathode material [704].
The starting powder, produced through an aqueous solutionsolid
doping method, was sintered at 1500 8C for 3 min. For compar-
ison, the same powders were also sintered in a tungsten wire
furnace at 1800 8C for 2 h. It was found that the maximum
secondary emission coefcient of the SPS material could be equal
to 3.84, much higher than that of rare earth oxidemolybdenum
cathode made by traditional sintering method. The grain size was
less than 1 mm and rare earth oxides were distributed uniformly
in the material.
Fe1.5 wt.%Mo pre-alloyed powders and 1.5 wt.% nano-sized
SiO2 (10 nm) which was added to the iron alloy in order to increase
the thermal stability of the nanostructure, were rst co-milled. The
resulting mixture (21 nm mean crystallite domain size) was
sintered in a SPS-1050 apparatus [705]. Sintering was performed at
56 MPa, 100 8C/min heating rate, temperature in the range 800
825 8C, 1 min holding time. SPS results indicated that the sample
sintered at 800 8C was still nanostructured (76 nm) while when the
sintering temperature was increased to 825 8C, grains growth
occurred with some grains even larger than 1 mm.
A bulk dense nanostructured material was fabricated by
processing via SPS milled Fe40Al (at.%) powder with Y2O3
dispersions (0.2 at.%) [706]. A 515S SPS apparatus was employed
to consolidate the powders under an uniaxial pressure of 70 MPa,
a sintering temperature of 1050 8C, 210 8C/min heating rate,
without any dwell time at the sintering temperature. The SPS
material had relative density of about 99.7% and displayed a fairly
heterogeneous microstructure consisting of nano-(80300 nm) Fig. 100. Secondary electron SEM micrographs at high magnications showing the
and micrometric (up to 10 mm) grains (cf. Fig. 100). Such a details of the heterogeneous microstructures present in the Y2O3/FeAl sample
structural heterogeneity with different sized grains was reported sintered by SPS: (a) a general view showing three types of zones (labeled A(A0 ), B
and C); (b) the structure in the ultrane-grained zone A where ne oxides are
to be caused by the fact that, under the adopted SPS conditions,
homogenously distributed and (c) the structure in the coarse-grained zone C where
large temperature differences in the range 570670 8C, due to oxide particles display signicant variability in size and distribution. Adapted from
rapid heatingcooling and also to the lack of holding stage applied, Ji et al. [706].
could be present.
Nanocrystalline FeCo alloy dispersed MgO nanocomposites
were fabricated by PECS starting from a mixture of FeCo and MgO
powders obtained via a solution chemical route and hydrogen
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
reduction [707]. Fully densied (98% relative density) MgO/
20 vol.%FeCo alloy nanocomposites were obtained after sintering
for 5 min at 1473 K, 200 K/min heating rate and under a pressure of
100 MPa. Dense sintered nanocomposites show a bimodal
distribution of the particle size of metallic Fe dispersions, that
is, 1050 nm for intragranular dispersions and 300500 nm for
intergranular dispersions at grain boundaries. It was found that
fracture toughness increased with increasing FeCo volume fraction
and the highest value of 2.35 MPa m1/2 was obtained for MgO/
40 vol.%Fe composites. Magnetization response to applied uniaxial
stress in the nanocomposites was observed by the magnetostric-
tion effects of FeCo dispersions.
2.9.7. Other ceramic-metal and ceramic intermetallic composites
SPS was recently applied to prepare boron-ber-reinforced Ti-
matrix composites using Ti foils and B bers alternatively stacked
following the procedure schematically represented in Fig. 101
[708]. The latter ones were bonded in a SPS-1020 apparatus under
a pressure of 32 MPa, heating rate of 1.7 K/s and holding
temperatures of 973, 1073, 1173, and 1273 K for 600 s.
A good bonding between the boron ber and the Ti-matrix was
achieved when the process was performed at 1073 K. If the holding
temperature was higher than 1173 K, a TiB2 layer was formed
along the interface between the ber and the matrix, along with
the occurrence of the crystallization of amorphous boron in the
vicinity of the tungsten core in the ber. The thickness of TiB2 layer
and the amount of crystallized boron is augmented with increasing
the sintering temperature. The composite produced by the SPS
process at 1073 K with 17.2 vol.% boron ber presented a tensile
yield stress of 706 MPa when deformed at room temperature. This
value was about 80% of the yield stress estimated by a force-
equilibrium equation of a composite taking into account the
direction of ber axis.
Bulk AlxC and (Al5 wt.%Si)xC composites (x = 050 mol%)
were obtained after consolidation by SPS of Al (spherical or ake),
Fig. 101. Processing of boron-ber-reinforced titanium matrix composites, using
SPS process: (a) Ti foils and B bers are laminated alternately; (b) bonding between
Ti foils and B bers by pulsed current hot pressing (hatched areas in (b) are heated
zones by spark discharge) and (c) formation of B-ber-reinforced Ti-matrix
composite. Adapted from Mizuuchi et al. [708].
211
AlSi alloy, and carbon powders [709]. Sintering was obtained under
vacuum in a SPS-1050 machine under a mechanical pressure in the
range 20100 MPa, 500550 8C sintering temperature and 5
30 min holding time. It was observed that the relative densities of
the composites sintered did not depend signicantly on sintering
time and temperature, while it increased when the applied pressure
was augmented. In addition, it was seen that when x was less than
30 mol%, composites density was affected by particle shape of Al. In
particular, when using the Al ake, the composite sintered at high
applied pressure of over 60 MPa exhibited high densities if
compared with AlC composite obtained from spherical Al particles.
It was also found that (Al5 wt.%Si)C composites sintered at 550 8C
showed considerably higher density than those of pure AlC
composites produced at the same temperature, thus indicating that
it is likely the partial formation of liquid phase at lower temperatures
in AlSi alloy than in pure Al.
A suitable material for high temperatures low-friction applica-
tions, the Cugraphite composite, was prepared by HEHR
consolidation using Cu and graphite powders as starting material
[710]. Different Cux graphite compositions, i.e. x = 2.44.8 wt.%,
and graphite particles sizes, i.e. 574 mm, were considered.
Consolidation experiments were carried out using a 10 MJ high
power generator with a peak discharge current of 130 kA at 100 ms
and peak duration less than 2 s, under an applied pressure of
462 MPa. The density of the obtained samples depended upon the
composition of the starting mixture and the graphite character-
istics. The maximum density value, i.e. 97%, was obtained for the
case of the Cu2.4 wt.% graphite using 200 mesh (<74 mm)
graphite powders. In addition, it was found that the HEHR
consolidated specimens exhibited hardness values between 14 and
46% higher than a conventional Cugraphite sintered commercial
compact. In addition, wear properties measurements showed that
all the Cugraphite samples consolidated by HEHR displayed much
better tribological characteristics in comparison with the reference
Cugraphite commercial sample.
More recently, the same HEHR technology and Cugraphite
system were further investigated for the development of
composite electrical brushes [711]. In particular, new experiments
were aimed to examine the effect of temperature on the homopolar
pulse consolidated (HPC) brush wear rate for an apparent brush
current density of 180 A/cm2, a brush downforce of 44.5 N, and
rotor surface sliding speeds of 10 and 40 m/s. At a sliding speed of
10 m/s, it was seen that wear rate decreased suddenly as the
temperature increased from 80 to 103 8C. In additions, these
experiments indicated that brush wear rate is generally augmen-
ted by increasing brush bulk temperature. At a sliding speed of
40 m/s, it was found that brush wear rate increased by several
times as the brush bulk temperature approached 149 8C.
The SPS technique was applied to fabricate binary composites
Gdx(Gd5Si2Ge2)1x (x = 0.3, 0.5, and 0.7) with magnetocaloric
effect starting from pure Gd metal and Gd5Si2Ge2 alloys [712]. The
latter one was previously prepared by levitation melting using Gd,
Si and Ge powders. The two starting components, i.e. Gd and
Gd5Si2Ge2, once cut in cuboids were then joined by SPS to form a
layered composite. The latter one was obtained under a tem-
perature of 700 8C, 50 MPa pressure, and 2 min sintering time. A
good sintering joint was obtained with a transition layer of about
10 mm. The magnetocaloric effect of the composites was studied
by directly measuring adiabatic temperature change (DTad) with a
magnetic eld change of 1.5 T. It was found that with increasing x
from 0.3 to 0.7, DTad peak shifted from 286 to 293 K and the peak
values of DTad slowly increased from 1.6 to 2.0 K. In particular, the
composite with x = 0.7 showed a DTad ranging from 1.1 to 2.0 K at a
magnetic eld change of 1.5 T in a temperature range of 260
300 K, which adapted to work as a room-temperature refrigerant.
212 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 102. Relative density vs. sintering temperature for 5 vol.% SiCAl2O3 superfast
sintered by SPS. Adapted from Gao et al. [718].
Titanium/010 wt.% hydroxyapatite hybrid biomaterials were
fabricated by SPS starting from Ti and HA powders [713]. Sintering
was carried out in vacuum at a temperature of 900 8C and 25 MPa
mechanical pressure. It was found that the bending strength for the
obtained biomaterials was stronger than that of human bone. In
particular, the Ti/48 wt.%HA hybrid material showed 4 GPa
Vickers microhardness, 400 MPa bending strength and osteocon-
ductivity properties.
Different bulk NiCrxCr2O3yAg composites (x = 2025, y = 0
24 wt.%) with interesting tribological characteristics were
obtained by SPS using NiCr, Cr2O3, and Ag powders blended in
appropriate proportions [714]. During SPS experiments, the
processed sample were subjected to an applied pressure of
50 MPa and heated to 830 8C in 10 min, being the latter tem-
perature value maintained for 3 more minutes. It was found that
friction coefcient of the obtained products decreased when
increasing Ag content. The optimum wear losses and friction
coefcient were obtained when using 15 wt.% Ag.
Nanocrystalline Fe24 at.%AlxC (x = 1, 2, 4 at.%) alloy powders
produced by mechanical alloying from Fe and Al powder in
presence of methanol were consolidated in vacuum in a SPS device
at 10731273 K for 300 s, 2 K/s heating rate under 64 MPa [715
717]. The compacts with 1 at.% carbon content and densied at
1273 K had a relative density higher than 99.5% and consisted of
grains of Fe3Al of about 1 mm and with nano-k-carbides (Fe3AlC0.5)
precipitates. On the other hand, the samples prepared with higher
carbon content (2 or 4 at.%) are made of Fe3Al of about 80 nm grain
sized, nano-k-carbides and small amount of large a-Fe grains of
Fig. 103. Vickers hardness (a), bending strength (b) and fracture toughness (c) vs. sintering temperature for 5 vol.% SiCAl2O3 superfast sintered by SPS. Adapted from Gao
et al. [718].
about 1 mm in diameter. Regarding the corresponding mechanical
properties, it was found that specimens with 1 and 2 at.% C
exhibited improved mechanical properties at room temperature
when compared with the ordinary Fe3Al casting. For instance, for
the case of 2 at.% C, yield strength and rupture strain were
2150 MPa and 0.14, respectively.
2.10. Ceramicceramic composites
2.10.1. Al2O3-containing composites
The intergranular SiCAl2O3 nanocomposite was obtained by
SPS (Dr. Sinter 1020, Sumitomo Coal Mining) starting from 5 vol.%
SiCAl2O3 produced by heterogeneous precipitation method.
Densication was carried out at different sintering temperature,
with a heating rate of 600 8C/min, under an applied pressure of
40 MPa and without soaking time [718]. The better result in terms
of densication and mechanical properties was obtained at
1450 8C as shown in Figs. 102 and 103, respectively. Vickers
hardness was 19 GPa and bending strength was 980 MPa, which is
much higher than that of monolithic Al2O3 (350 MPa). Also
fracture toughness was signicantly improved by the addition of
nano-SiC as compared with that of Al2O3 ceramic. Moreover,
microstructural studies revealed that nano-SiC particles were
mainly coated by g-Al2O3 and consisted of many ne particles
which size was about 10 nm.
Al2O35 vol.%SiC and Al2O320 vol.%SiC nanocomposites were
fabricated by SPS (Dr. Sinter 515S, Sumitomo Coal Mining) at
11001500 8C (200 K/min heating rate), at 40 MPa for 5 min [719].
Densication behavior and mechanical properties were studied. It
was found that as the volume fraction of SiC was increased, the
onset for densication of Al2O3SiC composites was delayed. In
addition, full-dense Al2O3, Al2O35 vol.%SiC and Al2O320 vol.%SiC
were obtained at 1200, 1300 and 1400 8C, respectively. Mechanical
tests showed that the fracture strength increased from 663 MPa of
pure Al2O3 to 693 and 812 MPa for Al2O35 vol.%SiC and Al2O3
20 vol.%SiC nanocomposites, respectively. The fracture toughness
showed a similar trend, thus increasing from 2.95 MPa m1/2 of the
pure Al2O3 to 3.07 MPa m1/2 and 3.66 MPa m1/2 for the 5 vol.% SiC
and 20 vol.% SiC compacts, respectively. The improvement of
mechanical properties have been attributed to the increased rate of
densication and to microstructural changes, as well as the effect
of ne SiC dispersion.
SPS (Dr. Sinter 2040, Sumitomo Coal Mining) apparatus was
used to consolidate Al2O340 wt.%TiC nanocomposite powders
synthesized by HEBM [720]. Sintering was performed a 1480 8C
(heating rate 50 8C/min) for 4 min at 50 MPa and full densication
(99.2%) was achieved. The nal products exhibited very ne
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 104. Back-scattered electron (BSE) SEM images showing the cross-section of the
TiN/Al2O3 laminate composite. The insert show a crack-free composite with a
clean boundary between the TiN and Al2O3 layers. Layers with light and dark
contrast are TiN and Al2O3, respectively. Adapted from Zhang et al. [726].
microstructure and TiC and Al2O3 grain sizes were about 200 and
400 nm, respectively. Vickers hardness equal to 21.0 GPa, 944 GPa
of exural strength, 3.874 MPa m1/2 of fracture toughness, and
1.2787  105 S/m of electrical conductivity were measured.
PECS technique was used to fabricate g-alumina matrix/silicon
carbide composites. a-alumina was added as a seed to g-alumina
in order to improve densication [721]. When sintered by PECS at
1450 8C, compacts reached a density of 3.8 g/cm3, which is higher
than the value obtained by pressureless sintering methods (3.0 g/
cm3). Vickers hardness and fracture strength of PECS samples
sintered at 1450 8C were 17 GPa and 500 MPa, respectively.
Al2O3TiC composite powders synthesized by high-energy ball
milling were consolidated near to theoretical density (99.6%) in SPS
at 1450 8C for 4 min at 50 MPa [722]. The nal product showed ne
microstructure with grain sizes of both Al2O3 and TiC less than
1 mm. Flexural strength of 650 MPa, hardness of 19.1 GPa, fracture
toughness of 4.5 MPa m1/2 and electrical conductivity of 2.3828 
105 V1/m were measured.
High dense (97% of the theoretical value) Al2O3Ti3SiC2
composites with different Ti3SiC2 contents (0, 10, 20, 30, 50, 70,
90, 100 wt.%, respectively) were prepared by SPS at 1300 8C and
30 MPa, starting from attrition milled Al2O3 and Ti3SiC2 powder
mixture [723,724]. Besides Ti3SiC2 and Al2O3 also a small amount
of TiC was detected by X-ray diffraction and no evidence of reaction
between Ti3SiC2 and Al2O3 was observed. In agreement with the
percolation theory, the electrical conductivity resulted to strongly
depend on Ti3SiC2 volume fraction and the percolation threshold
was observed at 1020 vol.% Ti3SiC2. From the measurement of the
mechanical properties it was found that Vickers hardness decrease
with increasing the Ti3SiC2 amount, while the fracture toughness
was strongly improved by the addition of the toughening phase
Fig. 105. Backscattered electron image of Al2O3-TiNi SPS-RS compact (a) and mechanically mixed TiN and Al2O3 sample (b) fabricated by SPS at about 1400 8C for 6 min.
Adapted from Wang et al. [727].
213
Ti3SiC2. Specically, such mechanically properties increases from
3.2 MPa m1/2 for the pure Al2O3 to 9.3 MPa m1/2 for pure Ti3SiC2.
Al2O3Ti3SiC2 composites with functional graded composition
were also fabricated by SPS. Powder mixtures with varying weight
fraction of Ti3SiC2 (0100 wt.%) by increment of 10 were stacked
layer by layer in a graphite die and then sintered at 1350 8C under a
pressure of 25 MPa [725]. The hardness distribution across the
entire functional graded samples was evaluated by Knoop
indentation test. It was found that the length of indentation
increased as the Ti3SiC2 content increased. This indicated that
hardness gradually decreases when Ti3SiC2 content is augmented.
Microstructure was also investigated as a function of layer com-
position. The typical network structure of Ti3SiC2 was observed
when Ti3SiC2 weight fraction increased up to 50 wt.%. In agreement
with results reported above percolation region was observed at
2030 wt.% Ti3SiC2.
Pure Al2O3 and pure TiN tapes obtained by a water-based
process were consolidated by SPS (Dr. Sinter 2050, Sumitomo Coal
Mining) at 1400 8C for 3 min under uniaxial pressure of 50 MPa and
at 1500 8C for 5 min at 75 MPa, respectively [726]. TiN/Al2O3
laminate composites were also fabricated by SPS from Al2O3 and
TiN tapes. Densication was performed at 1500 8C (heating rate
100 8C/min) for 510 min at 75 MPa. Cracks free TiN/Al2O3
laminates were obtained (cf. Fig. 104). SEM studies revealed that
Al2O3 layers were free of pores, whereas only a few pores were
found in the TiN layers. Anisotropic mechanical behavior was
observed. Specically, a hardness of 20 GPa was measured for
Al2O3 layers, which is consistent with dense ne-grained Al2O3,
while the hardness of TiN was in the range 1115 GPa because of
the presence of pores.
Al2O3TiN nanocomposites were synthesized by in situ RS (SPS-
RS) at 1400 8C, under a pressure of 60 MPa, at different dwelling
time (06 min) starting from a mixture of TiO2, AlN and Ti powders
[727]. The obtained samples consisted of cubic TiN (46 vol.%) and
a-Al2O3 (54 vol.%). It was found that the relative density increased
with dwelling time and full density (99%) was achieved after 6 min.
Microstructure investigation revealed ne structure with TiN
particles homogeneously distributed in the Al2O3 matrix (cf.
Fig. 105a). The average grain size was less than 400 nm. The
Vickers hardness, fracture toughness and bending strength of
samples from SPS-RS were 17.8 GPa, 4.22 MPa m1/2 and 746 MPa,
respectively. For the sake of comparison, Al2O3/TiN composites
were also prepared at 1420 8C under 60 MPa, using mechanically
mixed TiN and Al2O3. High dense samples (99.1%) with more
homogeneous structure (cf. Fig. 105b), slightly higher hardness
and fracture toughness were obtained in the last case as compared
to SPS-RS compacts.
The SPS (Dr. Sinter 2050, Sumitomo Coal Mining) was also
applied for the production of duplex TiN/a-Al2O3 composites and
214 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
graded laminates starting from mixtures with different TiN
volume fraction (0, 20, 40, 50, 60, 80 and 100, respectively)
[728]. Densication was performed at 1500 8C (heating rate
100 8C/min) for 5 min, at 75 MPa [728]. High densities in the
range 99100% of theoretical one were achieved for composites
containing up to 60 vol.% TiN, while pure TiN reached only 95%. It
was also found that the addition of TiN effectively inhibited the
signicant grain growth observed for the monolithic Al2O3. To
prepare the laminated structures, precursors were stacked with
graded composition in a graphite die, and sintered at 1500 8C for
5 min at 75 MPa. Each layer showed full densication, except for
pure TiN. Hardness determined for each layer gradually decreased
from the layer as the TiN content increased. No cracks were
observed in multilayered structure, thus indicating the low stress
level inside the laminates. In contrast, when pure Al2O3 and pure
TiN were laminated alternatively cracks easily developed perpen-
dicular to the TiN/Al2O3 interfaces.
Al2O3-based composites containing BaF2, CaF2 and SrF2 as solid
lubricant (Al2O331BaF219CaF2, Al2O331BaF219CaF25SiO2,
Al2O350CaF2 and Al2O350SrF2) were prepared by SPS at
different temperatures, in the range 11231573 K, and with
different holding time (0.31.2 ks) depending on composition,
under a pressure of 40 MPa [729]. Microstructure, high tempera-
ture friction and wear properties were investigated. Interesting
results were obtained for Al2O331BaF219CaF2 (mass%) compo-
sites sintered at 1273 K for 0.6 ks. A ne lamellar structure, which
consisted of BaF2 and CaF2 phases, was observed. Moreover,
Al2O331BaF219CaF2 exhibited the lowest friction coefcient
between room temperature and 1073 K, and showed the lowest
wear rate at 873 K.
WC32 at.%Al2O3 nanocomposites powders were obtained by
reactive ball milling and subsequently sintered using the PAS
technique at 1963 K for 0.18 ks under a pressure of 19.638.2 MPa
[730]. Consolidation process led to high dense (99.2% of the
theoretical value) samples, which maintained their nanocrystal-
line structure. WC ne grains (about 50 nm) were found to be
homogeneously distributed and perfectly interfacially bonded
with the ceramic Al2O3 matrix. The average hardness, the Youngs
and shear moduli of the nanocomposites were 16, 422 and
184 GPa, respectively. Moreover the fracture toughness resulted
signicantly improved (15 MPa m1/2), as compared to that of the
pure nanocrystalline WC (4 MPa m1/2).
Nb substrates were coated with Mo(Si, Al)250 wt.%Al2O3, B-
doped Mo5Si3SiO2, Nb3Si5Al2, Cr-doped (Si,Al)2 and NiAl by SPS
[731]. Microstructure and oxidation behavior were investigated.
Bonding to Nb substrate was achieved only for the B-doped Mo5Si3
SiO2 composition, by sintering at 1773 K, under a pressure of 40 MPa
and with a holding time of 0.6 ks. An interlayer of 5 mm thickness
was observed between Nb substrate and B-doped Mo5Si3
5 wt.%SiO2 outlayer. Moreover, Nb substrates coated with B-doped
Mo5Si35 wt.%SiO2 interlayer and B-doped Mo5Si32 wt.%SiO2 out-
layer exhibited good oxidation resistance at 14731673 K.
2.10.2. SiC-containing composites
SiCmullite nanocomposites with 5 and 10 vol.% SiC, respec-
tively were prepared by SPS (SPS 1020 Sumitomo Coal Mining Co.)
starting from nano-sized SiC and mullite powders [732]. Different
results on sintering were observed depending on the composite
composition. Both 5 and 10 vol.% SiC/mullite reached a relative
density of 96% at 1400 8C and full density at 1500 8C. At 1400 8C
both composites exhibited ne microstructure with grains of about
280 and 240 nm for the case of 5 and 10 vol.% SiC, respectively. At
1500 8C mullite grains become coarser and less uniform and a
typical intragranular structure was observed with SiC particle
entrapped inside mullite grains. Strength increased with sintering
temperature. In particular, strength resulted improved (466 and
454 MPa for 5 and 10 vol.% SiC, respectively) as compared to
monolithic mullite (200300 MPa), while toughness did not
change signicantly.
A series of SiC-whiskers mullite matrix composites obtained by
wet chemistry containing up to 30 vol.% of SiC were consolidated
by SPS at 13001400 8C with a holding time of 320 min under a
pressure of 50 MPa [733]. When sintering monolithic mullite at
1300 8C for 3 min at 50 MPa the relative density reached the 99.5%
of the theoretical value and a ne equiaxed-grained structure was
obtained. Grain growth developed at 1400 8C with the formation of
elongated grains. In contrast, grain growth of mullite matrix
resulted suppressed by SiC addition and when SiC-whiskers
mullite composites were sintered at 1300 8C for 3 min, a density
of 99% independent of SiC content was obtained. A slighter increase
to 99.399.6% was observed at 20 min. For the sake of comparison
the same composites were also consolidated by HP between 1550
and 1700 8C and a density of 98% was reached in 40 min holding
time at 30 MPa [733]. It was also found that hardness increased
with SiC content from 12.8 GPa for mullite to 13.8 GPa for the
composite characterized by 30 vol.% SiC. Correspondingly, fracture
toughness increased from 2.1 to 4.5 MPa m1/2.
Reaction bonded Si3N4 matrix composites reinforced with
SiCrod particulates have been fabricated by nitriding Si powders
compacts containing the SiCrod particulates [734]. High dense
composite were obtained by increasing green density before
nitridation by means of SPS (T = 12001400 8C, P = 20100 MPa,
heating rate 110170 8C/min). It was found that density sig-
nicantly increased with sintering temperature at 20 MPa for both
pure SiCrod and the composite compact containing 34.6 vol.%
SiCrod. For higher SiCrod (54.9 vol.%) content density changed
slightly with temperature, thus indicating that densication of Si
matrix was delayed by SiCrod addition. However, density increased
effectively with increasing pressure.
b-SiC/(010 wt.%) Si3N4 sintered materials were prepared by
SPS at 2000 8C, under a pressure of 50 MPa for 5 min [735]. The
relative density of the sintered products was higher than 80% of the
theoretical value and it was also found that it increased when Si3N4
content was augmented, thus suggesting that Si3N4 is effective in
promoting SiC densication. Moreover, the nitride was found to
stabilize b-SiC structure. All sintered samples exhibited n-type
conduction and the carriers concentration increased with increas-
ing Si3N4 content. Thermoelectric properties resulted improved by
the addition of Si3N4.
Si3N4/SiC nanocomposites was obtained by SPS (Dr. Sinter 1050,
Sumitomo Coal Mining Co.) technique from SiCN amorphous
powders, synthesized by polymer precursors pyrolysis, and Y2O3 as
additive [736,737]. Sintering was conducted at 63 MPa, at 1600
and 1700 8C, with a heating rate of 100 8C/min and a holding time
of 10 min. When adding 1, 3, 5, 8 wt.% Y2O3, Si3N4/SiC nanocom-
posites were consolidated, within 10 min at 1600 8C, to a density of
2.96, 3.07, 3.09, 3.02 g/cm3, respectively. Further increase in
temperature, i.e. 1700 8C, did not give rise to higher density even
with a higher level of additives. During SPS, crystallization was
found to occur thus obtaining a crystalline composite of Si3N4 and
SiC. Moreover, with higher content of Y2O3, a large amount of
continuous glassy phase was present around grain boundaries and
a micronano microstructure was formed. This microstructure was
constituted by a submicron-sized matrix of SiC and Si3N4 with
nano-sized SiC particles entrapped in some of the Si3N4 grains. On
the other hand, nanonano structure was achieved with decreas-
ing additive weight fraction. In particular, when sintering was
performed at 1600 8C transition from micronano to nanonano
microstructure took place when Y2O3 amount was equal or lower
than 3 wt.%.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Si3N4/SiC composites with the additions of La2O3 (15 wt.%),
Y2O3 (9 wt.%), and SiO2 (3 wt.%) were fabricated by SPS (Dr. Sinter
2040, Sumitomo Coal Mining Co.) at different temperatures
ranging from 1550 to 1900 8C, for 5 min under a pressure of
49 MPa [738]. Specically, the composition investigated was
La0.19Y0.17Si2.73O0.75N3.5/(14.6 wt.%) SiC. Results were compared
with those obtained by HIP. It was found that open porosity
decreased with increasing temperature for both SPS and HIP
processes. Specically, it was completely eliminated by SPS after
10 min of heating rate at 1900 8C and 5 min dwell time. All SPSed
samples consisted of SiC, a- and b-Si3N4, Y3.5La6.5(SiO4)6N2. A new
phase was also detected when heating below 1800 8C. The
complete a to b transformation was achieved at 1900 8C with
the formation of elongated b-Si3N4 grains. The same results was
obtained by HIP at 1750 8C after 160 min of sintering duration.
Si3N4/SiC nanocomposites with 3 wt.% Y2O3 as additive were
fabricated by SPS from amorphous SiCN powders derived from a
polymeric precursor [739]. The effect of SPS parameters on the
sintering behavior of SiCN was investigated. It was found that the
average grain size increased with dwell time and sintering
temperature, while it decreased with pressure. The grain size also
decreased with heating rate. Density slightly decreased with dwell
time, sintering temperature and heating rate. These ndings
revealed that grain growth and densication already occurred at
temperatures lower than 1600 8C.
Si3N4/SiC/TiCxN1x nanocomposites have been produced by
reactive consolidation through the use of PECS (Dr. Sinter SPS 1050,
Sumitomo Coal Mining), starting from pyrolyzed amorphous TiC
N and nanocrystalline TiO2 [740]. Full-dense ceramics were
obtained at 1600 8C (240 8C/min) in 3 min under a pressure of
63 MPa. Nano-TiC0.3N0.7 grains were found to form a connected
matrix in which microsized aggregates of nano-Si3N4 and nano-SiC
grains were dispersed. The obtained ceramic exhibited excellent
electrical conductivity along with good mechanical properties
including 14 GPa hardness and 6.7 MPa m1/2 fracture toughness.
Laminated Si3N4 + SiCw/BN + Al2O3 (w = whiskers) ceramics
were rapidly prepared by SPS (SPS-1050, Sumitomo Coal Mining
Co.) [741]. Specically thick lms (0.2 mm) of Si3N4 + SiCw were
formed and, in order to introduce weak surfaces, each layer was
coated with a slurry of BN containing 36 vol.% Al2O3. After drying,
the Si3N4 + SiCw/BN + Al2O3 layers were stacked and pressed in a
graphite die and subsequently sintered at 1650 8C (reached in
13 min) with a dwell time of 15 min under a pressure of 22 MPa.
Layered compacts having each Si3N4 + SiCw matrix layer 120 mm
thick were obtained. A density of 3.18 g/cm3 was achieved, which
was higher than that of hot pressed samples (3.08 g/cm3) obtained
at higher temperature (170 8C higher) and in longer runs duration
(>2 h). b-Si3N4 and SiCw phases were found to be signicantly
textured and, together with hexagonal BN, they were detected as
the main phases after SPS. The arrangement of hard Si3N4 + SiCw
and soft BN + Al2O3 layers was considered the main reason for
improving the ceramic toughness.
The simultaneous synthesis and densication of layered, single-
and functional graded material (FGM) composites with formula
xMoSi2(1  x)SiC was performed by SPS starting from elemental
reactants [742]. Several composition ranging from 100% MoSi2 to
100% SiC were investigated by varying the x molar fraction from 0
to 1.0. Specically, single composition samples were obtained for
each x value in order to measure the physical characteristics of the
various compositions. Syntheses were performed at 1200 and
1300 8C under a pressure of 63 or 25 MPa depending on sample
dimensions. X-ray diffraction patterns showed that reactions were
always complete. A third phase of Mo4.8Si3O0.6 appeared in
addition to MoSi2 and SiC depending upon the carbon content in
the starting mixture. In particular, it decreased with decreasing x.
215
When x = 0.8 only a little evidence of the third phase was found.
The amount of Mo4.8Si3O0.6 slightly increased at x = 0.5 and became
signicant for x = 0.3. Furthermore, the relative densities of the
obtained samples increased from 76 to 98.6%, as x increased. The
Youngs modulus and Poissonss ratio, obtained from single
composition samples, were found to decrease with decreasing
density. Further experiments were performed on two layers
(x = 0.3 and 0.7, respectively) to evaluate thermal stress and layer
cohesion, and on ve layers graded samples (from x = 0.9 to 0.5 and
from x = 1 to 0.6, respectively) for mechanical testing.
For a bilayer sample with x = 0.3 and 0.7 no cracks along the
interface were found, thus indicating a good integration between
layers. In contrast, vertical cracks in the Mo rich side were formed,
due to the stress resulting from the large difference in the thermal
expansion coefcients of MoSi2 and SiC, which is about 40% at
1200 8C. On the other hand, it was observed that layers that were
10% different in composition (FGM composites) did not exhibit
cracking, since the thermal expansion coefcient varied by only 3%,
as calculated using a linear rule of mixture. Thus, by tailoring
composition between adjacent layers, thermal cracking could be
prevented. Furthermore, no smoothing of the interface between
layers was observed. This fact was explained by the authors
considering the solid nature of the reaction product and the lack of
a large concentration difference in a liquid phase, which can act as
driving force for bulk motion of such a phase during reaction.
In order to investigate the effect of time on the interface
composition, a series of two layer samples (x = 0.3, x = 0.7) were
also produced by FAPASA at different times from 5 to 20 min under
a current and a pressure of 1750 A and 95 MPa, respectively. The
samples exhibited slight differences in grain size and morphology.
No difference in the concentration prole was evident and all
specimens showed a step change in concentration.
Synthesis and simultaneous consolidation of fully dense MoSi2
and MoSi2SiC composites was performed by SPS at 1673 or
1873 K, starting from Mo, Si and C [743]. The oxidation behavior of
the composites was also studied. It was found that simultaneous
Mo and Si oxidation was suppressed in the accelerated oxidation
region at 773 K, due to the formation of a protective SiO2 layer.
The effect of AlN addition on the sintering behavior of SiC
powders, with stacking disordered microstructure, was investi-
gated by taking advantage of the SPS technique. Specically, SiC
(0, 1, 3 mol%) AlN powders, synthesized by mechanical alloying,
were sintered at temperatures ranging from 1500 to 1900 8C
(100 8C/min heating rate) for 10 min under a pressure of 70 MPa
[744]. It was found that the relative density of the consolidated SiC
and SiCAlN samples slightly changed, from 60 to 68%, as the
sintering temperature was increased from 1500 to 1600 8C.
However, when sintering was performed at 1700 8C the relative
density strongly increased to 98 and 99% for SiC1 mol%AlN and
SiC3 mol%, respectively. Further increase was observed at
1800 8C, being the corresponding densities 99.4 and 99.8% in
SiC1 mol%AlN and SiC3 mol%, respectively. In contrast, a
sintering temperature of 1900 8C was necessary to consolidate
SiC powders to a density of 99%. TEM observation showed that
dense SiC1 mol%AlN samples obtained at 1700 8C consisted of
ner grains (50 nm) as compared to SiC sintered at 1900 8C
(500 nm). Furthermore, a disorderorder transformation was
found to occur for SiCAlN samples during sintering between
1700 and 1800 8C.
Dense lossy AlNSiC composites doped with 6 wt.% Y2O3 were
fabricated by SPS (2040 Sumitomo) from AlNSiCY2O3 mixtures
with different SiC weight fractions. Sintering was performed under
a pressure of 30 MPa, at different temperatures in the range 1560
1620 8C, and a heating rate of 100 8C/min [745]. All sintered
samples exhibited near to full density (>98%) and consisted of AlN
216 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
and SiC as major phases. Yttrium aluminates (YAlO3 and Y4Al2O9)
were the second major phases depending upon the AlN/Y2O3 ratio
in the starting mixture. A coreshell structure, where the core was
AlN and the shell was SiC, was formed during sintering as a
consequence of the different grain sizes of AlN and SiC. The
macroscopic dielectric properties of the composites were also
investigated. It was observed that materials produced by SPS
exhibited much stronger uctuation in permittivity as compared
to those fabricated by HP. It was also found that the dielectric
properties of AlNSiC at microwave range can be tailored by
controlling the SiC content.
SPS was also used to prepare C40 Mo(Si0.75Al0.25)2/(10, 20 vol.%)
SiC materials containing micro- and nano-scale structure and Mo/
Mo5Si3 retained phases from mechanically alloyed powders [746].
The SiC particles with average grain size around 1 mm resulted
uniformly distributed in the structure. All the composites showed
high hardness values around 14 GPa, which was not sensitive to SiC
content. In contrast, indentation toughness strongly depends on
SiC volume fraction. It was found that toughness increased from
1.84 to 2.48 MPa m1/2 by adding 20 vol.% SiC to Mo(Si0.75Al0.25)2.
n-type Bi2Te3/x vol.% nano-SiC (x = 0, 0.1, 0.5, 1.0) composite
powders were synthesized by MA and subsequently consolidated
by SPS (Sumitomo SPS-1050) at 673 K (80 K/min) for 5 min under a
pressure of 50 MPa [747]. Compared to Bi2Te3 matrix, Bi2Te3 with
dispersed nano-SiC powders showed reduced grain size. The latter
decreased from 1 to 0.5 mm as SiC volume fraction increased in the
range 01.0. The relative density of all the sintered sample was
higher than 95%, although it decreased by adding SiC, from 98.7 to
95.8% for the Bi2Te3 matrix and Bi2Te3/1.0 vol.%SiC composite,
respectively. The Vickers hardness increased linearly from 0.62 to
0.79 GPa as 1.0 vol.% SiC was added. The highest fracture toughness
of 1.34 MPa m1/2 and Youngs modulus of 42.7 GPa were obtained
for 0.1 and 0.5 vol.% SiC addition, respectively. Also thermoelectric
properties resulted improved by the addition of moderate nano-
SiC particles.
Nano-sized b-SiC powders were sintered with AlN and Y2O3 as
sintered additives by SPS [748]. A relative density of 95% was
achieved when sintering at 18002000 8C for 10 min. From XRD
analysis, it was found that the secondary phase Y2O3 decreased
with increasing sintering temperature and b-SiC monophase was
observed at 2000 8C. Signicant SiC grain growth was found
between 1800 and 1900 8C. Grain size was found to decrease with
the addition of AlN.
An SPS apparatus (SPS-2040 Sumitomo Coal Mining Co.) was
employed to obtain dense sintered bodies from YAG5 vol.%SiC
powders synthesized by heterogeneous precipitation method
[749]. Densication was conducted at 13501550 8C (200 8C/min
heating rate) for 1 min at 50 MPa. High density (98% relative
density) was achieved at 1500 8C. Sintered samples consisted of
pure YAG and SiC and no phase transformation occurred during
sintering. SEM and TEM observations showed a ne intragranular
microstructure. Nanoscale SiC particles resulted well distributed in
the matrix being most of them located within YAG grains.
SiCTiC composites with different content of TiC (15, 30,
45 wt.%) were prepared by SPS at 1750 and 1800 8C, under a
pressure of 40 MPa. In general, it was found that density increased
with rising temperature [750]. The maximum value reached was
98% for SiC30 wt.%TiC when sintering at 1800 8C for 20 min. In
contrast, when sintering by HP in the presence of additives at
temperature of 1820 8C, a holding time of 1 h was necessary to
achieve high density. Vickers hardness of SPSed samples increased
with increasing both sintering temperature and TiC weight
fraction. Maximum fracture toughness of 6.2 MPa m1/2 and
bending strength of 646.2 MPa were measured for SiC30 wt.%TiC
composite. It was also observed that TiC grains located on grain
boundary of SiC inhibited SiC grains growth. By SEM observation, it
was found that two fracture mechanisms existed: transgranular
and intergranular.
TiC/SiCmicro and TiC/SiCnano composites (Ti/C molar ratio = 1:0.9)
were also synthesized in one step by SPS, using Ti, C and nano-SiC as
starting materials [751]. Synthesis and simultaneous densication
was performed at 1480 8C at different holding times in the range 2
8 min, under a pressure of 70 MPa. It was found that the sintered Ti/
C/SiC samples consisted of pure TiC and SiC after 8 min, without any
reaction occurring between SiC and Ti. A relative density of 97.9%
was achieved for samples containing nano-SiC, while the corre-
sponding relative density of micro-SiC-composites was only 94% of
the theoretical value as shown in Fig. 106. The size of SiC powders
was found to strongly affect the composite microstructure.
Specically, micronano type microstructure, with submicrometer
TiC matrix and nano-sized SiC particles embedded in TiC grains was
obtained from nano-SiC, while micrometer TiC matrix and SiC were
formed from microsized SiC.
SiC/TiC laminar ceramics composites from electrophoretic
deposition were sintered to 98% relative density by SPS at
1800 8C for 5 min, under a pressure of 35 MPa. In contrast, only
a relative density of 80.2% was achieved when sintering was done
by pressureless method at 2000 8C for 2 h [752].
SiC reinforced-TiC matrix composites with different content of
SiC were fabricated at 1600 8C by SPS [753]. High relative densities
(99%) were achieved. It was found that the presence of SiC
inhibited TiC grains coalescence and increased fracture toughness
of the composites due to the crack deection mechanism.
TiC/20 wt.%SiC composites were prepared at 1600 8C by SPS
under 70 MPa for 1 min, starting from commercially available
powders of TiC, nano-SiC and micro-SiC [754]. It was found that
higher density (99% of the theoretical value) was achieved when
using nano-SiC as compared to microsized SiC addition (about 95%
relative density). Distribution of nano-SiC particles within the
matrix resulted also more uniform. Moreover, grain growth of the
TiC monolithic matrix was hindered by the addition of nano-SiC.
For both micro-SiC and nano-SiC composites, a transgranular
fracture mode was observed. TiC/SiCnano composite fracture
toughness was higher (5.76 MPa m1/2) than that of TiC/SiCmicro
composite (4.91 MPa m1/2).
Submicron-structured TiS2/SiC composites were in situ fabri-
cated by SPS using TiC and Si as starting materials [755]. Full
densication (99% relative density) was achieved at 1250 8C with
Fig. 106. Relationship between the relative density and dwelling time during the
synthesis of TiC/SiCmicro and TiC/SiCnano composites by SPS. Adapted from Wang
et al. [754].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
a holding time of 6 min. The obtained composites exhibited ne
microstructure with SiC grains <200 nm.
SiC/C composites were synthesized through a pulse current
sintering device under N2 atmosphere, at 1400, 1600 and 1800 8C
(500 8C/min heating rate), at different holdings times (5 or 30 min)
under a pressure of 40 MPa [756,757]. A mixture of wood charcoal
and SiO2 powders (3245 mm) was used as starting material. The
SiO2 concentration was varied in the range 050 wt.% based on the
dry weight of wood charcoal. When sintering samples with 50 wt.%
SiO2 at 1400 8C, SiO2 was mainly detected, suggesting that it
melted and covered all fractured surface of the specimens. By
increasing temperature to 1600 8C, SiO2 disappeared and b-SiC
appeared. Specically, the formation of b-SiC (1 mm thick layer)
was found to be more pronounced on the surface of the wood
charcoal and, as a result, large pores were observed. b-SiC particles
resulted close packed among each other and charcoal became
denser. However, the bulk density strongly decreased at 1600 8C
(1.25 g/cm3) as compared to that reached at 1400 8C (1.75 g/cm3).
The maximum in the bulk density (2.25 g/cm3) was reached after
30 min at 1800 8C. Electrical and thermal properties were also
measured as a function of sintering temperature and SiO2 content.
When considering 50 wt.% SiO2 samples, thermoelectric properties
were found to generally improve with a temperature increase and
a maximum in the gure of merit was obtained at 200 8C for
samples heated at 1400 8C for 30 min.
20 vol.% short carbon ber-reinforced SiC matrix was produced
by SPS (2040 Sumitomo Coal Mining Co.) at different temperatures
in the range 15501650 8C, for 3 min, at 25 MPa [758]. For
comparison a monolithic SiC ceramic was also fabricated at
1550 8C under 15 MPa pressure. It was found that density
increased with sintering temperature, thus achieving 95% of the
theoretical value at 1650 8C. By SEM investigations, carbon bers
were found to be homogeneously distributed in the SiC matrix. At
high sintering temperature some cracks were formed within the
matrix, lowering mechanical properties of the composite as
compared to that of monolithic SiC. However, the presence of
carbon-dispersed bers was found to be effective in promoting
non-catastrophic fracture behavior.
With the nal goal of reducing friction of SiC, a novel porous
carbon called rice bran carbon (RCB) was recently used to prepare
SiC/RCB composites through PECS method [759]. Specically, a
mixture of RBC powders with different particle size (50, 30, and
10 microns) and SiC powders doped with Al4C3 and B4C additives
were prepared by ball milling and subsequently sintered by SPS
(1050 Sumitomo Coal Mining Co.) at 1600 8C for 5 minutes at
40 MPa. The SiC/RBC composites were consolidated to relative
densities in the range 81.887.3%, much higher than that of
monolithic RBC (62.0%) and much lower than that of monolithic SiC
(99.8%) obtained under the same sintering conditions. The relative
density of SiC/RBC composites was found to increase with
decreasing RBC particle size. It was also found that SiC/RBC
composites exhibited ner microstructure as compared to mono-
lithic SiC, where grain growth was found to proceed rapidly (from
0.3 to 25 mm) during sintering. Moreover, SiC/RBC composites
had a friction coefcient much lower than that of the monolithic
SiC, exerting a solid lubricant effect during sliding. SiC/RBC
composites showed also superior mechanical strength, lower
friction coefcient and better wear resistance, as compared to
conventional SiC/graphite composites.
2.10.3. Si3N4-containing composites
Si3N4 powders coated with 20 nm sized TiN particles have been
sintered by SPS at 1600 8C. A relative density of 91% was obtained
when sintering Si3N425 vol.% TiN [760]. The formation of a glassy
phase from Si3N4 was found to play an important role in
217
densication process. Microstructure of ceramic containing 25
and 32.5 vol.% of TiN consisted of a continuous TiN network in a
Si3N4 matrix. The electrical resistivity (about 1  104 V cm) was
much lower than that of a mechanical mixture of nano-sized TiN
and Si3N4 particles (1 V cm).
The 1032.5 vol.% TiN/Si3N4 composite particles obtained by
depositing TiO2 onto Si3N4 particle surface were consolidated by
SPS (Model 501L, Sumitomo Coal Mining Co.) at 1600 8C under a
pressure of 39 MPa [761]. The relative density of the ceramic
containing more than 25 vol.% TiN was 96%, in contrast with the
one containing less than 17.5 vol.% TiN which did not densify
(<60% density). The low electrical resistivity (103 V cm) of
composite Si3N4/17.5 and 25 vol.% TiN makes these ceramics
suitable for electric discharge machining.
a-Si3N4/b-Si3N4 multilayered ceramics were successfully
fabricated by adopting a fast SPS system (SPS-1050, Izumi
Technology, Japan) [762]. In order to prevent a-b-transition, a-
Si3N4 starting powders were mixed with Al2O3 (4 mass%) and MgO
(1 mass%), while Y2O3 (4 mass%) and Al2O3 (2 mass%) were added
to b-Si3N4 powders as sintering additive. Green samples were
sintered at different temperatures (18231923 K, 340 K/min
heating rate) and holding times (5120 min) under a pressure of
40 MPa. The effect of sintering temperature and time on the
strength of the laminated composites was investigated. It was
found that exural strength reached its maximum value (903 MPa)
for 10 min holding time, but it did not change when sintering
temperatures were higher than 1923 K. Moreover, fracture
toughness increased with decreasing layer thickness.
A nano-Si3N4/5 wt.% nano-C composite was successfully
fabricated by SPS treatment starting from an amorphous mixture
of b-Si3N4, Al2O3 (1.42 wt.%) and carbon (5 wt.%) obtained through
high-energy ball milling [763]. Full density was achieved after
sintering at 1600 8C (300 8C/min heating rate) for 5 min under a
pressure of 30 MPa. Crystallization occurred after sintering and the
only phase detected was b-Si3N4. A nano/nano homogeneous
microstructure was also observed. Nano-size (10 nm) carbon
grains resulted homogeneously dispersed in nano-sized (70 nm)
silicon nitride grain boundaries. The hardness of the nanoceramic
was comparable to that of conventional Si3N4, while Youngs
modulus was signicantly decreased. For the sake of comparison,
SPS was also employed to densied unmilled b-Si3N4, Al2O3 and
carbon powders. After sintered at 1600 8C for 5 min, unmilled
powders reached only 85% of the theoretical density. Full density
was achieved at 1780 8C while SiC and b-Si3N4 were formed. Phase
composition was found to be not uniform throughout the
specimen.
Si3N4 samples doped with 7.5 wt.% Y2O3 and 2.5 wt.% Al2O3
were fully densied by SPS at 1500 and 1800 8C (heating rate
200 8C/min) under a pressure of 50 MPa [582]. In the samples
quenched from 1500 8C, about the 85% of the submicron-sized
nearly equiaxed a-Si3N4 grains were retained, while the samples
quenched from 1800 8C consisted of elongated grains of b-Si3N4. It
was also found that the phase transformation occurred in few
minutes. Grain growth was found to strongly depend on heating
rate and on the amount and composition of the added sintering aid.
Dense (95% of the theoretical density) MoSi2-based composite
reinforced with 20 vol.% Si3N4 rod-like crystals were fabricated by
SPS (P = 50 MPa, T = 1723 K, heating rate 100 K/min, holding time
5 min) [764]. Sintered products consisted of Si3N4 crystals well
distributed in the MoSi2 matrix. No reaction between Si3N4 and
MoSi2 was observed. Mechanical properties of MoSi2 were
improved by the addition of 20 vol.% Si3N4. Specically, the
composite exhibited higher hardness as compared to monolithic
MoSi2. The exural strength was about 60% higher and fracture
toughness about 40% better than those of monolithic MoSi2.
218 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Besides, yield strength and low temperature oxidation resistance
resulted improved.
2.10.4. Ti3SiC2-containing composites
The simultaneous synthesis and densication of Ti3SiC2 was
investigated by PAS method, starting from ball milled Ti, Si and C
elemental powders [324]. The PAS process was comprised of two
stages in which a pulsed and a steady current were applied,
respectively. Specically, 100 A, a holding time of 99 s and a load of
1000 kg were used during the rst stage; 18003500 A, leading to a
maximum temperature in the range 15252500 8C, a load of 1000
2000 kg, along with a holding time of 02 h were the conditions
adopted during the second stage. Results were found to strongly
depend on the experimental conditions adopted. For example,
when using high current at relative short times (010 min), high
temperatures were reached (20002500 8C) but sintered products
showed the presence of TiC in addition to the desired Ti3SiC2 phase.
The conditions providing the best results were found as follows:
30 V, 100 A, 34.4 MPa, 99 s total pulsing time with 10% on, for the
rst stage; 1800 A (T = 1525 8C), 34.4 MPa, 2 h holding time at
sintering temperature, for the second stage. Under the optimal
conditions, near to full density was achieved. The microhardness of
the SPSed samples ranged from 6 to 7 GPa for an applied force of
about 14 N. Chemical and thermal stability at high temperature
as well as oxidation behavior were also investigated.
Ti3SiC2/10 vol.%Al2O3 composite was prepared by SPS at
different temperatures ranging from 1200 to 1400 8C (100 K/min
heating rate) at 40 MPa, with holding time varying in the range 5
15 min [765]. Good densication was achieved at 13001350 8C,
when holding time was set to 5 min. X-ray diffraction patterns
showed the presence of Ti3SiC2, Al2O3 and some amount of TiCx. For
sintering temperature higher than 1350 8C, Ti3SiC2 peaks were
found to drop substantially, thus indicating that decomposition
occurred. Hardness reached its maximum value (8.18 GPa) at 1300
and markedly decreased as the sintering temperature was
augmented. The exural strength (600 MPa) did not change
signicantly with increasing temperature, while fracture tough-
ness strongly decreased beyond 1300 8C. The properties of
composites were found not to be affected by the holding time.
Ti3SiC2(20 vol.%)SiC nanocomposite was prepared by SPS-RS
from elemental powders of Ti/Si/C and Al as sintering aid [766].
Powders were reacted by SPS (SPS-2040, Sumitomo Coal Mining Co.,
Japan) at different temperatures from 900 to 1300 8C (heating rate
100200 8C/min) 70 MPa and 6 min of holding time. When
experiments were performed at 900 8C, SPS products consisted of
Ti, Si and C with two new phases, i.e. TiCx and Ti5Si3Cy. In the
temperature range 9001000 8C, the Si amount decreased and
completely disappeared at 1100 8C. However, pure Ti3SiC2/SiC was
obtained at 11501300 8C. On the basis of these results it was
proposed that some C and Si diffuses into Ti particle to form TiCx and
Ti5Si3Cy that subsequently react with the remaining C and Si to form
Ti3SiC2 and SiC. Microstructure was found to be ne with Ti3SiC2
grains of about 5 mm in length and SiC average grain size of about
100 nm, being the relative density of the compacts of about 98% after
reaction at 1280 8C. With its ne microstructure Ti3SiC2(20 vol.%)-
SiC showed improved mechanical properties at room temperature.
Ti3SiC2TiC composites were synthesized by PDS starting from
TiH2, SiC, TiC, Si, and C powder mixtures at different molar ratios:
TiH2/Si/1.5TiC, 2TiH2/SiC/TiC, 2.8TiH2/1.4SiC/TiC, 3.5TiH2/1.75SiC/
TiC, 4TiH2/2SiC/TiC. Dense Ti3SiC2TiC composites (relative
density over 97%) were obtained in 15 min, at 1300 8C (50 8C/
min), at 50 MPa, from the (2.84)TiH2/(1.42)SiC/TiC mixture
having low TiC molar content [767]. The obtained specimens
exhibited well compacted structure with (0 0 1) texture of the
Ti3SiC2 phase. Good mechanical performances were observed.
SPS was also used to in situ fabricate Ti5Si3/TiC composites at
1200 8C (100200 8C heating rate), 60 MPa and 8 min holding time,
using SiC and Ti as starting materials. The effect of the starting SiC
particle size on Ti5Si3/TiC production has been investigated [768].
Specically, complete synthesis and densication was achieved
when starting from nano-sized or microsized SiC particles. On the
contrary, when microsized SiC was used, the resulting SPS product
consisted of TiC, Ti3SiC2, Ti5Si3 and free SiC phase. All the samples
exhibited the same microstructure with ne TiC grains (less than
200 nm). Furthermore, it was found that the fracture toughness of
all composites exceeded that of monolithic samples. The max-
imum value was found for Ti5Si3/TiC composites obtained from
microsized SiC.
Ti and nano-sized SiC powders were also used to in situ
synthesize submicrostructured Ti5Si3/TiC composites by SPS [769].
Compacts with relative density of 98.8% were obtained at 1260 8C
in 8 min. Fracture toughness of Ti5Si3/TiC was 4.2 MPa m1/2, which
was higher than that of monolithic Ti5Si3 (2.5 MPa m1/2).
Ti5Si3 and Ti5Si320 vol.%ZrO2 composites were synthesized
and consolidated in one step by FAPA from powders of pure Ti, pure
Si and pure ZrO2 [89]. The powder mixture was joule-heated by DC
current until densication was attained, under a pressure of 10, 30
or 60 MPa. The maximum temperature reached was 1000 8C with a
heating rate of about 1200 8C/min and process duration of 1 min. It
was found that for monolithic Ti5Si3 reaction occurred at 950 8C
under 60 MPa, and a relative density of about 98% was reached. The
latter one was higher than that attained by conventional HIP (72%).
Complete formation of Ti5Si320 vol.%ZrO2 composite took place
when temperature was 1000 8C at 60 MPa. The density of the
composite increased nearly linearly as the pressure was varied
between 10 and 60 MPa. The corresponding change for Ti5Si3 was
from 89 to 98%. Mechanical properties were also tested. The
fracture toughness of Ti5Si3 resulted improved by a factor of three
when adding ZrO2.
Ti3SiC2/3Y-TZP (3 mol% yttria-stabilized tetragonal zirconia)
composites, with Ti3SiC2 volume fraction varying in the range 0
50 vol.%, were fabricated by SPS (1020 Sumitomo apparatus) at
1300 8C under a pressure of 50 MPa [770]. The effect of Ti3SiC2
content on room temperature mechanical properties and micro-
structure were investigated. A relative density higher than 97% of
the theoretical value was reached for each sample. Grain size was
found to increase with Ti3SiC2 content. Both the Vickers hardness
and the bending stress decreased by adding Ti3SiC2, while the
elastic modulus increased with increasing Ti3SiC2 content, owing
to the elasticity of Ti3SiC2 (E = 320 GPa) in the 3Y-TZP
(E = 210 GPa). Also the fracture toughness increased and its
maximum value (9.88 MPa m1/2) was achieved by adding 50 vol.%
Ti3SiC2. The increase in fracture toughness involved multiple
toughening behaviors such as cracks deection, cracks bridging
and transformation toughening effects.
By further increasing Ti3SiC2 volume fraction up to 100 vol.%, 3Y-
TZP/Ti3SiC2 composites with different 3Y-TZP contents (040 vol.%)
were also obtained at 1300 8C [771]. No reaction occurred between
3Y-TZP and Ti3SiC2, but some t-ZrO2 to m-ZrO2 transformation took
place during fracture of the sintered composites, suggesting that the
deformation involved the mechanism of phase transformation
toughening. In agreement with results reported above, Vickers
hardness monotonically increased with 3Y-TZP content. The
bending strength and fracture toughness showed opposite beha-
viors at about 30 vol.% 3Y-TZP, reaching a minimum the former and
its maximum value (11 MPa m1/2) the latter.
Ti2AlCTi3AlC2Ti3SiC2 composites in the TiAlSiC quatern-
ary system were synthesized by SPS starting from Ti, Al, Si and
carbon black powders [772]. Dense products were obtained at
1100 and 1200 8C (heating rate 80 8C/min) with a holding time of
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
8 min. For samples obtained at 1100 8C, two kinds of grains
appeared, a plate like one with grain size of 16 mm and an equiaxed
one with grains of 5 mm. Distribution of grains was not homo-
geneous. In contrast, for samples obtained at 1200 8C, these two
kinds of grains exhibited smaller difference in grain size in a range
512 mm and distribution was more homogeneous.
2.10.5. Zirconia-containing composites
SPS (Eltech Co., Korea) processing of yttria (2, 2.5, 3 mol%)-
stabilized-ZrO2/30 vol.% ZrB2 composites was carried out at
1200 8C (600 8C/min heating rate) with a holding time of 5 min
at 40 MPa [773]. The developed composites reached high density
in the range 9598.5% of the theoretical value. Full densication
was also obtained by HP and HIP under higher temperature (1400
1450 8C), higher pressure (110 MPa) and longer duration time (1 h)
as compared to SPS. SPS compacts exhibited ne microstructure
with ZrB2 having an average grain size of about 23 mm and ZrO2 in
the range 100300 nm. Moreover, it was found that ZrO2
tetragonal structure was retained after SPS. The ZrO2/30 vol.%
ZrB2 showed optimum hardness in the range 1214 GPa. Tough-
ness varied between 6 and 11 MPa m1/2 depending on Y2O3
stabilization in the ZrO2 matrix.
2 mol% yttria-stabilized-ZrO2/TiN composites (2YZrO2/TiN)
with 3590 vol.% TiN content were densied by PECS (HP D 25/1,
FCT Systeme, Germany) at 1500 8C (200 8C/min heating rate) for
2 min at 56 MPa [774]. All sintered sample, except the one with
90 vol.% TiN, exhibited full density after 2 min dwelling time.
Samples with 35 and 40 vol.% TiN showed a densication behavior
similar to that of pure 2YZrO2, where full densication was
reached before the sintering temperature and pressure were
achieved. It was also found that when changing matrix phase from
2YZrO2 to TiN, densication took place at longer times and 813%
residual porosity had to be removed during the dwell period at
1500 8C. The mechanical and electrical properties of the compo-
sites were also analyzed as a function of TiN content.
ZrO240 vol.%WC ceramic composites were fully densied by
PECS at 1450 8C (heating rate 200 8C/min) within 4 min under an
applied pressure of 60 MPa [775]. The inuence of the size and
morphology of the WC starting powders as well as the type and
amount of ZrO2 stabilizers on the mechanical properties of the
composites were investigated. It was observed that 2 mol% Y2O3-
stabilized-ZrO2 matrix exhibited better mechanical properties, i.e.
Vickers hardness of 16.2 GPa, toughness of 6.9 MPa m1/2 and
exural strength of 2000 MPa, as compared to 1.75 mol% Y2O3
stabilized and 1 mol%Y2O3 + 6 or 8 mol%CeO2 co-stabilized ZrO2
WC composites (14.5 GPa hardness, 6.4 MPa m1/2 toughness and
900 MPa exural strength).
The FAPAS method was applied for the simultaneous synthesis
and densication of WSi2 and WSi220 vol.%ZrO2 composite from
W, Si and ZrO2 powders [776]. Complete synthesis and densica-
tion of WSi2 and WSi220 vol.%ZrO2 was achieved in about 1 min,
under a pressure of 60 MPa, at 1220 and 1250 8C, respectively. For
the case of WSi2/20vol.%ZrO2 obtained at 60 MPa, it was found
that the 17.5% of the total shrinkage took place prior the ignition
while the remaining 82.5% occurred during synthesis. The
corresponding values for WSi2 were 25.8 and 74.2%. The nal
relative densities of the synthesized products were investigated
as a function of the applied pressure. It was found that when
pressure was increased from 10 to 60 MPa, relative density of the
monolithic WSi2 changed in the range 92.097.8%, while that of
WSi2/20 vol.%ZrO2 varied in the range 93.097.5%. Grain sizes of
WSi2 were found to be larger as compared to the composite,
suggesting that ZrO2 addition was effective in reducing grain
growth. Vickers microhardness and fracture toughness were also
increased by the addition of 20 vol.% of ZrO2.
219
2.10.6. Borides-containing composites
SPS was employed to investigate the synthesis of (Ti,W,Cr)B2
solid solution from elemental powders [112]. The synthesis and
simultaneous consolidation was performed at different tempera-
tures. Nearly pure solid solution was synthesized at 1900 8C for
10 min under an applied pressure of 64 MPa. Both density and
microhardness exhibited a dependence on temperature, thus
drawing a signicant augmentation from 74 to 94% and from 7 to
22.7 GPa, respectively as temperature increased in the range 1400
1900 8C.
TiB2B4C composites were prepared using the P2C technique
starting from powder mixture of TiB2 and B4C [777]. The starting
powders were mixed in different weight ratio of TiB2 and B4C and
then consolidated to near theoretical density by P2C at 1700 8C
under a pressure of 88 or 54 MPa, for 10 or 30 min depending on
the composition of the starting mixture. No pulsed voltage was
applied to composite powder mixture prior to consolidation since
it was previously revealed that no signicant improvement in
sinterability occurred when pulsing powders. Microhardness
measurements revealed a gradual increase in hardness with an
increase of TiB2 content in the starting mixture. It was also found
that exposure time and applied pressure signicantly affect
properties and microstructure. Specically, conditions adopted
(10 min, 88 MPa) to sinter B4C5 wt.%TiB2 and B4C15 wt.%TiB2
samples promoted high hardness and ner microstructure as
compared to B4C25 wt.%TiB2 sample (30 min, 54 MPa). The latter
one exhibited signicant particles size growth and grain coarsen-
ing due to longer exposure time to temperature.
The inuence of consolidation temperature on microstructure
development and microhardness of TiB2B4C composites obtained
by P2C technique was also investigated [778]. Temperature was
varied from 1650 to 1800 8C at 54 MPa with a dwell time of 30 min.
A signicant increase in particle size and grains was observed for
samples consolidated at 1800 8C as compared to composite
samples obtained at lower temperature (cf. Fig. 107). Microhard-
ness increased from 33.79 to 45.16 GPa as temperature was
augmented from 1650 to 1700 8C, respectively, and subsequently
decreased for further increase in consolidation temperature
(30.47 GPa at 1800 8C). The obtained results suggested that
1700 8C was the optimal temperature for consolidation.
Dense nanometric TiB2TiC composites were recently obtained
by FAPASA apparatus using elemental Ti, C and B powders that had
been mechanically activated by high energy ball milling [779].
Specically, two different route were used: (1) reactants were ball
milled to produce TiB2 and TiC products which were subsequently
consolidated by FAPASA; (2) reactants were ball milled without
product formation and then reacted/consolidated by FAPASA. In
both cases heating was performed by the application of AC current
in two steps, 800 A for about 5 min and 1800 A for 3 min, under a
pressure of 30 MPa. It was found that no signicant amount of TiB2
and TiC were formed until after 3 h of milling treatment and before
sintering. Dense TiB2TiC composites with relative density ranging
from 96.3 to 98.6% were obtained and no signicant changes with
milling time were observed, regardless of whether a product was
formed during milling or not. In contrast, the microhardness
showed a strong dependence ranging from 9.3 to 20.6 GPa as the
milling time increased in the range 110 h. This result was
attributed to the difference in crystallite size.
The simultaneous synthesis and consolidation of the TiC/TiB2
composite has been investigated starting from Ti, B4C and C
powders using SPS (SPS 515, Sumitomo Coal Mining) under current
controlled mode [780]. In particular, the mechanism of formation
of the composite TiCTiB2 was studied by applying a constant
pulsed electric current of 800 A and mechanical pressure of
20 MPa, for different time intervals, ranging from 1 to 10 min. It
220 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 107. Optical micrographs of the polished and etched surface of TiB2B4C samples consolidated at 1650 8C (a); at 1700 8C (b) and 1800 8C (c), showing agglomeration of the
B4C phase (gray) of varying sizes and shapes. Adapted from Srivatsan et al. [778].

was found that the application of the current for 60 s did not result The effect of ball milling pre-treatment of the starting Ti, B4C
in signicant interaction between reactants. As the reaction time and C powder mixture on the synthesis of dense TiC/TiB2
was increased to 2 min, besides reactants, the desired end-phases, composites was recently investigated through the combined use
TiB2 and TiC, were also present in the nal product. It was found of a SPEX mill and SPS [781]. Specically, the milled powders were
that TiC is the rst phase formed, while TiB2 formation occurred processed in SPS under optimized operating condition (I = 1100 A,
afterwards. Two intermediate borides were also detected, i.e. TiB P = 20 MPa, 4 min dwell time). It was seen that when unmilled
and Ti3B4, which were gradually converted to TiB2 as the SPS reactants were used, amorphous carbon was converted to TiC
holding time was augmented. A complete conversion to the
desired product was achieved after 8 min.
In addition, the dependence of the synthesis time t*, i.e. the
minimum time interval during which the applied current results in
complete conversion, on the current intensity was investigated.
The time required for full conversion decreased from 960 to 180 s
as the current was augmented from 700 to 1100 A as shown in
Fig. 108. The effect of the applied electric current on product
densication was also investigated. It was demonstrated that
higher applied currents produce denser composites (cf. Fig. 109).
Specically, while the relative density of the end product obtained
when a current intensity of 800 A is applied for 8 min is about 84%,
it increases up to 87% when 1100 A are provided for 3 min.
Moreover, to reach relatively high dense products the electric
currents needs to be applied for time intervals longer than those
required for achieving complete conversion. A pure dense product
with a relative density of 98% was obtained when an electric pulsed
current of 1100 A and a mechanical pressure of 20 MPa were Fig. 108. Effect of the applied current on the time needed to obtain full conversion of
applied for about 4 min, 1 min after full conversion was achieved the initial reactants into the nal desired TiCTiB2 product (P = 20 MPa). Adapted
(cf. Fig. 110). from Locci et al. [780].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 109. Effect of applied electric current on the density of the obtained spark
plasma sintering TiCTiB2 samples (P = 20 MPa, theoretical density = 4.678 g/cm3).
Adapted from Locci et al. [780].
through a combustion reaction with Ti, while the complete
conversion was achieved through a relatively slow reaction
between Ti and B4C. In contrast, powder ball milled for 24 h
reacted completely under combustion regime. SPS product density
was observed to increase from about 97 to 100% of the theoretical
value when the original powders were milled for 6 h, while further
increase of the milling time led to a slight decrease in product
density.
AlN-(050 wt.%) TiB2 composites doped with 6 wt.% Y2O3 were
sintered by SPS (2040, Sumitomo Coal Mining Co.) under a uniaxial
pressure of 30 MPa, with a heating rate of 150 8C/min, for 4 min at
different temperatures in the range 15401610 8C depending on
composition [782]. All samples were densied to near theoretical
density (98%). XRD analysis revealed that AlN and TiB2 were the
major phases, while YAlO3 and Y3Al5O12 were the main secondary
phases depending upon the AlN/Y2O3 ratio. It was also found that
mechanical properties of the sintered samples increased with TiB2
content. Crack deection was found to be main toughening
mechanism.
The synthesis of TiNTiB2 nanocomposites was performed
by SPS (1050 Sumitomo Coal Mining, Co.) starting from Ti, BN and
Fig. 110. Densities of TiCTiB2 end products obtained by spark plasma sintering as a
function of the application time of the applied current (I = 1100 A, P = 20 MPa).
Adapted from Locci et al. [780].
221
B mechanically activated powders [783]. Specically, synthesis
and simultaneous densication were performed at 70 MPa by
heating reactants for times ranging from 1 to 12 min at a rate of
100 8C/min. Products consisted of dense (9096% relative den-
sities) nanometric TiNTiB2 with TiN and TiB2 crystallite sizes in
the range 3771 nm and 59125 nm, respectively.
The NbC and NbB2 powders, obtained by MASHS process, were
used as starting material to fabricated NbC/NbB2 compacts by SPS
at 1800 8C (10 min dwell time) [784]. Compacts with relative
density of 94%, ne grain size and homogeneous microstructure
were obtained. The Vickers hardness was of 19.8 GPa, which
results higher than 14.3 and 16.6 GPa for the compacts densied
from 2Nb/2B/1C without MASHS and commercial powders of
NbC/NbB2, respectively.
Compacts for high temperature structural application with
different composition in the NbSiB system were prepared by SPS
according to three different routes: (1) blending elemental
powders and sintering blended powders; (2) pre-sintering blended
powders, milling pre-sintered compacts and sintering pre-sintered
milled powders; (3) mechanical alloying elemental powders and
sintering MA powders [785]. Densication was performed by SPS
at different temperatures in the range 17732073 K for 5 min
under a pressure of 40 MPa. Density of MA powder compacts was
generally lower than those of compacts obtained following routes
(1) and (2). Better results in terms of products composition and
microstructure features were obtained when starting from pre-
sintered blended powders. Compacts with composition in the line
Nb5Si3Nb5Si3B2NbB2 showed high hardness at room tempera-
ture and high compressive strength at high temperature as
compared to those with composition away from the line. Hardness
and strength decreased with increasing volume fraction of NbSi2.
Regarding the oxidation resistance, Nb5Si3B2 was found to be
superior to Nb5Si3, but signicantly lower than NbSi2.
High dense MgB2, MgB2(5 mol%)SiC and MgB2(5 mol%) B4C
ceramics have been recently fabricated by the FAST method [351].
Specically, MgB2 was consolidated at 960 8C (190 K/s heating
rate) for 280 s, under a pressure of 63 MPa, while doped ceramics
were sintered at 1000 8C (200 8C/min heating rate) with a holding
time of 120 s for MgB2(5 mol%)SiC and 160 s for MgB2(5 mol%)
B4C, respectively, at 63 MPa. All sintered samples had a relative
density above 90% of the theoretical values. The smaller density
was observed for MgB2(5 mol%) B4C, because of a non-complete
chemical reaction between two components and probably due to a
lower sintering temperature. Moreover, the onset temperature of
the densication process was found to be lower (920 8C) for pure
MgB2 sample, and higher for the doped superconductor samples
(955 and 960 8C for MgB2(5 mol%)SiC and MgB2(5 mol%) B4C,
respectively). The XRD pattern for the undoped samples revealed
that the main phase was MgB2 with MgB4 and MgO as minor
impurities. The latter phases were found also in the doped samples.
The addition of SiC resulted in the formation of an extra impurity
phase MgSi2 for MgB2(5 mol%)SiC ceramic. Moreover, it was
found that all samples had the same Tc = 38.5 K, while super-
conducting transition width, impurities and crystal quality were
different depending on the doping.
Ultra-high temperature HfB230 vol.%SiC ceramics were suc-
cessfully prepared by SPS (FCT Systeme GmbH, Rauenstein,
Germany) starting from a mixture of HfB2 and b-SiC [85,786].
Full densication was achieved at 2100 8C (heating rate 100 8C/
min), with a dwell time of 2 min, under a pressure of 30 MPa (cf.
Fig. 111). The entire SPS process lasted about 30 min. The XRD
analysis detected a limited amount of HfO2 in addition to HfB2 and
SiC. Microstructure and thermomechanical properties of SPS
samples were compared to those ones obtained by the reactive
HP (RHP) process. In the latter case, a mixture of Hf/Si/B4C (molar
222 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 111. Relative density (rd) vs. time of HfB2SiC samples prepared by spark plasma sintering (a) and hot pressing (b). The dot part of the densication curves covers the
isothermal stages. Adapted from Bellosi et al. [85].
ratio 2.2/0.8/1) was in situ converted into HfB2SiC and then
directly hot pressed. Complete densication (99.2%) was obtained
at 1950 8C (cf. Fig. 111), at 50 MPa of applied pressure with a
holding time of 10 min, after a complete thermal program which
lasted about 3 h. SEM microanalysis showed a grained structure
with uniformly faceted HfB2 grains being the SiC particles
intergranularly dispersed within the diboride skeleton, for both
SPS and RHP systems. Some residual microcracking was also
observed. It was also found that the SPSed specimens exhibited
good fracture toughness and exural strength. In particular, the
values measured at room temperature did not decrease appreci-
ably at 1500 8C. In contrast, the RHP samples did not retain the
original exural strength at high temperature. The role played by
SiC in enhancing densication of HfB2 during SPS was also widely
discussed [87].
The densication behavior, microstructure and properties of
HfB2SiC were compared with similar systems obtained by HP
[85]. It was found that a temperature of 1900 8C (heating rate 8 8C/
min) was needed for HfB2SiC when sintering by HP. In addition, it
was also seen that SPS allowed dense materials to be prepared
without the addition of sintering aids. In contrast, by employing HP
at temperature below 1900 8C, the nal relative densities of
additive-free HfB2SiC did not exceed 85%.
Experiments were also performed by adding 2 vol.% of TaSi2 as
sintering aid to HfB2 and SiC mixture [787]. The effect of TaSi2
addition on the sintering behavior of HfB2SiC was investigated
comparing SPS and HP technique. From XRD analysis, it was seen
that TaSi2 phase disappeared in the sintered compacts, and gave
rise to cubic (Ta, Hf) mixed carbides. Both SiC and TaSi2 were
recognized as activators of an enhanced sinterability of HfB2 at
elevated temperatures. It was found that the presence of a liquid
phase within the temperature range 14001800 8C favored not
only rearrangements of loose powder particles, but also more
effective heat transfer. TaSi2 was found to be not fully benecial for
improving the resistance to oxidation. In general, compared to a
composition free of network modiers, the external borosilicate
glass modied by Ta increased its own permeability to oxygen.
The fabrication of dense HfB215 vol.%MoSi2 composites was
investigated by taking advantage of SPS (FCT Systeme GmbH,
Rauenstein, Germany) technique [788]. Starting materials con-
sisted of HfB2 and MoSi2 commercial powders. Sintering was
performed at 1750 8C (100 8C/min heating rate) for 5 min at
30 MPa. A relative density of about 95% was obtained after
consolidation in SPS. Sintered specimens exhibited a ne structure
with some residual porosity. It was also found that the addition of
MoSi2 led to an improvement of the mechanical properties as
compared to monolithic HfB2. Results were also compared to those
obtained after consolidation by HP at 1900 8C (900 8C/h heating
rate) and P = 30 MPa. The nal microstructures were very similar,
but HP samples exhibited higher density (99%) and better
mechanical properties.
With the nal goal of obtaining fully dense ZrB225 vol.%SiC
composite (ZrB2/SiC molar ratio equal to 2), two different synthesis/
sintering routes have been recently proposed [789]. Both processes
start from commercial powders Zr, B4C and Si, and take advantage
of the SPS apparatus. Using the RSPS (Reactive Spark Plasma
Sintering) method, it was possible to synthesize and consolidate in
a single step the desired UHTC material. An investigation of the
evolution of the synthesis process, revealed that, under the
experimental conditions considered (T = 1900 8C, holding time
10 min, P = 20 MPa), the initial reactants were transformed
gradually to ZrB2 and SiC, thus reaching their complete conversion
within 8 min of SPS total time (cf. Fig. 112). However, in order to
produce highly dense samples, the electric current needed to be
applied for time intervals longer than those required for obtaining
the complete conversion (cf. Fig. 113). Finally, a pure and
completely dense product (99.5%) was obtained when the total
SPS time was 20 min (cf. Figs. 113 and 114). The second synthesis/
sintering route, i.e. SHS-SPS, consisted in two steps. Specically, the
starting reactants were rstly reacted by SHS to form the ZrB2SiC
composite. Thus, the obtained powders, were subsequently
consolidated by SPS. As shown in Fig. 115, it was found that in
this case the optimal operating conditions able to guarantee the
obtainment of a fully dense material (>99.5%) were (T = 1600 8C,
total time = 30 min) or (T = 1800 8C, total time = 20 min), while the
applied pressure is equal to 20 MPa. Regarding the characteristics
of the obtained products investigated, i.e. hardness, fracture
toughness, and oxidation resistance, the obtained results are
similar and, in some cases, better as compared to similar UHTC
products synthesized by competitive methods. In particular, it was
found that Vickers hardness and fracture toughness were about
15.9  0.4 GPa, and 4.1  0.6 MPa m1/2, respectively, when consider-
ing RSPS. On the other hand, for the case of SHSSPS method, it was
found that Vickers hardness value using 1 kg load was about
16.7  0.4 GPa, while fracture toughness was 5.0  0.3 MPa m1/2.
These values are slightly better than those obtained when considering
products prepared by RSPS.
ZrB2 reinforced by nano-SiC whiskers has been recently
prepared by SPS (510L Sumitomo Coal Mining) [790]. Specically,
a mixture of commercially available ZrB2 and b-SiC (0, 5, 10,
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 112. XRD patterns of ZrB2SiC RSPS products obtained for different values of the
time interval during which the pulsed electric current is applied (T = 1900 8C,
heating rate = 190 8C/min, P = 20 MPa): (a) Reactants; (b) t = 3 min; (c) t = 4 min; (d)
t = 4.5 min; (e) t = 5 min; (f) t = 5.5 min; (g) t = 6 min; (h) t = 8 min and (i) t = 10 min.
Adapted from Licheri et al. [789].
Fig. 113. Densities of ZrB2SiC end-products obtained by RSPS as a function of the
SPS holding time tT (T = 1900 8C, heating rate = 190 8C/min, P = 20 MPa). The dotted
line indicates the theoretical density of ZrB2SiC (ZrB2/SiC molar ratio equal to 2).
Adapted from Licheri et al. [789].
223
Fig. 114. SEM back-scattered micrographs of RSPS ZrB2SiC product at different
magnications (a) 200 and (b) 2000 (TD = 1900 8C, heating time = 10 min, total
time = 20 min, P = 20 MPa). Adapted from Licheri et al. [789].
Fig. 115. Effect of dwell temperature on relative density of SPSed ZrB2SiC powders
synthesized by SHS (heating time = 10 min, P = 20 MPa.). Adapted from Licheri et al.
[789].
224 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
15 vol.%) were used as starting materials along with AlN (0, 3,
5 vol.%) and Si3N4 (0, 3, 5 vol.%) added as sintering aids.
Densication was performed at 1550 8C with a holding time of
5 min under a pressure of 40 MPa. It was found that the addition of
SiC whiskers improved densication and inhibited grain growth of
ZrB2-based ceramics. The relative density of ZrB2SiC composites
reached the maximum value of 97% of the theoretical one with an
average grain size of 23 mm (cf. Fig. 116). Mechanical properties
of ZrB2SiC ceramics increased with increasing SiC volume
fraction. In particular, exural strength and fracture toughness
changed from 416 to 545 MPa, and from 5.46 to 6.81 MPa m1/2,
respectively, as the SiC content was augmented in the range 0
15 vol.%. Moreover, it was observed that the relative density of
ZrB2SiC composites increased by the addition of AlN and Si3N4.
Full density (100%) was achieved for ZrB210 vol.%SiC with the
addition of 5 vol.% AlN.
ZrB2SiC was also recently synthesized by reactive sintering
RSPS (FCT Systeme GmbH, Rauenstein, Germany) at different
temperatures in the range 17501800 8C, for 5 min, at 50 MPa,
with a heating rate of 100 8C/min [791]. The maximum relative
density of 96.6% of the theoretical value was achieved at 1800 8C.
ZrB2/1520 vol.%MoSi2 composites were recently fabricated by
SPS at 1750 8C (100 K/min heating rate, 30 MPa pressure, 7 min
holding time), starting from commercial powders of ZrB2 and
MoSi2 [85,792]. For the sake of comparison, sintering was also
carried out using HP and pressureless sintering at 1800 and
1850 8C, respectively. Near fully dense materials (9899%) were
fabricated. Vickers hardness, Youngs modulus and the linear
thermal expansion coefcient were similar for all samples. A ne
microstructure was observed for all the specimens. However,
when considering HP and SPS samples, they resulted negatively
Fig. 116. Scanning electron micrographs of polished and acid-etched sections of the ZrB2SiCw composites: ZB = ZrB2, ZBSw-1 = ZrB25 vol.% SiCw; ZBSw-2 = ZrB210 vol.%
SiCw; ZBSw-3 = ZrB215 vol.% SiCw. Adapted from Wang et al. [790].
affected by the formation of silica-based phases, which caused the
degradation of the high temperature strength.
ZrB2 and ZrC powders, synthesized by MASHS in air from Zr/B/
C (2:2:1) mixture, were densied by SPS (SPS 510L Sumitomo Coal
Mining Co.) at 1800 8C, for 5 min under an applied pressure of
40 MPa [793,794]. For the sake of comparison, commercial
powders mixture ZrB2/ZrC (1:1) were also compacted by SPS.
The composite obtained using the MASHS powders exhibited
higher relative density (98%) and better mechanical properties, i.e.
Vickers hardness of 17.8 GPa and fracture toughness of
3.8 MPa m1/2, as compared to compact from commercial mixture
(89% relative density, 16.6 GPa Vickers hardness and of
3.4 MPa m1/2 fracture toughness). These ndings were explained
considering the ner and more homogeneous microstructure
obtained from MASHS powders.
ZrB2ZrC with eutectic composition (ZrB2:ZrC = 59.9:40.1%)
was prepared by SPS at 1800 8C for 5 min dwell time, at 50 MPa
from attrition-milled ZrB2 and ZrC powders [795]. Grain orienta-
tion distribution showed that (0 0 0 1) planes of ZrB2 in the SPS
compacts were weakly oriented in direction normal to the
specimens surface, while ZrC grain had a random orientation.
High angle grain boundaries were found to be prevailing with
respect to low angle boundaries.
The effect of lanthanum addition (15 wt.%) on the sintering
behavior of ZrB2ZrC composites during SPS process was also
investigated [796]. When adding 3 wt.% of lanthanum at the
optimum sintering conditions (1800 8C, 5 min dwell time, 50 MPa)
full-dense product (99% relative density) was obtained. From
microscopic investigation, it was found that lanthanum was a very
effective sintering aid for ZrB2ZrC composites. Lanthanum
containing phase crystallizes at the grain boundaries from the
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 117. SEM back-scattered micrographs of SPS ZrB2ZrCSiC product at different magnication: (a) 1000 and (b) 10000 (T = 1800 8C, t = 10 min). Adapted from Licheri
et al. [797].
liquid phase during SPS without decreasing of the mechanical
properties. This nding seemed to be very interesting, since the
addition of lanthanum inhibited densication of the same com-
position ZrB2ZrC during pressureless sintering.
SHS-SPS method was recently used to fabricate ZrB240
vol.%ZrC12 vol.%SiC. Complete densication (cf. Fig. 117) was
achieved under the optimal conditions of 10 min total time and
with a maximum temperature of 1800 8C at 20 MPa [797].
Regarding mechanical properties of the completely dense product
obtained under the optimal conditions, it was found that Vickers
hardness value using 10 kg load was about 16.9  0.2 GPa, while
fracture toughness was 5.99  0.47 MPa m1/2.
ZrB230ZrC10SiC (vol.%) composite was fully densied by SPS
at 2100 8C (100 8C/min heating rate) and 30 MPa for 2 min dwell
time [85,798]. For comparison, the same composition was also
densied through hot pressing with the addition of a sintering aid
(3.7 vol.%Si3N4) at 1870 8C and 40 min of soaking time. In both
cases full density was achieved and sintered specimens exhibited
similar microstructure features. The comparison between SPS and
HP applied to a poorly sinterable systems like ZrB2ZrCSiC
showed the former to be a very rapid fabrication process (SPS
23 min instead of 140 min by HP) leading to rened and
homogeneous microstructure. Moreover, all SPS sintered speci-
mens had a ne microstructure with average grain sizes of about
1.52 mm, and free of residual foreign phases, in contrast with the
corresponding hot pressed materials.
Three kinds of composites, ZrB2SiCZrC, ZrB2SiCZrN and
ZrB2SiCAlN, were synthesized in situ by RSPS using Zr, Si, B4C, BN
and Al as starting materials [791]. RSPS (FCT Systeme GmbH,
Rauenstein, Germany) process was carried out for 5 min, at 50 MPa,
with a heating rate of 100 8C/min. It was found that by increasing the
sintering temperature from 1750 to 1800 8C the samples density
signicantly increased, thus indicating that temperatures as high as
1800 8C are needed to achieve complete densication. Instead of
forming ZrN and AlN, Zr(C,N) solid solution was detected in ZrB2
SiCZrN and ZrB2SiCAlN composites. When compared to HP
(T = 1800 8C, heating rate 10 8C/min, P = 20 MPa), SPS resulted in
more homogeneous and ner microstructure.
2.10.7. Other ceramicceramic composites systems
TiC/C composite was synthesized by reaction between sand-
wiched Ti foils and nanocrystalline graphite powders using SPS (Dr.
Sinter 1050 Sumitomo Coal Mining Co.) [799]. Specically 40 Ti
layers coated with carbon were placed in a graphite die to form a
pellet which was heated in SPS to 1450 8C (100 8C/min heating
rate) under a pressure of 40 MPa for 2 min. The actual temperature
of the samples was estimated to be 15501600 8C. After sintering,
Ti foils coated with graphite powders were transformed into TiC/C
composite. The original layered structure disappeared after SPS,
but carbon distribution somehow indicated the traces of the layers.
225
Although the prepared TiC/Ti nanocomposite had a porosity of 15%,
the bending strength and fracture toughness at room temperature
achieved 480 MPa and 6.5 MPa m1/2, respectively.
Full-dense (9899% relative density) ultra-hard WC-6 wt.%ZrO2
nanocomposites were prepared by SPS at 1300 8C for 5 min under a
pressure of 30 MPa, starting from submicron sized WC powders
and nanometric yttria-stabilized-ZrO2 powders [86]. After SPS
sintering, samples retained their original ne microstructure with
100 nm ZrO2 particles and submicrometric WC grains. It was also
found that the attainment of full densication was independent on
the yttria stabilizer content in ZrO2 particles. Full densication was
also obtained by sintering through pressureless method, at 1700 8C
with a holding time of 1 h. Independently on the sintering process,
i.e., SPS or pressureless sintering, good hardness (2124 GPa),
which was higher than that of SPS processed WC6%Co compacts
(15 GPa), was obtained.
The C40 Mo(Si0.75Al0.25)2/(10, 20, 30 vol.%) Al2O3 composites
were consolidated by SPS (Dr. Sinter 2050, Sumitomo Coal Mining)
at 1350 8C for 3 min under a pressure of 75 MPa [800]. Starting
Mo(Si0.75Al0.25)2/xAl2O3 was obtained from elemental Mo, Si, and
Al powders with the addition of Al2O3 by mechanical alloying. It
was found that the microstructure and properties of the
Mo(Si0.75Al0.25)2/(10, 20, 30 vol.%) Al2O3 sintered materials was
strongly dependent on phase composition of MA powders.
Specically, for Mo(Si0.75Al0.25)2 with 10 and 20 vol.%Al2O3 compo-
sites, decomposition of Mo-solid solution and the presence of
Mo5Si3, formed during MA, were observed along with the formation
of micron and submicron structures. The corresponding hardness
and toughness were 13.914.6 GPa and 1.781.8 MPa m1/2, respec-
tively. In contrast, the addition of 30 vol.%Al2O3 suppressed the
formation of solid solution during milling and led to the C40
Mo(Si0.75Al0.25)2/Al2O3 structure with intergranular distribution of
Al2O3. This resulted in a drop of the hardness to 10.2 GPa and in an
improvement of fracture toughness to 3.67 MPa m1/2.
Along these lines Mo(Si,Al)2/SiC and Mo(Si, Al)2/ZrO2 compo-
sites were also produced by SPS [800]. The operative wear
mechanism and wear resistance were analyzed and discussed as a
function of the microstructure and the mechanical properties of
the samples. SPS of mechanical alloyed powders led to the
formation of ultra-ne micron and submicron Mo(Si,Al)2 compo-
site structure containing retained Mo and Mo5Si3 phases apart
from Mo0.63Si0.27Al0.10 wt.%/30 vol.%Al2O3. Some porosity (about
2 vol.%) was observed for Mo0.63Si0.27Al0.10, Mo0.63Si0.27Al0.10/
10 vol.%Al2O3 and Mo0.63Si0.27Al0.10/20 vol.%Al2O3, while all other
samples have been found fully dense after sintering. In general,
Mo(Si0.75Al0.25)2-matrix composites exhibited high hardness, in
the range 12.914.8 GPa, and improved fracture toughness by the
addition of the second phase.
Using PAS process, submicron sized a-silicon nitride powders,
with 5 wt.%Y2O3 and 5 wt.%Y2O3 + 5 wt.%MgAl2O4, were consoli-
226 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
dated to 99% of the theoretical density at 1750 8C in less than 5 min
[801]. No stress or temperature effects were observed indicating
that consolidation occurred by liquid phase sintering. The PAS
process was found to preserve ne and equiaxed structure which
was effective in promoting superplastic deformation processes.
Dy2O3 (20 wt.%) dispersed carbides or nitride matrix compo-
sites were sintered using the SPS (Dr. Sinter 515S) technique
[802]. Specically, Dy2O3ZrC, Dy2O3TiC, Dy2O3ZrN, and
Dy2O3TiN composites were heated at 17732000 K (75 K/min
heating rate) for 14 min. The effect of additive on densication
of carbide- and nitride-based matrix was investigated. Densica-
tion of Dy2O3 dispersed composites was found to be enhanced as
compared to monolithic matrices. This nding was attributed to
the role of Dy2O3 in removing the oxide surface and enhancing
diffusion. The addition of Dy2O3 resulted also in an increase
of the relative density for all matrices except in TiN matrix
composites.
Dense composite materials (98.6% relative density) consisting
of Super Sendust (86.5Fe6Si4Al3.5Ni wt.%) and MgFe2O4, with
alloy/ferrite composition of 75/25 vol.%, were fabricated by SPS at
850 8C (830 8C/min heating rate) for 5 min at 130 MPa [803].
Microstructure observation revealed no apparent grain growth and
ne ferrite grains (0.6 mm) located at the grain boundaries of large
spherical Super Sendust alloy grains of 30 mm. Moreover, the
obtained composites exhibited high saturation magnetization
density and high electrical resistivity.
LiFePO4/C composite electrodes for rechargeable lithium
battery were prepared by SPS (515S Sumitomo Coal Mining Co.)
at 600 8C, 5 min [804]. The obtained composite consisted of 10 mm
sized agglomerates of LiFePO4 and C particles. This resulted in a
higher electrode density. Charged/discharged tests for the cell
using LiFePO4/C composites showed superior performance as
compared to the cells obtained using LiFePO4 and C blended
powders.
Transparent ceramics were fabricated through sintering by SPS
(Dr. Sinter 2050, Sumitomo Coal Mining) method starting from
nanocrystalline YAG powders with spherical morphology and
particle diameter in the range 34  17 nm [805]. The SPS specimens
exhibited relative density ranging from 83 to 99% by application of
100 MPa for 3 min at 12501550 8C as shown in Fig. 118. The average
grain size ranged between 180 and 1300 nm (cf. Fig. 118). Dynamic
densication to transparency was found to occur by nanograin
rotation and sliding mechanism.
Fig. 118. Relative density (RD) and mean grain size (GS) vs. SPS temperature of
nanocrystalline-YAG powder compacts uniaxially cold pressed at 100 MPa and
spark plasma sintered for 3 min at 100 MPa. Two different grain growth regimes
below and above 1400 8C are visible. Adapted from Chaim et al. [805].
SPS was also used to fabricate Ti2AlCTi3AlC2 composites
starting from TiC, Al, and Ti ball mixed powders [806]. Pure and
dense Ti2AlCTi3AlC2 composites were obtained when sintering at
1300 8C for 8 min at 30 MPa.
P2C method was applied to consolidated B4C powders, with
Al2O3, TiB2 and graphite (1 or 3 wt.%) added as sintering aids, at
1650 8C (heating rate 25 8C/min) for 5 min under a pressure of
32 MPa [287]. It was found that the relative density of B4C was
increased from 81 to 97% by the addition of 1 or 3 wt.%Al2O3. In
contrast, TiB2 and graphite did not show any signicant effect over
B4C density. Moreover, the 97%B4C + 3 wt.%Al2O3 dense samples
showed a little porosity, but some amount of Al as second phase
was also detected. From SEM investigations, it was seen that
B4C + 1 wt.%Al2O3 ceramics consisted of Al2O3 particles located at
the B4C boundaries. The density improvement in Al2O3-doped B4C
was believed to be due to pinning of B4C grain boundaries by Al2O3
particles, thus preventing microstructural coarsening.
2.11. HA-containing materials
Pure hydroxyapatite (HA) was rather easily sintered to high
density and has been reported to be fully densied at a
temperature as low as 800 8C, but higher temperature are required
for densication of oxide/HA composites. The temperature needed
was found to be dependent on the type and volume of the
reinforced material used [582]. For example, in the zirconium
oxide/HA system, sintering temperature as high as 1400 8C has
been employed.
The sintering behavior of HA powders, synthesized by reacting
orthophosphoric acid with calcium hydroxide, was studied at
different temperatures ranging from 850 to 1100 8C (50 8C/min
heating rate, 5 min dwell time), under a mechanical load of 30 MPa
on an SPS apparatus (SPS-1050 Sumitomo Coal mining) [807]. No
phase change was observed when the samples were sintered at
temperatures of 900 or 950 8C. However, when sintered at 1000
and 1100 8C, HA started to decompose and the formation of b-
tricalcium phosphate (b-TCP) was observed. The density increased
rapidly with the sintering temperature up to 950 8C (cf. Fig. 119).
After sintering at 950 8C for 5 min, the measured density was close
to the theoretical value, i.e. a relative density of 99.6%. Average
grain size and average grain area were found to increase with
temperature (cf. Fig. 120). Microhardness and Youngs modulus
increased with the sintering temperature up to 950 8C. It was
also reported that spray-dried HA powders made by reacting
Fig. 119. Relative density of HA sintered by SPS. Adapted from Gu et al. [807].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 120. Average grain size and grain area of HA. Adapted from Gu et al. [807].
orthophosphoric acid with calcium hydroxide were also con-
solidated by SPS (Dr. Sinter, SPS 1050, Sumitomo Coal Mining) at
1050 8C (100 8C/min) heating rate at pressure level of 30 MPa
[808]. Bioactivity and the formation of apatite layer on SPS
compacts were also investigated by soaking HA compacts in
simulated body uid.
HA powders prepared by spray-drying method were sintered by
SPS (Dr. Sinter, Sumitomo Coal Mining Co.) at different tempera-
tures in the range 7001200 8C (100 8C/min heating rate) for 5 min
under a pressure of 30 MPa [809]. For the sake of comparison HA
samples were prepared also by HP. Fully densied samples were
obtained by SPS at 700 8C, while in case of the HP sintering, full
densication (>99%) was achieved at 1200 8C. The XRD results
showed that only HA was present after SPS at 700 8C or HP at
1200 8C, respectively. Equiaxed and very ne structure (500 nm
grains size) was obtained by SPS at 700 8C as compared to HP.
Grains coarsening was observed with increasing SPS temperature.
Large bone like apatite layer was observed on the surface of HA
samples prepared by SPS at 1200 8C after 2 days in simulated body
uid. No precipitation and growth of bone like crystals on HA
sintered by HP was observed.
SPS was also applied as post-treatment for plasma spray HA
coating [810]. HA powders were prepared by wet chemical
method and subsequently spray-dried in order to obtain sphe-
rical particles. A heat treatment at 900 8C was performed to
achieve complete crystallization. HA powders were then plasma
sprayed on a Ti substrate. Plasma-sprayed samples were cut into
3 mm disks and subjected to SPS sintering at various tempera-
tures (500700 8C) and duration (5 and 30 min) with a heating
rate of 100 8C/min and under a pressure of 10 MPa. Evolution of
crystallinity and microstructure was investigated. In particular, it
was found that HA decomposed during plasma spray and phases
such as b-TCP, a-TCP (a-tricalcium phosphate), tetracalcium
phosphate (TTCP), CaO and a large amount of amorphous calcium
phosphate (ACP) were present within the coating. In the case
of SPSed samples, the crystallinity increased with increasing
sintering temperature and the composition also changed. Speci-
cally, brief SPS duration aided the formation of metastable b-
TCP whose amount increased as temperature was augmented. On
the other hand, relatively prolonged SPS duration assisted the
formation of HA in the coating. HA coating treated in SPS for
5 min showed surface activity after in vitro incubation (up to 12
days) tests. The thickest apatite layer was found in the coating
sintered at 700 8C for 5 minutes.
227
Spheroidized HA powders, obtained by using a radio frequency
inductively coupled plasma (ICP) torch, were consolidate by SPS
(Dr. Sinter 1050, Sumitomo Coal Mining Co.) [811]. The powders
were rst heated to 600 8C with a rate of 200 8C/min and then
temperature was increased to 900, 1000, 1100, 1150 and 1200 8C,
respectively with a rate of 100 8C/min. A pressure of 34 MPa was
applied. The inuence of sintering temperature on densication
was investigated. It was found that by varying the sintering
temperature in the range 9001000 8C the specimens density
could be increased from 77.3 to 91.2%. Microstructure consisted of
many pores connected together without signicant grain growth.
With the increase of sintering temperature to 1100 and 1150 8C
pores become isolated and grain boundaries formed a continuous
network. Density reached 96.2% at 1100 8C (3 min holding time).
For higher temperature (1200 8C), the spheroidized powders
exhibited a signicant grain growth. The effect of sintering
temperature on the mechanical properties of the solidied sample
was also considered. The highest Youngs Modulus (105 GPa) and
hardness (6.2 GPa) were obtained after sintering at 1100 8C. In
vitro tests conrmed the bioactivity of the SPS samples.
In order to better elucidate the sintering differences of RF
plasma spheroidized HA using SPS and conventional sintering
methods, further experiments were performed [812]. Conven-
tional processing was conducted at temperatures in the range
10001400 8C using a dilatometer furnace under nitrogen for
various periods (2 and 5 h) at different heating rates (5, 10, 20 8C/
min). The effect of both sintering temperature and heating rate
on microstructure and phase composition was investigated. SPS
compacts exhibited near full density of 3.04 g/cm3 when sintered
at 1100 8C for 3 min (heating rate 100 8C/min), while a con-
solidated HA with a maximum density of 2.86 g/cm3 was
obtained by the conventional process at 1200 8C for 5 h at a
heating rate of 10 8C/min. It was also found that HA was the
dominant phase in the samples densied by SPS at temperature
between 1000 and 1200 8C. On the other hand, a large amount of
TTCP, and a-/b-TCP was detected in the ceramic samples
consolidated using the conventional process. Furthermore,
compared with those samples prepared by conventional route,
SPS samples exhibited ner grain size.
HA nanoparticles produced by hydrothermal synthesis were
consolidated by SPS (heating rate 100 8C/min; uniaxial mechanical
stress 50 MPa) [813]. For the sake of comparison, sintering was also
carried out starting from commercial powders. Regarding con-
solidation of hydrothermal HA powders, optimal sintering para-
meters were found to be 825 8C for 3 min, and compacts with
relative density of 98.6% were obtained. On the other hand,
commercial powders were consolidated at 950 8C for 3 min thus
reaching a relative density of 98.4%.
Transparent HA sintered body with high crystal orientation and
relative density of 99.7% was fabricated by PECS at 1200 8C with
heating rate of 50 8C/min under a pressure of 50 MPa [814]. The
orientation indexes of the planes parallel and perpendicular to the
pressure direction were also calculated.
Several types of HA powders with different average particle size
and morphology were consolidated by SPS [815]. Sintering was
performed at different temperatures in the range 8731273 K,
with heating rate of 100 K/min under pressure levels ranging from
22 to 66 MPa. Mechanical properties of HA sintered compacts were
evaluated as a function of sample porosity. In general, it was found
that three-point bending strength, compressive strength and
Youngs modulus decrease about exponentially with increasing
porosity.
HA and b-TCP ceramics were prepared by SPS (Dr. Sinter-511S,
Sumitomo Coal Mining Co.) at temperatures in the range 800
1000 8C for 10 min with a heating rate of 25 8C/min at a uniaxial
228 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
pressure of 60 MPa [816,817]. Transparent HA was obtained at
900 8C. The b-TCP ceramics sintered at 800, 900 and 1000 8C had
relative densities of 70, 95, and more than 99%, respectively.
Vickers hardness also increased from 2.5 to 5.0 GPa with increasing
sintering temperature. From microstructural investigation, few
pores were found after sintering at 800 and 900 8C and average
grain sizes were in the range 0.81.0 mm. Transparent b-TCP,
having almost no pores and grain sizes of 1.5 mm, was obtained at
1000 8C for 10 min.
Ultra-ne HAcalcium phosphate (HACaP) and ZrO2HA
calcium phosphate (ZrO2HACaP) obtained by radio frequency
suspension plasma spraying (RFSPS) were consolidated by SPS (Dr.
Sinter 1050, Sumitomo Coal Mining Co.) at 1000 and 1100 8C,
respectively, for 5 min under a pressure of 11.1 MPa [818,819].
Dense products (>96%) with nanomorphology were obtained.
After sintering, HACaP compacts were composed of HA, b-TCP,
and trace amounts of a-TCP. In the ZrO2HACaP compacts almost
all the t-ZrO2 phase was converted to c-ZrO2. HACaP compacts
exhibited better mechanical properties as compared to samples
consolidated by other conventional method. Furthermore the
mechanical properties improved in the presence of nano-ZrO2. The
HACaP compacts studied in vitro revealed a bioactive apatite
layer after 1 week immersion in simulated body uid.
HAZrO2 composites compacts with improved mechanical
properties were fabricated from combination of RFSPS and SPS
techniques [820]. Sprayed powders were sintered at 10501100 8C
at various sintering pressures ranging from 4.5 to 17.3 MPa for
5 min. Sintered compacts consisting of HA as major phase, a- and
b-calcium phosphate (TCP), cubic, tetragonal, monoclinic ZrO2 and
CaZrO3 were obtained. Phase composition did not vary appreciable
with pressure. It was also found that densication increased with
increasing sintering pressure. Specically, porosity was <3% when
sintering was performed at 17.3 MPa, whereas it resulted to be
about 42% at 4.5 MPa. In addition, fracture toughness was found to
increase with porosity. Possible reasons of these ndings were
discussed and a 2D model was proposed. It was also reported that
ZrO2HA (4060 vol.%) composites were sintered by SPS at 1100 8C
without any detectable decomposition of HA. It was found that SPS
is effective in increasing HA stability since the short duration
sintering process reduce, the loss of structural water from the HA
[821].
Laminated and functionally graded HA/yttria-stabilized tetra-
gonal zirconia (HA/Y-TZP) composites for orthopedic applications
were obtained by SPS [822]. HA and Y-TZP powders with
submicron sized particles were mixed by ball milling in order to
obtain four mixtures with different compositions of 10, 20, 30 and
40 wt.%Y-TZP, respectively. Functionally graded composites con-
sisting of symmetric layers with graded compositions were
subsequently fabricated using SPS (SPS 1050, Sumitomo Coal
Mining Co.). Sintering was performed at different temperatures
from 1100 to 1250 8C (heating rate 100 8C/min), and various
holding times (520 min) at 30 MPa. For the sake of comparison
pure HA compacts were also produced by SPS at 9501050 8C with
5 min holding time. Functionally graded HA/Y-TZP composites
were successfully densied at 1200 8C within 5 min by SPS. Y-TZP
grains were homogeneously dispersed in the HA matrix and the
average grain size of the HA in layered compacts was reduced by
half. In addition, no phase changes were observed. With increasing
sintering temperature to 1250 8C, HA decomposed into a-TCP
while the Y-TZP second phase (tetragonal ZrO2) remained stable.
On the other hand, there was no phase change when sintering HA
compacts at 1100 8C. HA/Y-TZP functionally graded composites
exhibited improved mechanical properties as compared with pure
HA compacts. In particular, the microhardness and Youngs
modulus increased stepwise from the pure HA layer to the
40 wt.%Y-TZP layer across the functionally graded laminated
composites.
Nanopowders of 40 vol.%HA + 60 vol.%t-ZrO2 (3Y) (Y-TZP)
synthesized by two step precipitation route have been sintered
by SPS (Dr. Sinter 1020, Sumitomo Coal Mining, Co.) [823].
Sintering was carried out at different temperatures at a heating
rate of 200 8C/min for 3 min, under a pressure of 50 MPa. After
holding at the sintering temperature, pressure was released and
samples were cooled below 600 8C in 2 min. HAZrO2 (3Y) compact
with a relative density of 97.3% of the theoretical value was
obtained at 1150 8C. HA and Y-TZP grains were found to be
homogeneously distributed in the bulk sample, with particle sizes
of about 100 and 50 nm, respectively. No reaction between HA and
ZrO2 was observed.
HA40 wt.% YSZ composites were fabricated by SPS starting
from submicrometric HA and YSZ powders [824]. Sintering was
carried out at 10501250 8C for 5 min. For comparison HA
compacts were sintered at 9001050 8C for 5 min. Dense HA
YSZ composites obtained at 1150 8C consisted of pure HA and YSZ
and no phase changes were observed. However when sintered at
1200 8C, HA started to decompose into TCP. Meanwhile, ZrO2
remained to be tetragonal phase, even when sintered at 1250 8C.
The density of the obtained specimens increased with increasing
sintering temperature from 1050 to 1200 8C reaching a maximum
of about 93% of the theoretical one. At 1250 8C, it slightly decreased
due to the decomposition of HA into TCP, the density of which was
lower than that of pure HA (cf. Fig. 121). Regarding product
microstructure, t-ZrO2 was found to be homogeneously distributed
in the HA matrix and located at the grain boundary of HA. After
sintering at 1200 8C, HA grains grew up to 1 mm. Furthermore,
mechanical properties increased with temperature and were found
to be signicantly higher than those of the pure HA.
Reinforced HA composites have been fabricated by SPS at 950 8C
(heating rate 100 8C/min, holding time 10 min, P = 20 MPa) [825].
Reinforcement were 20 vol.% chopped 316L bers of 1 mm length
and 5 mm diameter. Sintered compacts exhibited dense structure
but a mild degree of microcracking in the HA matrix and near the
316L bers was observed. A comparison with HP technique was
also carried out. Full-dense composites were obtained by HP under
875 8C at 140 MPa for duration of 180 min. Microcracks were still
found in the dense HA and near the 316L bers.
In order to improve mechanical properties of pure HA, further
experiments were performed by adding increased amount of
reinforcement bers to pure HA [826]. In addition, reinforced
bioglass-316L composites were also produced by SPS to investigate
whether the microcracking problem encountered in the HA316L
ber composites could be prevented. Specically, HA-and bioglass
Fig. 121. Relative density of the HA-YSZ composites vs. sintering temperature.
Adapted from Miao et al. [824].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
(45S5)-based composites reinforced with 30 vol.% 316L bers were
densied at 950 (heating rate 100 8C/min) and 850 8C (heating rate
50 8C/min), respectively. The pressure level on the specimens was
kept constant to 90 MPa throughout the sintering process.
Sintering duration was in the range 520 min. It was found that
the sintered HA-316L composites showed no decomposition of the
HA phase. Regarding the microstructure, a preferential orientation
of the 316L bers was observed. Microcracks were formed around
316L bers. As a result, HA-316L ber composites exhibited
decreased bending strength as compared to pure HA. In contrast,
the bioglass 45S5-316L ber composites showed no microcracks
and, thus, had improved bending strength as compared with the
pure 45S5 bioglass.
Ti3SiC2/HA composites with different amount of Ti3SiC2 (0
50 vol.%) were obtained by SPS (Dr. Sinter 1020 Sumitomo Coal
Mining Co.) at temperature of 1200 8C (heating rate 200 8C/min)
under a pressure of 60 MPa, with a holding time of 5 min [827,828].
The relative densities of all the samples were higher than 96% of
the theoretical value. From XRD analysis, it was seen that compacts
consisted only of HA and Ti3SiC2, thus indicating that no signicant
chemical reactions occurred between HA and Ti3SiC2. Mechanical
properties of the obtained composites were studied. It was seen
that the Vickers hardness decreased, while the elastic modulus
increased as the volume fraction of Ti3SiC2 was augmented.
Furthermore, the bending strength and the fracture toughness of
the ceramic composite was signicantly improved by adding
Ti3SiC2.
Nanostructured SiO2-doped hydroxyapatite (SiHA) was fabri-
cated by SPS [829]. Specically, amorphous SiHA powders were
prepared through an aqueous precipitation route by adding
different amounts of SiO2 (1, 3, 5 wt.%) to pure HA. Pure spray-
dried HA and spray-dried SiHA microsized powders were
subsequently consolidated in SPS (SPS 1050, Sumitomo Coal
Mining Co.) at 1000 8C with a dwell time of 3 min at a heating/
cooling rate of 100 8C/min. When starting from pure HA, no other
phases than HA were detected by XRD characterization. In
Fig. 122. Fracture morphologies of various HA-based SPS compacts: (a) ceramic HA; (b) ceramic 1SiHA; (c) ceramic 3SiHA and (d) ceramic 5SiHA. Adapted from Xu and Khor
[829].
229
contrast, when SiHA was densied under the same working
conditions, it was found that HA became less stable and the
secondary phase b-TCP was detected in all the compacts doped
with silica. It was also found that intensity of b-TCP peaks
increased as the amount of silica was augmented. After sintering,
the density of pure HA was about the 97.9% of the theoretical value,
and decreased with increasing of doping level, thus reaching a
value of 94.8% at 5 wt.% of silica. Furthermore, few pores were
observed in the pure ceramic HA compact while some inter-
granular porosity occurred in the SiHA samples, as shown in
Fig. 122. By measuring mechanical properties it was observed that
low hardness was obtained for the doped samples as a
consequence of the low bulk density. On the other hand the
Youngs modulus increased with increasing silica content. This fact
was mainly attributed to the ability of silica in suppressing grain
coarsening during SPS. Bioactive response was also taken into
account and it was observed that the presence of silicon and TCP in
SiHA samples enhanced cell proliferation ability when compared
to pure HA.
Due to its unique benecial properties such as antimicrobial
activity and corrosion resistance, silver has received much
attention for the fabrication of implant materials [830]. Regarding
this aspect, HAAg composites represent a valid bioceramic. HA
5 vol.%Ag composites were fabricated starting from both Ag-coated
HA powders synthesized by the electroless deposition process and
Ag ball milled HA powders. The analysis of the microstructure and
material properties depending on the initial powders was
performed. In both cases, sintering was performed at 40 MPa, at
1000 8C for 2 min. For the sake of comparison, pure HA was
sintered under the same conditions. The relative densities of the
SPSed samples were 96.4, 99.1 and 99.2%, when starting from pure
HA, Ag ball milled HA and Ag-coated HA powders, respectively. All
the samples consisted of HA and b-TCP. Equiaxed grains with size
of about 400800 nm were formed from pure HA. In the case of ball
milled HA5 vol.%Ag composite, some microcracks were observed
near the larger sized Ag grains (210 mm), while they were not
230 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
found at the interface with ne Ag particles (100200 nm). For the
case of the electroless deposited 5 vol.% Ag-coated HA composite,
Ag particles with less than 200 nm in diameter were found to
be homogeneously distributed in the HA matrix or at grains
boundaries. Also several twins and shrinkage cavities were
observed in the Ag particles. Regarding the mechanical properties,
it was found that hardness decreased with the addition of Ag. It
was also seen that with the addition of Ag particles, the value of
crack length decreased, being this fact an indication of the fracture
toughness increase. On the other hand, the bending strength in
electroless deposited Ag-coated HA was higher with respect to the
case of pure HA. However, its value strongly decreased in the ball
milled sample, due to the presence of microcracks and cavities near
the larger sized Ag particles.
Functionally graded materials by combining Ti or Ti alloys with
HA have been also developed to enhance mechanical properties of
HA [831]. A material for articial bone preparation with a radially
graded structure consisting of Ti in the centre and HA on the
surface was recently developed by SPS.
With the nal goal of improving mechanical properties of HA,
Ti(3090 vol.%)HA composites were prepared by SPS at 1150 8C
under 40 MPa [832]. The obtained high dense specimens were
characterized in terms of mechanical properties, biocompatibility
and osteoconductivity. It was found that the Youngs modulus of
the composites in the entire range of compositions was higher than
that of pure HA. Both the Vickers and the fracture toughness
increased with increasing Ti. No inammatory reactions were
observed around the implants in the entire range of composition.
Bone formation was better in HA-rich composites. From X-ray
analysis, Ti, HA and CaTiO3 were detected, being the presence of
the latter one supposed to be related to the high hardness and
biocompatibility of the composites.
A mixture of CaHPO42H2O and Ca(OH)2 was reacted to produce
HA through the SPS technique [833]. The mixed starting powders
were heated at different temperatures from 300 to 1200 8C, for
10 min at various pressure levels in the range 20670 MPa. For
comparison with SPS samples, the mixed powders were also
reacted at the temperature range 5001200 8C in air in a furnace. It
was found that CaHPO42H2O and Ca(OH)2 started reacting at
300 8C under high pressure (600 MPa) in SPS but reaction was not
complete. HA with small amount of impurities was obtained when
heating at 500 8C for 10 min under a pressure of 670 MPa. The same
product was obtained in furnace, where reaction started near
600 8C and resulted completed at 1200 8C. A linear relationship
between the temperature of HA formation and the pressure was
also observed when performing reaction with SPS. Specically, the
temperature increased with decreasing pressure. Actually, HA was
obtained in 10 min at 500, 600, 700, 1000, 1150 8C under 670, 600,
470, 120 and 20 MPa, respectively. Crystal sizes obtained at 500 8C
under 670 MPa were similar to that obtained at 1150 8C at 20 MPa.
2.12. Chalcogenides
SPS technique was used to fabricate the n-type Bi2(Te,Se)3
materials with both high mechanical and thermoelectric proper-
ties [834]. The starting alloys were prepared by the zone melting
method at 973 K. The solidied ingots were then crushed in order
to obtain powders at different sizes (96120, 120180 and 180
380 mm, respectively). Sintering was performed by SPS equipment
(SPS 2040) in the temperature range of 673713 K (heating rate
50 K/min) for 5 min (holding time) under a pressure of 60 MPa in
vacuum. The relative densities of the sintered materials were
higher than 98%. The mechanical properties were measured by
three-point bending test and results compared with those
obtained for the zone-melted ingots. It was found that bending
strength of the sintered materials increased slightly with the
decrease of particle size of the starting powders and, in particular,
it resulted to be higher (6782 MPa) with respect to that obtained
for the zone-melted materials (10 MPa). The improvement of
mechanical strength was attributed to the smaller grain size and
denser bonding between powders. This result was an indication of
the capability of SPS samples to sustain cutting load and improve
the reliability for the applications especially in miniature thermo-
electric modules. The optimal gure of merit, which is an
indication of the quality of the thermoelectric materials, reached
about the 90% of that of the zone-melted materials.
P-type thermoelectric Bi0.5Sb1.5Te3 compounds were prepared
by SPS at different temperatures, ranging from 300 to 420 8C,
starting from powders with particle sizes of 75, 76150, 151
250 mm, respectively [835]. As the sintering temperature
increased, the electrical conductivity of the compound was greatly
changed due to an increase in the relative density.
P-type thermoelectric material (Bi0.24Sb0.76)2Te3 was sintered
by PDS process at different temperatures to investigate the effect of
sintering temperatures on thermoelectric properties [836]. Sinter-
ing was performed by using an SPS machine (Dr. Sinter SPS 1020
System) at temperatures in the range 345495 8C. The sintering
conditions of 54 MPa pressure and 10 min of holding time were
considered to be optimal, by varying pressure and holding time
from 25 to 75 MPa and from 5 to 60 min, respectively. Each
experiment was performed by applying an initial axial pressure of
16 MPa, which was raised to 54 MPa, and kept constant during
sintering, when temperature reached 200 8C. Density increased
with increasing sintering temperature. Full-dense samples were
obtained for temperature higher than 445 8C. Regarding the
thermoelectric properties, it was seen that both electrical and
thermal conductivity of the material increased as sintering
temperature was augmented. Seebeck coefcient was found to
be higher in the longitudinal than in the transverse direction and,
in general, showed a decreasing tendency with an increase in
sintering temperature. This was observed particularly when
densication was performed at temperature higher than 445 8C.
In terms of gure of merit, the optimal sintering temperature was
found to be 445 or 465 8C (cf. Fig. 123).
Textured p-type (Bi,Sb)2Te3 has been fabricated by means of
zone melting and SPS [837,838]. Melted zone ingots were cru-
shed into ake like powders with various particle sizes (96120,
Fig. 123. Effect of sintering temperature on the room temperature gure of merit of
the (Bi0.24Sb0.76)2Te3 materials after PDS processing at 54 MPa for 10 min, in both
the longitudinal and transverse directions. Adapted from Keawprak et al. [836].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
120180 and 180380 mm, respectively) and then sintered by SPS
(SPS 2040 equipment) in the temperature range 653693 K (50 K/
min heating rate) at 60 MPa for 5 min. The performance of SPS
samples was characterized in terms of crystallographic orientation
of crystal grains. Both mechanical and thermoelectric properties
were also investigated in comparison to those of zone-melted
materials. The relative densities of the sintered samples were
higher than 98%. The bending strength (measured along the crystal
growth direction) of the SPS samples reached about 80 MPa, which
was 68 times larger than that of the melted zone material (about
10 MPa). Temperature dependence of electrical conductivity was
also considered for both SPS and zone-melted materials. It was
found that for sintering temperatures higher than 673 K, the SPS
sample had higher electrical conductivity than the zone-melted
material. The Seebeck coefcient of SPS materials sintered at
temperature higher than 673 K is smaller with respect to that of
the melted-zone sample. Thermal conductivity of SPS samples was
lower than that of zone-melted material in the whole temperature
range. In general, the gure of merit was improved for the SPS
material and its maximum value in the direction perpendicular to
the pressing direction reached about the 115% of that of the zone-
melted ingots.
Zone melting and subsequent SPS treatment was also used to
fabricate p-type (Bi2Te3)x(Sb2Te3)1x thermoelectric materials
with various chemical compositions (x = 0.16, 0.20 and 0.24)
[839]. The bending strength of the sintered materials was about
65 MPa, which was 57 times higher than that of the zone-melted
crystal.
The consolidation of the 4 wt.% Te-doped p-type Bi0.5Sb0.5Te3
compounds was performed by SPS in the temperature range from
250 to 350 8C [840]. The density of the sintered compacts was
increased to 99.2% of the theoretical density by carrying out
consolidation at 350 8C for 2 min. The highest gure of merit was
also obtained.
BiTeSb compounds were developed by SPS for p- and n-type
thermoelectric applications [841]. The typical materials
20%Bi2Te3 + 80%Sb2Te3 for p-type and 95%Bi2Te3 for n-type
thermoelectric materials were selected. The elemental powders
were mixed in the proper ratio and melted at 973 K in a sealed and
evacuated quartz tube. A rocking furnace was used to ensure
composition homogeneity without any segregation. The melted
ingots were crushed and sieved to powders having of less than
100 mesh. Powders were subsequently treated in SPS at 623 K
(100 K/min heating rate) under a pressure of 50 MPa, for 5 min
holding time. The electrical, thermal, thermoelectric and mechan-
ical properties were obtained by experiments and adopted for
nite elements analysis. The temperature and the stress distribu-
tion as well as the coefcient of performance in the thermoelectric
coolers were obtained by calculations.
Starting from elemental powders p-type 25%Bi2Te375%Sb2Te3
thermoelectrical materials with high density were prepared by MA
and PAS [842]. The effect of sintering temperature on micro-
structure and thermoelectric properties of the as-PASed samples
was taken into account. Sintering was performed at different
temperatures, ranging from 593 to 713 K, at 40 MPa for 10 min. In
general, relative density increased as the sintering temperature
was augmented. Highly compact sample with relative density of
99.4% was prepared, when sintering temperature was 683 K. A
preferentially oriented microstructure was obtained. Vickers
microhardness of the as PASed samples was also measured and
compared with that corresponding to zone-melted materials. It
was found that sintered compacts exhibited microhardness twice
higher than that of single crystals prepared by zone melting.
Regarding thermoelectric behavior of the p-type 25%Bi2Te3
75%Sb2Te3 compacts, it was seen that Seebeck coefcient and
231
electrical resistivity decreased and increased, respectively, when
sintering was performed between 593 and 683 K. When sintering
temperature is above 683 K, the electrical resistivity did not
change signicantly, while the Seebeck coefcient decreased
slightly.
A (Bi,Sb)2Te3 alloy powder was sintered by PDS followed by
rotary-die equal channel angular pressing (ECAP) process [108].
Starting material was a oriented ingot having chemical formula of
(Bi0.24Sb0.76)2Te3, with 4.0% excess of Te and 1.8% excess of Se as a
dopant. Ingot was crushed to powders with particle size lower
than 210 mm, under Ar atmosphere. Powders were subsequently
consolidated by PDS method, using an SPS machine (DR. Sinter
SPS 1020 System): during the rst stage a uniaxial pressure of
12.5 MPa was applied while temperature was increased to 473 K
at a heating rate of 20 K/min. In order to allow sample degassing,
temperature was held for 20 min at this level. At the end of the
degassing period, the pressure was increased to 54 MPa and
temperature raised to 618 K at heating rate of 10 K/min.
Mechanical load was held until 1 min before the end of sintering
period (10 min) at 618 K. After sintering, some samples were
treated with ECAP by performing 4 or 8 pressing cycles in order to
achieve uniform deformation. X-ray diffraction patterns showed
that both, as sintered and sintered ECAP samples, consisted of a
single-phase having a rhombohedral Sb2Te3 structure. Micro-
structure of fracture surface was also considered. It was seen that
PDS samples had a stronger preferred orientation as compared to
ECAPed samples. In addition, very coarse grains (200 mm) were
observed in the PDS materials. Grain size slightly decreased after
ECAP treatment. With reference to thermoelectric properties, it
was established that the Seebeck coefcient of the materials
decreased after ECAP processes. On the other hand electrical
conductivity was increased after ECAP. Generally, the gure of
merit showed higher value either for PDSed or PDS-ECAPed
samples.
Starting from p-type (Bi2Te3)0.2(Sb2Te3)0.8 and n-type
(Bi2Se3)0.05(Bi2Te3)0.95 alloys obtained by shear extrusion, thermo-
electric solder free pn module in BiTe system was successfully
fabricated by SPS solid bonding technique (T = 523 K, P = 10.4 MPa,
0.3 ks holding time) for thermoelectric generator applications
[843]. The power generation characteristic for different solder-free
pn modules was investigated. Typically, the temperature
difference between cold and hot sources for conventional modules
is limited (about 100 K), resulting in lower output power. On the
contrary, soldering less devices prepared by SPS were permitted to
operate at relatively high temperature, and large temperature
difference (180 K) can be applied to obtain larger output power.
N-type Bi2Te2.85Se0.15 solid solution with ne microstructure
was prepared under similar conditions at different temperatures,
ranging from 593 to 713 K, at 30 MPa for 15 min [844]. A ne and
preferentially oriented microstructure (cf. Fig. 124) with the basal
planes (0 0 l) perpendicular to pressing direction was formed. Both
Seebeck coefcient and electrical resistivity of n-type
Bi2Te2.85Se0.15 specimens decreased with increasing PAS tempera-
ture, while thermal conductivity increased with increasing
sintering temperature. Power factor and gure of merit for both
p-type and n-type samples increased with increasing sintering
temperature when holding temperature was below 683 K. Then,
they decreased when the holding temperature was over 683 K.
A group of Cu-doped CuxBi0.5Sb1.5xTe3 (x = 00.4) alloys have
been fabricated by SPS (SPS 1030) and their microstructure and
thermoelectric properties were compared with those of a typical
ternary Bi0.5Sb1.5Te3 alloy [845]. Starting alloys were prepared by
zone melting and sintering was performed at 623 K (heating rate
60 K/min), for 3 min under a pressure of 40 MPa. In general,
thermoelectric properties improved for the Cu-doped alloys as
232 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 124. SEM fractographs of the Bi2Ti2.85Se0.15 as-PASed samples sintered at 683 K
(a) parallel and (b) perpendicular to pressing direction. Adapted from Fan et al.
[844].
compared to the undoped ones. Better results in terms of gure of
merit were obtained for x = 0.05 at 442 K, being approximately two
times that of typical ternary Bi0.5Sb1.5Te3 alloy at room tempera-
ture.
P-type pseudo-binary BiSbTe alloy with Ga substitution for
Sb in raw mixtures were prepared by SPS (SPS 1030) [846]. Starting
zone-melted alloys, GaxBi0.5Sb1.5xTe3 (x = 0, 0.05, 0.1, 0.2, 0.4)
were ball milled and then sintered at 623 K under a pressure of
40 MPa. The effect of Ga addition on densication behavior was
considered. It was seen that density increased and reached its
maximum value at x = 0.1, and then monotonically decreased up to
x = 0.4 (cf. Fig. 125). In general the changes of density depend
both on masses of substituted and substituting atoms and on the
changes in unit cells parameters. Thermoelectric measurements
showed that a proper Ga substitution for Sb can improve the
thermoelectric performance near room temperature. In particular,
when x = 0.1, a large ratio between electrical and thermal
conductivity was obtained without a noticeable loss of Seebeck
coefcient.
It was recently established that a proper substitution of Cu and
Ag atoms for Sb in the Bi0.5Sb1.5Te3 alloy is essential for improving
thermoelectric performance [847 and references therein]. The
second phase Ag0.36Sb0.558Te that naturally precipitated in the Ag-
doped AgxBi0.5Sb1.5-xTe3 (x = 0.050.4) was assumed to play an
Fig. 125. The relationship between mean density and Ga molar fraction x for the Ga-
doped GaxBi0.5Sb1.5xTe3 (x = 00.4) alloys prepared by spark plasma sintering.
Adapted from Cui et al. [846].
important role in reducing the thermal conductivity at higher
temperature because of lattice distortion. A group of pseudo-
binary (Ag0.365Sb0.558Te)x(Bi0.5Sb1.5Te3)1x (x = 01.0) alloys
were prepared using SPS and the effect of ternary alloy
Ag0.365Sb0.558Te on the thermoelectric properties was evaluated.
Specically, two mixtures consisting of pure elements Ag, Bi, Sb,
Te in a stoichiometric ratio of Ag0.365Sb0.558Te and Bi0.5Sb1.5Te3
were sealed in two different vacuum quartz and melted for 10 h at
1323 K. A 30 s rocking treatment was conducted every 1 h in
order to ensure homogeneous composition. After quenching, the
two ingots were, once again, sealed and melted in vacuum
tubes according to a stoichiometry of (Ag0.365Sb0.558Te)x
(Bi0.5Sb1.5Te3)1x (x = 01.0). The obtained ingots with different
x molar ratio were ball milled and the resulting powders sintered
by SPS (SPS 1030) at 623 K, with a pressure of 40 MPa. Densities
of the (Ag0.365Sb0.558Te)x(Bi0.5Sb1.5Te3)1x samples with x in
the range 0.0250.4 were measured, resulting little higher
(6.55  103 to 6.63  103 kg/m3) than that of Bi0.5Sb1.5Te3
(6.50  103 kg/m3). X-ray diffraction patterns of the sintered
products consisted of peaks belonging to common homo-
logous series (Ag0.365Sb0.558Te)x(Bi0.5Sb1.5Te3)1x with rhombo-
hedral Sb2Te3 structure. Regarding thermoelectric properties,
it was found that the pseudo-binary alloys (Ag0.365Sb0.558Te)x
(Bi0.5Sb1.5Te3)1x exhibited superior thermoelectric performance
as compared to the ternary Bi0.5Sb1.5Te3.
Following the same synthesis and sintering method described
for the (Ag0.365Sb0.558Te)x-(Bi0.5Sb1.5Te3)1x alloys, Ag-doped n-
type (Bi2Te3)0.9(Bi2-xAgxSe3)0.1 (x = 00.4) was prepared by SPS at
623 K under a pressure of 40 MPa [848]. Densities of the obtained
compacts were in the range 4.688.05 kg/m3. XRD analysis
for (Bi2Te3)0.9(Bi2xAgxSe3)0.1 alloys showed a typical rhombohe-
dral structure as that of (Bi2Te3)0.9(Bi2Se3)0.1. From thermoelec-
trical characterization, it was found that the Ag substitution
for Bi can noticeably alter physical properties of the (Bi2Te3)0.9
(Bi2xAgxSe3)0.1 alloys with the enhancement of the Seebeck
coefcient at the expense of electrical conductivity. Specically it
was seen that the gure of merit increased with increasing Ag
content.
High dense (>96% of the theoretical values) p-type FeSi2-based
Fe66.7Si30.7Mn2.5Cu0.1 and Bi2Te3-based Bi0.5Sb1.5Te3 alloys were
prepared by SPS and electrical properties (Seebeck coefcient and
electrical conductivity) were measured in a wide range of
temperature, under vacuum [849]. The thermal conductivity
was theoretically evaluated by considering the thermal and
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
electrical conductivity of the same materials obtained by SPS. The
optimal junction temperature of the p-type segmented FeSi2
Bi2Te3 thermoelectric materials has been determined.
To reduce sulfur content and obtain high gure of merit at high
temperature, g-Tb2S3x system with low sulfur content was
studied [850 and references therein]. The a-Tb2S3 compound was
synthesized by reacting Tb4O7 with Tb2S3 at 1323 K for 36 ks. In
order to reduce the sulfur content, the synthesized powders were
heat treated under vacuum at 1853 K at different holding times
ranging from 3.6 to 18.0 ks, before sintering [850]. Resulting
products were subsequently sintered by PECS (SPS 511S Sumitomo
Coal Mining) at 1673 K (heating rate 0.42 K/s), under a pressure of
50 MPa. After being held at high temperature for 3.6 ks, the
powders were cooled at a rate of 0.84 K/s to 873 K, followed by
slow cooling to room temperature. After PECS, g-Tb2S3x was
formed. On the other hand, long-term heat-treated samples
consisted of g-Tb2S3x and monoclinic Tb5S7. The g-Tb2S3x
compounds exhibit a n-type metallic conduction in the tempera-
ture range 3001000 K. As the sulfur content decreased, the
electrical resistivity and the magnitude of thermopower
decreased, while the power factor increased. The thermal con-
ductivity remained unchanged over the whole temperature range
investigated. An improvement with respect to thermoelectric
properties was reached by decreasing sulfur content.
Sintered PbTe materials with average grain sizes of 28309 mm
were prepared by the SPS technique [851]. Sintering was carried
out at temperatures ranging from 732 to 803 K for durations of 6
9 min. The densities of the sintered PbTe were higher than 99% of
the theoretical value.
2.13. Polymer-containing materials
Preforms of plain carbon steel powderlow density poly-
ethylene composites were produced by high voltage EDC [852]. A
relatively low density preform was obtained by connecting the
powder mix in a tube across a charged capacitor bank. Above a
certain voltage, the oxide layers of the metal particles are broken
and a heavy transient current passes through the powder
column. Owing to combined electrothermal and electromagnetic
effects, the powder mix consolidated into a preform in a period of
approx. 50 ms.
A thermosetting polyimide (PI) was consolidated by the spark
plasma system [47]. A pressure of 147 MPa was necessary to obtain
a dense thermosetting polyimide body with intrinsic properties.
Polyacrylonitrile (PAN)-based carbon ber tows were coated
with a commercial, heat-crosslinkable polyetherimide (Ultem)
powder [853]. Then, an electrical current was applied across the
powder-coated ber tows (towpreg) to melt the thermoplastic
powder and form rigidized composites. The results showed that
resistive heating was a feasible route for making inatable
composite structures in space rigid.
A cellular solid of a NiP alloy containing polymer for passive
damping was fabricated using SPS [854]. The obtained results
showed that this cellular structural solid of NiP alloy containing
polymer has a high capacity for damping.
2.14. Functionally graded, coatings and laminated materials
A novel method of pulse electric discharge resistance con-
solidation with temperature gradient control has been developed
by Kimura and Toda [855] for the design and fabrication of FGMs.
Using a stepped graphite die with a temperature difference of more
than 700 K within a width of 7 mm, a ve layered materials graded
from TiAl intermetallic to partially stabilized zirconia (PSZ) can be
fabricated. This structure showed full densication throughout its
233
cross-section without any discontinuity and an increasing hard-
ness from 650 HV at the TiAl nanocrystalline layer to 1560 HV at
the PSZ layer, varying according to a mixture rule.
A FGM laminated with ve layers composing of Al, Ti and Al3Ti
phases was prepared from an equimolar mixture of Al and Ti
powders by combination of ball milling and PCPS processes [856].
The volume fraction of Al3Ti phase in the laminated layers
increased with increasing milling period of Al50 at.%Ti mixed
powder. This resulted from the accelerated formation of Al3Ti in
the PCPS process due to renement of Al and Ti composite particles
during milling. The average value of Vickers hardness for each
laminated layer of the FGM increased with increasing content of
Al3Ti phase in the layer. The average hardness values of the ve
layers were 28, 165, 258, 425 and 520 HV, respectively.
FGMs were fabricated from thermal conductive composites,
formed by thermoplastic polyimide and AIN powders, and Cu
powder using a spark plasma system [857]. The thermal
conductivity of FGMs prepared at 39.2 and 245 MPa was 35 and
60 W/mK, respectively.
SPS technique was employed to perform boriding of mild steel
[858], tungsten [859] and molybdenum [860], thus obtaining FGM
with wear-resistant surfaces. A pack boriding mixture that
contained a silicon carbideboron carbide powders was utilized.
The process was performed in the temperature ranges 7001000,
10001400 and 10001400 8C, for 30 min. SEM and XRD revealed
that the microstructure and phase composition of the obtained
layers were constituted by FeB and Fe2B, WB and MoB,
respectively.
Through simultaneous eld activated reaction and densica-
tion, two- and ve-layer graded composites of Nb5Si3 and Nb were
formed [861]. The product microstructure consisted of Nb particles
in a matrix of Nb5Si3 with the composition ranging from 3.4 to
55.8 vol.%Nb (2090 mol%Nb) for the ve-layer samples. The
microhardness decreased with increasing vol.%Nb, from 1199 to
732 Hv over the indicated range. Fracture toughness measured by
indentation increased from about 21 to 30 MPa m1/2 over the
composition range of 3.436.0 vol.%Nb.
Three kinds of full compositional distribution (from 0 to
100 wt.%W) W/Cu FGMs with high density were fabricated by
resistance sintering under ultra-high pressure [862]. The sintering
mechanism of W is mainly in the solid state. Thermal shock test in
air demonstrated that the grading at the interface between W and
Cu is effective for the reduction of thermal stress, but obvious
transverse and vertical cracks occurred in the pure W layer.
A four-layer FGM was also obtained by SPS technology, starting
from powders of nano-WC/10%Co, nano-WC/12%Co, micro-WC/
15%Co and stainless steel disk [863]. The other three-layer FGM
was made from powders of nano-21%Al2O3/ZrO2, nickel and
stainless steel. The SPS processing led to FGM free of internal stress.
The titanium/hydroxyapatite (Ti/HA) and other FGM implants
with the concentration changed gradually in the longitudinal
direction of cylindrical shape were rst fabricated by powder
metallurgy to optimize both mechanical properties and biocom-
patibilities or change bioreactivity in each region [864,865].
Electric furnace heating, high frequency induction heating and
SPS methods were used for sintering. It was found that SPS could
make the stable Ti/HA FGM.
A CuSn alloy composite layer containing MoS2 as solid
lubricant was formed on A2014 aluminum base metal mixture
with the aim to improve the tribological properties of the Al base
metal [118]. Specically, after placing the CuSnMoS2 powders
on the A2014 base metal mixture, sintering was subsequently
performed at 690, 730, 770, and 810 K for 300 s at 45 and 90 MPa,
using an SPS apparatus (1050 Sumitomo Coal Mining Co.). High
pressure levels were found to accelerate plastic deformation and
234 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
high densities were achieved when higher pressure were applied
at low temperatures. In particular, a coated layer with density of
6.45 Mg/m3 was obtained at 770 and 730 K when pressure was set
to 45 and 90 MPa, respectively. The friction coefcient was
approximately 0.100.12, which is comparable to some commer-
cial items, while the specic wear was much lower than that of
commercial items used for automotive components.
A six-layer FGM of TiTiBTiB2 was rapidly fabricated by SPS in
vacuum [866]. Both B and TiB2 were used and reacted with Ti to
synthesize TiB. Adjusting the content ratio of B to TiB2 in individual
layers could control the amount of synthesized TiB by two steps
during sintering. The synthesized TiB has needle-like, agglomer-
ated and elongated morphologies. The content of agglomerated TiB
increased and that of needle shape TiB decreased with increasing
the target TiB volume fraction ranging from 20 to 60%. The
elongated TiB was observed in the other two layers with higher
target TiB volume fraction, which structure is similar to the
agglomerated TiB. The system of TiTiB2 has been also investigated
as FGM armor materials [867]. At low sintering temperatures with
short holding times (minutes), fully dense materials can be
obtained, beneting in little grain growth. The ballistic results
indicate a suitable composition, which does not have to be a pure
ceramic, for the outer high hardness armor layer.
TiB2/Cu FGMs were successfully fabricated via SPS, in which a
temperature gradient was achieved by using a specially designed
mold and a two-step sintering was performed [868]. The SEM
observations showed that the TiB2/Cu FGMs have dense micro-
structures. The XRD analysis suggests that no new phases were
introduced into the TiB2/Cu composites after mechanical milling or
SPS process.
SPS was applied to thermal spray coatings consisting of a
porous matrix [869]. Specically, a 3-mm thick carbon steel SS400
disk with 30 mm diameter, once thermally spray coated with
magnesia stabilized zirconia, was exposed to rapid heating under
vacuum at temperatures of 900, 950 and 1000 8C under
compressive load for 10 min. It was found that the as-sprayed
coating had high porosities of up to 22%, while after SPS treatment
the porosity fell to below 5%. The bond strength and microhardness
of the coating was also increased, as it may be seen in Fig. 126.
SPS combined with heat treatment was investigated to prepare
laminated ceramics from compositions having quite different
sintering temperatures [870]. Although the optimal sintering
temperature of BaNd2Ti4O12 (BNT) ceramics was much higher than
that of Bi4Ti3O12 (BIT) ceramics, sandwiched BaNd2Ti4O12/
Bi4Ti3O12/BaNd2Ti4O12 (BNT/BIT/BNT) composite ceramics were
successfully prepared with this new method. It has been shown
that the BNT layers and the BIT layer were well bonded and no
signicant diffusion between them was observed. The temperature
coefcient of dielectric constant of the laminated ceramic was
found to be much smaller than that of BNT ceramic.
More recently, SPS was applied to densify alumina/nickel
laminar materials previously obtained by tape casting and elec-
troless plating [871].
Ferroelectric/dielectric (BST64/MgO/BST64) multilayer ceramic
densied at 97% was obtained by SPS [872] at relatively low
temperature and short treatment times compared with conven-
tional sintering. It was found that in the multilayer composite the
Curie temperature of the ferroelectric part remained constant
while dielectric losses were well below 1%. On the other hand, a
decrease of permittivity was observed when increasing the MgO
content (cf. Fig. 127).
A Ni-based tri-layer composite substrate was obtained using
SPS at 900 8C under a pressure of 30 MPa by sintering together two
Ni5 at.%W layers on both sides of a metallurgically prepared
powder Ni12 at.%W inner layer [873]. The composite substrates
Fig. 126. Bond strength of magnesia stabilized zirconia coatings on carbon steel
after SPS treatments as a function of compressive load. Adapted from Prawara et al.
[869].
obtained by subsequent cold rolling and annealing had a very
sharp cube texture on the Ni5 at.%W outer layer and the yield
strength exceeded 320 MPa, while the magnetization behavior was
dramatically reduced.
While previous FGM systems were investigated at the
laboratory scale, large-size WC/Co FGM were fabricated by SPS,
as reported by Tokita [874]. Utilizing a fully automated produc-
tion-type SPS system, a square-shaped large size WC/Co cemented
carbide hard alloy FGM having four gradient layers of 100 mm
(width)  100 mm (length)  40 mm (thickness) was homoge-
neously fabricated in less than 1 h of continuous operation. The
hardness of the top and bottom layers containing 6 and 20 wt.%Co
were 20 and 9 GPa, respectively. Residual stress values of WC/Co
FGMs may be seen in Fig. 128 [874].
2.15. Systems for joining
Sintered silicon nitride ceramics were joined by employing
joule heating by an electric current through a joining paste
containing CaF2 [875]. The exural strength of the joint was found
to be dependent on the thickness of the joint layer. The thickness
was controlled by the time of joule heating. The maximum
strength was found to be around 300 MPa up to 800 8C. Strength
decreased rapidly above 900 8C because of softening of the joint
layer.
The PAS process was also tested by Sang et al. [876] to develop a
good diffusion bonding between a BN ceramic layer and the metal
substrate while sintering the ceramic layer. In contrast to HIP
techniques, sintering and coating in PAS can be completed in a very
short time (minutes as compared to hours).
WC bodies ranging from 70 to 95% of density ratio have been
spark sintered under different sintering conditions, and their
mechanical properties, such as hardness and bending strength,
have been measured [62]. High-quality diamond lms have been
deposited on these WC substrates using the microwave plasma
CVD method. A comparison study using indentation tests showed
that the adhesive strength of diamond lms on this binder-less
sintered WC is remarkably superior to that on WCCo. This result
was believed to be related to the increase in diamond nucleation
density obtained by CVD, the enhanced mechanical bonding
between the substrate and the diamond lm, and the well-
matching of thermal expansion coefcients caused by the absence
of cobalt.
An impact-electric current discharge joining machine, which
can simultaneously apply impact load and electric current, has
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 127. Dielectric permittivity of spark plasma sintered BST64/MgO/BST64 stack as a function of temperature at various MgO contents. For sake of comparison, the dielectric
permittivity of BST64 (Ba0.6Sr0.4TiO3) alone is also plotted. Adapted from Elissalde et al. [872].
been designed and manufactured to produce a high-strength joint
between materials [877,878]. The aluminum (A1100)-stainless
steel (SUS430) layered sheets were resistance-heated at 833 K for
0.43.6 ks under an applied pressure of 30 MPa after the pulsed
electrical discharge for 0.7 ks. The values of the joined area fraction
at the A1100SUS430 interface were changed from 25 to 70% for
the laminates resistance-heated for 0.43.6 ks at 833 K. It was
suggested, on the basis of the result of the thermal calculation, that
the maximum value (70%) of the joined area fraction was due to
inhomogeneity of the surface temperature on the SUS430 side at
the A1100SUS430 interface.
Joining of spheroidal graphite cast iron (FCD450) to stainless
steel (SUS304) has been also carried out [879]. Fracture stress and
area fraction of the actually joined portion at the FCD450/SUS304
interface was increased by increasing the amount and period of
electric current ow and with impact load, because joining state
was improved at the joint interface.
Fig. 128. Residual stress of 100 mm  70 mm  8 mm large-size WC/Co FGM with
four-layered sintered by SPS. Adapted from Tokita [874].
235
Joints composed of stainless steel and Ti were fabricated from
Cr-plated SUS304L alloy rods and Ti rods using vanadium foil as an
insert metal using a pulsed current hot pressing (PCHP) equipment
[880]. The joints fabricated at 1173 K from 20 mm thick Cr-plated
SUS304L rods and Ti rods showed the highest tensile strength of
340 MPa. SEMEDS analyses revealed that the Cr-plate layer was
left after PCHP process and no intermetallic compounds were
formed at the bonding interfaces. The cracks originally existed in
the Cr layer plated on SUS304L rods disappeared perfectly during
PCHP process at 1273 K. In contrast, the joints fabricated from 5-
mm thick Cr-plated SUS304L rods and Ti rods showed the lowest
tensile strength because of the formation of FeV intermetallic
compound in the bonded interlayer.
The inuence of bonding conditions and electric wave on local
heating phenomena remained unclear, as discussed by Chikui et al.
[881] and Chikui et al. [882]. To analyze these aspects, joints of
SUS304 stainless steel were formed under a variety of conditions of
the pulsed electric current bonding process. It was found that the
local heating efciency at the bonded interface becomes larger
with high resistance at the contact area when bonding pressure is
lower and the bonding surface is smooth. When the initial current
was high, local heating at the contact area is accelerated and joint
quality is better. However, the initial current was found to have an
optimum value. Above this value, the current tended to ow at the
center of the bonding area, making it difcult to heat the bonding
area uniformly. In addition, it was found that the frequency and
duty ratio of the electric current wave did not inuence local
heating phenomena. When the electrical power was high, local
heating at the contact area was accelerated. Direct current
delivered greater power than pulsed one, and heated the contact
zone more efciently than the pulsed current [883].
Magnetostrictive bulk Fe17 at.%Ga alloy was fabricated by
combining laminates of rapid-solidied ribbons (80 mm in
thickness) using the SPS joining (SPSJ) [884]. The laminated
sample made by the SPSJ maintained a unique metallurgical
microstructure of polycrystalline texture of columnar grains, as
well as the almost non-equilibrium metastable phase with little
evidence of the precipitates of the ordered phases, as found in the
236 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
as-spun ribbons. An excellent sintered sample exhibiting large
magnetostriction was obtained under a condition of compressive
stress of 100 MPa at a temperature of 973 K.
The characteristics of various metals bonded by DC pulse
resistance heat pressure welding using SPS process have been
investigated by Nakamura et al. [885]. Bonding strengths of 130
200 MPa between Al11.5mass.%Si alloy and Al20.0 mass%Si
alloy including SiC particles can be obtained with the application of
titanium powder at the interface. Sufcient bonding strength
cannot be obtained for the combination of cemented carbides.
Dissimilar steels can be bonded with a bonding ratio of more than
70%. Bonding strength is reduced for the combinations of titanium
alloy and other metals, because of the formation of some
intermetallic compounds at the interface.
Study on joining between piezoelectric ceramics and aluminum
was performed by SPS [886]. An insert material for a joining
between PZT and aluminum was the Sn3.5Ag alloy powder. The
joining samples were produced by SPS at 473 K for 300 s to 7.2 ks.
The maximum shearing stress of 25 MPa was obtained.
Ti mesh was bonded to a solid titanium substrate using PECS to
fabricate a porous surface of potential use in a titanium implant
[887]. During the PECS process, there was a temperature gradient
between the Ti mesh and Ti rod, which increased with increasing
the heating rate.
A dissimilar metal joint between sintered tungsten and ferritic/
martensitic steel (F82H) was fabricated by SPS [888]. The joint had
no defects in spite of the large difference in thermal expansion
coefcient between tungsten and F82H. It was considered that
formation of a compliant layer of the ferritic phase can lead to
successful bonding for the tungsten and F82H joint even without
an articial interlayer.
A reaction synthesis-based in situ joining technique was
developed for joining dissimilar nanocrystalline materials by use
of SPS [889]. Specically, joints between nanocrystalline Ni3Al and
TiC/Ni3Al were successfully produced at processing temperatures
of 1000 and 1100 8C for a hold time of 5 min. The joints exhibited
an average strength of 765 MPa.
2.16. Graphite/carbon-containing materials
A pulsed electric current sintering method was employed for a
graphitization process starting from dry wood charcoal obtained
from Sugi wood chopping [122,890,891]. In particular, the
graphitization process was performed using a pulse current
heating machine (Plasman) at 2200 8C for 5 min, and 50 MPa
pressure and in presence of Al (10 wt.%) from a solution of Al-
triisopropoxide which acted as catalyst [122,891]. During the
process, the intermediate plate-like Al4C3 phase was rst formed
but it subsequently dissociated into Al vapor and graphene sheets.
The latter ones, which exhibited a strong texture, contained also a
certain amount of diamond-like structure.
The same research group performed an analogous process on
the pulse current heating device where the graphitization of
biomass carbon was carried in presence of Al2O3 in the 030 wt.%
range [891,892]. The graphitization process was performed at
20002200 8C for 5 min, under 50 MPa. In this case, the plate-like
Al4C3 phase was formed along with CO as an intermediate reaction
product between Al2O3 and carbon. Then, under appropriate
temperature and CO pressure conditions, the carbide phase
dissociated to form solid graphite and Al vapor.
The baking process of natural graphite powders was investi-
gated in vacuum by SPS (SPS-1050) at a rate of 120 8C/min, in the
temperature and pressure ranges of 14001800 8C and 2040 MPa,
respectively, for 1518 min [81,893]. It was found that the
manufacture of the graphitic material was completed in 18 min
at 1800 8C without adding binders and additives. Including the
cooling period, the entire process duration was about 2 h, i.e. much
less than that (1 month or more) needed using conventional
methods. The bulk density and hardness of the samples were found
to increase with increasing of temperature and pressure. In
particular, the product density was 92% of the theoretical value and
the Shore hardness was 45 when the process was conducted at
1800 8C and 40 MPa.
The current status and the challenges for the development of
single-wall carbon nanotubes (SWCNTs) as well as carbon
nanotube composites have been recently reviewed by Zhan and
Mukherjee [894]. Here, we deal with ECAS processes where carbon
nanotubes are involved.
SWCNTs were successfully solidied without any additives by
hot pressing and SPS [895900]. The elastic modulus and fracture
strength of the SWCNT solid prepared by the SPS method were
about three and two times higher than those of the hot-pressed
SWCNT solid prepared under the same processing condition. The
enhancement of the mechanical properties of the SPS specimen
may be due to the formation of comparatively stronger bond
between SWCNTs.
SWCNTs synthesized by an arc discharge method and multi-
walled carbon nanotubes (MWCNTs) prepared by a CVD method
have been also solidied by SPS [901] by adding phenol resin
(50 mass%). The SWCNT solids showed signicant non-linear
deformation response, producing quasi-ductile fracture behavior,
and Youngs modulus and work of fracture were 1.6 GPa and
15.8 N mm, respectively. In contrast, the MWCNT solids showed
brittle fracture behavior, and Youngs modulus and work of
fracture were 1.5 GPa and 4.4 N mm, respectively.
CNTs/Fe/Al2O3 nanocomposites were prepared by thermal CVD
and SPS methods [902]. The dispersion of CNTs in the Fe/Al2O3
matrix were controlled by an attrition milling process. The effects
of CNTs dispersion on the mechanical and electrical properties of
the specimens were investigated. Fracture strength and electrical
conductivity of 5 vol.%CNTs/Fe/Al2O3 specimen were measured at
641 MPa and 2.93  1011 mS/m, whereas that of a 20 vol.%CNTs/
Fe/Al2O3 specimen were 208 MPa and 8.46  107 mS/m, respec-
tively. In comparison with an Al2O3 monolith, the specimen with
5 vol.%CNTs showed enhanced fracture strength and increased
electrical conductivity.
Thermal conductivities of fully dense multiwall carbon
nanotube/silica nanocomposites processed by SPS were evaluated
using a laser ash technique by Sivakumar et al. [903]. It was found
that incorporation of 5 and 10 vol.% carbon nanotube improved the
conductivities of the nanocomposites, and this improvement was
enhanced with increasing sintering temperature and duration. A
maximum conductivity of 4.08 W/(m K) was measured for 10 vol.%
carbon nanotube-containing nanocomposites sintered at 1050 8C
for 10 min.
SPS has been applied to develop carbon nanotube reinforced
silicon nitride composites [904,905]. For sake of comparison, hot
isostatic pressing has been also used for composite processing.
Nearly full compacted composites with superior mechanical
properties have been obtained in the case of novel sintering
method, whereas the conventional sintering resulted in porous
samples.
Fully dense nanocomposites of SWCNTs with nanocrystalline
alumina (Al2O3) matrix at sintering temperatures as low as 1150 8C
have been obtained by SPS [906]. A fracture toughness of
9.7 MPa m1/2, nearly three times that of pure nanocrystalline
alumina, can be achieved. A study was also performed on electrical
properties of nanoceramics reinforced with ropes of SWCNT [907].
In addition, anisotropic thermal properties have been found [908].
The introduction of ropes of SWCNTs gives rise to a decrease in the
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
transverse thermal diffusivity with increasing carbon nanotube
content, while it did not change the in-plane thermal diffusivity.
Thermoelectric properties of single-wall carbon nanotube/ceramic
nanocomposites have been also investigated [909]. The thermo-
electric power of the composites increased with increasing
temperature, showing a p-type value of 50.4 mV/K at 644 K that
is comparable to that of pure SWCNT.
Carbon nanotubes-nano-WC-Co composites were prepared by
SPS [910]. It was shown that with small amount of carbon
nanotube additions, the density of the composites can be
enhanced but the grain size has marginal increase. The sintered
nanocomposites combine superior hardness to toughness
relationships over that of the pure nanocrystalline WCCo
cermets fabricated under the same process. The extraordinary
mechanical properties of carbon nanotubes, the toughing and
bonding role of carbon nanotubes occurred in the nano-WCCo
matrix, as well as the SPS technique used may be responsible of
such behavior.
Dense Al2O3/SWCNT composites using SPS method have been
prepared by Wang et al. [911]. Vickers and Hertzian indentation
tests revealed that these composites are highly contact-damage
resistant, as shown by the lack of crack formation. However, direct
toughness measurements showed that these composites are as
brittle as dense Al2O3. This type of unusual mechanical behavior
was also observed in SPS-processed, dense Al2O3/graphite com-
posites. It was argued that the highly shear-deformable SWNTs or
graphite heterogeneities in the composites helped to redistribute
the stress eld under indentation, imparting the composites with
contact-damage resistance.
Carbon nanotube reinforced alumina matrix nanocomposite
was fabricated by solgel process and followed by spark plasma
sintering process [912]. Hardness and fracture toughness were
increased due to an enhanced load sharing of homogeneously
distributed carbon nanotubes and to a bridging effect of carbon
nanotubes during crack propagation, respectively. Similar results
were obtained by Cha et al. [913] when fabricating CNT/alumina
nanocomposites by means of a molecular level mixing process
followed by an in situ SPS.
Full-dense yttria 3 mol% stabilized zirconia matrix composites
containing 0.11 wt.% of MWCNTs and SWCNTs were fabricated by
SPS (Dr. Sinter 1020 Sumitomo Coal mining Co.) apparatus at
1300 8C for 5 min, under an applied pressure of 20 MPa [914]. It
was found that fracture toughness increased from 5.24 to
5.52 MPa m1/2 as the MWCNT content was increased from 0.1 to
0.5 wt.%, but it decreased to 4.47 MPa m1/2 with further increasing
of MWCNT content to 1.0 wt.%. The composites containing 0.5 wt.%
SWCNT showed similar fracture toughness (5.41 MPa m1/2) as that
of the matrix (5.28 MPa m1/2) [914]. Thus, the addition of carbon
nanotubes led to no signicant improvement on the mechanical
properties of the ceramic matrix.
A unique combination of acid treatment, aqueous colloidal
processing, and SPS has been used to fabricate high-density Al2O3/
single-wall carbon nanotube composites with well-distributed
SWCNTs and other carbon nanostructures (nano-onions, dia-
mond) at Al2O3 grain boundaries [915]. This approach could
be used to obtain well-controlled microstructures of ceramic/
SWCNT composites for tailored mechanical, electrical, and ther-
mal properties.
Alumina/multiwalled carbon nanotube composites with dif-
ferent MWNT contents ranging from 0.5 to 10 vol.% were prepared
by SPS [916]. The DC electrical conductivity and dielectric
properties of the composites were investigated and percolation
theory was applied to demonstrate the electrical property
transition from insulator to conductor. The experimental results
have shown that the electrical conductivity increased sharply as
237
the content of MWCNTs was close to percolation threshold of
0.79 vol.%. In the low frequency range, the dielectric constant
reached as high as 5000 when the content of MWCNTs was at
1.74 vol.% and nearly frequency independent.
SPS was used by Jiang et al. [917] to produce single-walled
carbon nanotube-toughened Al2O3-based composites that exhib-
ited excellent toughness (6.99.7 MPa m1/2), being at least two
times higher than that of single-phase alumina. Raman spectro-
scopy indicated that carbon nanotube cannot be retained at high
sintering temperature. A high compressive stress (2.0 GPa) in the
alumina matrix was also responsible for the improvement in
toughness. Similarly, dense Al2O3-based composites (99.0% of
theoretical) dispersed with carbon nanobers (CNFs) were
fabricated using PECPS for 5 min at 1300 8C and 30 MPa in a
vacuum [918]. High values of three-point bending strength
(800 MPa) and fracture toughness (5 MPa m1/2) were attained at
the composition of CNF/Al2O3 = 5:95 vol.% The values above were
25 and 5%, respectively, higher than those of monolithic Al2O3.
This might be due to the small Al2O3 grains (1.6 mm) of dense
sintered compacts, compared with that (4.4 mm) for the pure
Al2O3 ceramics, that allowed one to suppress grain growth during
sintering.
CNT reinforced Cu matrix (CNT/Cu) nanocomposites powders
were rst obtained by a novel fabrication process, named as
molecular level process, and then consolidated into CNT/Cu
nanocomposites by SPS [919,920]. The hardness and sliding wear
resistance of CNT/Cu nanocomposite were enhanced by two and
three times, respectively, compared to those of Cu matrix, due to
the effect of homogeneous distribution of CNTs in Cu matrix,
good bonding at CNT/Cu interfaces and high relative density of
nanocomposites.
Dense Fe3Al/CNT composite with CNT content of 5 vol.% has
been fabricated by SPS that retained the integrity of CNT in the
matrix [921]. Samples were synthesized at pressure of 30 MPa, and
temperature of 1273 K. The composites have microhardness of
8.7 GPa and compressive yield strength of 3175 MPa, about 95 and
56% increment over monolithic Fe3Al which was fabricated under
the same process.
Nanometer-sized SiC powders were mixed with 15 vol.% SiC-
coated MWCNTs and successfully sintered at 1800 8C by means of
PECS [922]. These composites showed superior microhardness of
30.6 GPa and toughness of 5.4 MPa m1/2 compared to monolithic
SiC ceramics, due to the improvement of adhesion between
MWCNTs and the SiC matrix by the SiC coating. The microhardness
and toughness of the monolithic SiC ceramics were 25.5 GPa and
4.8 MPa m1/2, respectively.
CNF dispersed b-SiC composites with the addition of 0.2 mass%
boron and 2.0 mass% carbon as sintering aids have been
synthesized and consolidated simultaneously from mixtures of
Si, amorphous C and B powders and CNF by PECPS [923]. CNF/SiC
composites sintered at 1800 8C for 10 min under 40 MPa in a
vacuum had about 96.0% of theoretical density and homogeneous
structures consisting of about 4.0 mm grains. A 10 vol.% CNF/SiC
composite exhibited a bending strength of about 720 MPa, a
Vickers hardness of about 26.0 GPa, and a fracture toughness of
about 5.5 MPa m1/2.
Sintered MWCNT disk was fabricated by SPS from MWCNT and
phenol resin mixture under 1273 K and 80 MPa in vacuum [924].
As the concentration of phenol resin in the sintered MWCNT disk
increases, the bending strength and Youngs modulus increased.
However, the inammatory response of such biomaterial was
observed in the tissue exposed to the surface of the sintered
MWCNT disk. This was believed due to the residual phenol resin in
the disk. The result indicated that the preparation of phenol free
MWCNT disk was recommended.
238 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
The diamond phase has been obtained directly from carbon
nanotubes by SPS at 1500 8C under 80 MPa pressure, without any
catalyst being involved [925]. Well-crystallized diamond crystals,
with particle sizes ranging from 300 nm to 10 mm were obtained.
After sintering at 1200 8C, the tips of the carbon nanotubes were
found to be open and the conversion from carbon nanotubes to
diamond started. The mechanism for carbon nanotube to diamond
conversion in SPS was described as that from carbon nanotubes to
an intermediate phase of carbon nano-onion, and then to diamond.
It was also shown that the MWCNTs were transformed into
micrometer-sized diamonds at 1500 8C and only 80 MPa during
SPS [926]. The resulting diamonds were single or agglomerated
crystalline particles, with diameters up to 100 nm, and are
sheathed with an amorphous carbon layer and a residue of a
few CNT layers.
Multiwalled carbon nanotube-BaTiO3 functional nanocompo-
sites were fabricated by SPS [927,928]. Through the analysis of the
temperature dependent shrinkage rate, it was found that the
incorporation of carbon nanotubes can effectively accelerate the
densication process of MWNT-BaTiO3 composites. Excellent
electrical and thermal conductivity of MWCNTs were proposed
to account for this unexpected sintering behavior. In addition, the
temperature dependence of resistivity showed abnormal metallic
conductance behavior in the 1 wt.% MWCNT-BaTiO3 nanocompo-
site.
MWCNT/nickel nanocomposite was rst prepared by slurry
mixing process and then sintered by SPS [929,930]. The relative
densities of the sintered composites containing up to 5 vol.% of
MWCNT were above 99%. The thermal conductivity is found to
increase 10% for composition with 3 vol.% MWNT.
MWCNTs-mullite composites were rstly fabricated with HP
and SPS [931].
6 mol of CaHPO42H2O (DCPD), 4 mol calcium hydroxide and
MWCNTs were rst mixed and sintered by using SPS at 5120 MPa
pressure, 12001250 8C, in vacuum or N2 atmosphere [932]. It was
found that the fracture toughness of sintered MWCNTs/HA
composite was increased.
MWCNT/3Y-TZP (3 mol% yttria-stabilized tetragonal poly-
crystalline zirconia) composites with different MWCNT contents
were prepared by SPS [933]. The DC conductivity of the composites
was found to follow a typical percolation behavior with a very low
percolation threshold between 1.0 and 2.0 wt.% MWCNT content.
The dielectric constant was greatly increased when the MWCNT
concentration was close to the percolation threshold, which was
attributed to dielectric relaxation, the space charge polarization
effect, and the percolation effect. The electrical conductivity of a
composite prepared by dispersing multiwall carbon nanotubes in
yttria-stabilized tetragonal zirconia matrix, and subsequent spark
plasma sintering, was investigated [934]. The experimental
analysis of the effect of temperature on the conductivity suggested
that for temperatures larger than 35 K, conduction can be
attributed to thermal uctuation-induced tunneling of the charge
carriers through the insulating zirconia separating by the multi-
wall carbon nanotube clusters.
It should be also noted that CNT bulk samples were fabricated
by SPS [935]. The phase structure and diameter of cylindrical
tubules of the CNTs were preserved even at high temperatures of
up to 2000 8C. The thermal conductivity was found to be as low as
4.2 W/(m K) at room temperature. This result was explained on the
basis of multiple physical elements including intensive tubetube
interactions. Bulk carbon nanotube SPSed samples prepared by
other authors [936] exhibited brittle fracture similar to that of
common ceramics. Fracture toughness was around 4.2 MPa m1/2
while exural strength was 50 MPa due to the weak bonding
between carbon nanotubes. Analogously, bulk multiwalled carbon
nanotube was prepared by SPS at 1700 8C under a pressure of
50 MPa in vacuum [937]. The density of the bulk sample reached
72% of the theoretical density of the carbon nanotube, 2 g/cm3.
Polyimide (PI)-based composites containing single-wall carbon
nanohorn aggregate (CNH) were fabricated using SPS by Tanaka
et al. [938]. For comparison, composites with CNT and traditional
graphite were also fabricated. The specic wear rate of composite
with CNH of only 5 wt.% was of about 108 mm3/N m, which was
two orders of magnitude less than that of PI alone. The wear
reduction ability of CNT seemed to be slightly inferior to that of
CNH, although it was considerably better than that of graphite.
2.17. Other systems
2.17.1. MgSiBi
N-type Bi-doped Mg2Si (Mg2Si:Bi = 1:x; 0.00  x  0.02) ther-
moelectric materials were prepared by SPS [939]. Reactants were
mixed together and then sintered at 10231053 K (heating rate
60 K/min) for 15 min at 30 MPa, in vacuum. SPS samples annealed
at 900 K exhibited density higher than 99%. Thermoelectric
properties of Bi-doped Mg2Si fabricated by SPS were characterized
by measurement of Hall effect at 300 K, and measurements of
electrical resistivity, Seebeck coefcient, and thermal conductivity
between 300 and 900 K. It was found that thermoelectric
properties strongly depend on Bi concentration. The sample of
x = 0.02 showed the maximum gure of merit (0.86 at 862 K), 1.5
times larger as compared with that of undoped Mg2Si.
2.17.2. SiGe
Dense bodies of both p- and n-type Si0.8Ge0.2 powders for
thermoelectric elements were fabricated by PCS [940]. Starting
powders were obtained by gas atomization of a mixture of Si and
Ge. Particular attention was placed on the understanding of the
effect of ball milling on the sinterability of the as prepared SiGe
powders. Specically, Si0.8Ge0.2 powders were ball milled (400 rpm
under Ar atmosphere) at different milling times (1100 h) and then
characterized in terms of phase composition, microstructure and
particle size distribution. Best results were obtained for powders
milled for 10 h, which were then consolidated by PCS (180 s
holding time, 49 MPa applied pressure) at different sintering
temperatures ranging from 1473 to 1533 K, and from 1273 to
1513 K, respectively. It was found that densication of as prepared
powders was abruptly promoted above 1500 K, while, after 10 h of
ball milling treatment, densication temperature decreased by
approximately 100 K. Densities of the samples obtained by PCS of
gas atomized and pulverized powders were more than 99% at 1523
and 1433 K, respectively. Furthermore, grain size and elemental
heterogeneity of dense bodies were both reduced for dense
samples fabricated from pulverized powders. The penetration
behavior of dopants (B and P) across the pn junction in the joined
SiGe semiconductors was also elucidated by the same authors
[114]. The pn joined samples were prepared by PCS at 1523 K, for
180 s under a pressure of 49 MPa. Thermoelectric properties of
dense bodies obtained by PCS from gas atomized and pulverized
powders were also taken into account. Regarding the thermo-
electric performance it was seen that ball milling treatment was
ineffective [941].
A Si0.8Ge0.2 multilayered thermoelectric element was also
successfully fabricated by simultaneous sintering and joining of Si
Ge powders with a sandwiched alumina cloth [942,943].
Specically, an alumina cloth of 30 mm in diameter and 2 mm
thickness was sandwiched as insulators between the p- and n-type
SiGe powders and the obtained sandwich was charged 10 times
inside a cylindrical carbide vessel having a inner diameter of
30 mm. Simultaneous sintering and joining were carried out by
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
PCS (SPS 1030 Sumitomo Coal Mining), at 1523 K for 180 s, under a
pressure of 49 MPa. After PCS treatment, the pn joints resulted to
be rmly connected each other without any cracks. In addition, the
alumina layer did not react signicantly with the SiGe layers.
2.17.3. CoSb-based
Single-phase CoSb3 skutterudite was successfully synthesized
by SPS, using ball milled (015 h) Co and Sb powders as starting
materials [944]. Sintering was performed by using a Sumitomo SPS
3.20 MK-V equipment, at different temperatures in the range 673
973 K and different sintering times in the range 530 min. When
temperature was in the interval 773973 K, CoSb3 alloy with
single-phase skutterudite was obtained. Density was found to
increase with increasing sintering temperature, but too high
temperature gave rise to lower densities due to the modest
decomposition. Also the microstructure resulted to be controlled
by sintering temperature. Specically nano-sized CoSb3 compound
with relative density of 97.4% and grain size of 100 nm was
synthesized at 873 K for 5 min (cf. Fig. 129).
CoSb3, grown by the vertical Bridgman method and subse-
quently annealed, was sintered under a pressure of 34 MPa, at
823 K for 10 min and at 923 K for 10 and 20 min, respectively
[945]. The density of the sintered CoSb3 varied from 85 to 98%
depending on the conditions adopted.
Also large size CoSb3 specimens were prepared by SPS in order
to assemble practical thermoelectric modules, starting from
planetary ball milled powders with average grain size of 30 mm
[946]. A relative density of 98%, larger than the theoretical density,
was achieved.
MASPS method was used to prepare LaxCo4Sb12 materials
(x = 0.12.0) [947]. Sintering was carried out in a Dr. Sinter SPS 3.20
equipment. Temperature was increased from room temperature to
500 8C with heating at 100 8C/min, from 500 to 650 8C at 33 8C/min
and, nally, it was held at 650 8C for 10 min. Pressure was kept
constant at 30 MPa. Bulk LaxCo4Sb12 compacts with relative
densities in the range 96100% were obtained as the La content
was increased from 0.1 to 2.0. From X-ray data, it was found that all
the compacts consisted of a skutterudite major phase. The non-
skutterudite second phase was found to increase with increasing
La content.
Filled skutterudite compounds (Ce,La)yFeCo3Sb12 with y = 0.1
0.3 were synthesized by solid-state reaction using powders of
Co, Sb, Fe, La and Ce as starting materials and subsequently
consolidated by SPS (Sumitomo SPS-3.20MK-V) at 900 K under
Fig. 129. TEM image of CoSb3 compound (L6) sintered at 873 K for 5 min. Adapted
from Zhang et al. [944].
239
a pressure of 30 MPa [948]. Heating rate was varied in the range
120150 8C/min. From XRD analysis, it was found that, after
sintering, skutterudite with small amount of Sb as impurity phase
was formed and the amount of Sb decreased with increasing lling
fraction of Ce and La. In addition, the lattice constant increased
linearly as y (lling effect of y) was increased, as an indication of
the fact that La and Ce were lled in the Sb voids. Regarding
the thermoelectrical characterization, it was observed that the
Seebeck coefcient of the compound increased with the lling
fraction of Ce and La, while the thermal conductivity and electrical
conductivity were greatly reduced. The compound Ce0.1La0.2Fe1.0-
Co3.0Sb12 exhibited the maximum value of the gure of merit.
Co-rich skutterudite compounds of FexCo4xSb12 (x = 01.0)
were synthesized by SPS at 8001000 K and the structural
morphologies and thermoelectric properties were studied [949].
It was seen that the lattice constant increased linearly with
increasing Fe content, and the electric conductivity increased with
increasing of substitution of Fe for Co sites. The Seebeck coefcient
shifted to high temperature values and thermal conductivity
decreased as the Fe content was augmented.
The lled skutterudite CeyFe1.0Co3.0Sb12 was prepared by in situ
SPS technology using Co, Sb, Fe and Ce powders as starting
materials [950]. Skutterudite phase appeared at 573 K and was
found to be the main phase with small amount of FeSb2 and Sb,
when temperature was in the range 673873 K and 0  y  0.3,
respectively.
Polycrystalline lled skutterudite compounds La0.75Fe3CoSb12
with ne grains and different porosities were fabricated by SPS
[951]. Experiments were conducted under a pressure of 60 MPa. All
the samples were heated at a rate of 100 K/min and sintered for
5 min at various temperatures ranging from 813 to 903 K. It was
found that specimen porosity increased with increasing sintering
temperature by considering the same starting powder size. The
average diameter of grains was about 4 mm.
Polycrystalline skutterudite Ba0.32PdxCo4xSb12 (nominally x
from 0 to 0.1) were synthesized by a melting method and sintered
by SPS at 850 K for 10 min [952]. A single skutterudite phase was
obtained when x  0.1. Density increased with increasing Pd
substitution from 97.7 to 98.9% of the theoretical density as x was
varied in the range 00.1.
2.17.4. ZnSb
Zn4Sb3 compounds with less cracks and high density were
prepared by gradient freeze (GF) or SPS and results were compared
[953]. Specically, stoichiometric quantities of Zn shots and Sb
ingots were melted in Ar atmosphere using an induction furnace.
The melt was quenched by gas atomizer in Ar atmosphere and then
ground and sieved. Powders with particle size of 100 mm or less
were subsequently consolidated by SPS at 673 K for 600 s, under
30 MPa. Compacts with densities of 95.1 and 95.3% were obtained
after SPS and GF, respectively. In both cases samples consisted of a
single-phase with a rhombohedral Zn4Sb3 crystal structure. A
systematic study of the low temperature dilatometric behavior and
thermoelectric and magnetic properties was also performed, for
both SPSed and GFed samples. Associated with structural tran-
sition from b to a, some anomalies in thermal expansion,
resistivity, thermopower and magnetic susceptibility for the SPSed
samples were found. The GF sample exhibited higher thermo-
electric performance and resulted a good candidate as thermo-
electric material for cryogenic use.
Dense Zn4Sb3 doped by 1 at.% of Hg was obtained by SPS under
argon at 673 K for 180 s while a mechanical pressure of 100 MPa
was applied [954]. Crack-free samples with a relative density
greater than 99% were obtained. Complete thermoelectric proper-
ties were measured in the temperature range 2400 K and the
240 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
inuence of Hg was investigated. It was found that Hg doping
signicantly affects the transport properties in the ordered a phase
crystal structure, while it displays a minor inuence on the
corresponding properties of the disordered b phase. The thermo-
electric gure of merit was found to be about 0.3 for both doped
and undoped Zn4Sb3 at 300 K.
2.17.5. ZrNiSn-based materials
ZrNiSn powders prepared by solid-state reaction from ele-
mental powders at 1173 K under a owing argon atmosphere,
were consolidated by SPS (SPS-1050, Izumi Technology Co. Ltd.,
Japan) at different temperatures, ranging from 973 and 1123 K, and
at different holding times in the range 1530 min [955]. The effect
of sintering temperature and holding time on the density was
studied. It was found that by increasing the temperature the
density generally increased. The best results were obtained when
sintering was performed under a pressure of 40 MPa, at 1123 K for
25 min. The density was about the 97.8% of the theoretical value.
X-ray diffraction patterns showed that sample consisted of a
single-phase. Fine grain size and homogeneous microstructure
were obtained. EDX analysis was conducted to quantify the atom
ratio in the ZrNiSn compounds. The account of each element was
found to be about the one-third (30 at.%) of the total compound.
Sb-, Hf- and Pt-doped ZrNiSn were also prepared and it was seen
that, as the dopants were added, diffraction peaks shift became
wider, thus indicating a change in the lattice constant and
substitution of the atoms.
(Zr0.6Hf0.4)0.7Ti0.3NiSn was prepared by arc melting from the
constituent elements followed by annealing at 1000 K for 2 days
under vacuum [956]. The obtained ingots were crushed and sieved
to powders with particle size of 75 mm. Sintering was subse-
quently performed by SPS at three different temperatures, 973,
1173, and 1373 K, respectively. Results were compared to those
obtained for arc-melted samples. Bulk densities measured after
SPS at 973, 1173, and 1373 K were about 70, 90, and 95%,
respectively. On the other hand, density of arc-melted sample was
100% of the theoretical value. From X-ray and SEMEDX analysis, it
was found that arc-melted samples exhibited grain boundary
structure, being grains composed of the half-Heusler compound
whose composition was (Zr0.6Hf0.4)0.7Ti0.3NiSn and grain boundary
constituted by TiSn-based alloy. On the other hand, microstruc-
ture of sample treated by SPS at 1173 and 1373 K did not present
grain boundary and some pores were present. From EDX, two
phases were found: a Ti-poor and -rich phases whose compositions
were (Zr0.6Hf0.4)0.9Ti0.1NiSn and (Zr0.6Hf0.4)0.6Ti0.4NiSn, respec-
tively. The effect of SPS temperature on thermoelectric properties
of (Ti,Zr,Hf)NiSn half-Heusler compounds was also studied.
Thermoelectric properties of sintered samples were measured
and compared with that of arc-melted samples. The power factor of
the SPS sample treated at 1173 K was about 5% lower than that of
the arc-melted sample, while thermal conductivity was reduced of
about 70%. Thermal conductivity was reduced, without degrada-
tion of electrical performance, by the SPS process. The gure of
merit of the SPS sample sintered at 1173 K reached a value 30%
higher than that of the arc-melted sample.
SPS was employed to fabricate the Zr0.5Hf0.5Ni0.8Pd0.2
Sn0.99Sb0.01/xZrO2 (x = 39 vol.%) nanocomposites for thermoelec-
tric applications [957]. The matrix material Zr0.5Hf0.5Ni0.8Pd0.2
Sn0.99Sb0.01 was obtained by mixing elemental powders with the
desired molar ratio. The powder mixture was then pressed into
pellets and heated at 1123 K under argon atmosphere for 72 h. The
obtained samples were then ground, pelletized and heated again.
The process was repeated three times in order to obtain a single-
phase sample. Subsequently, the obtained Zr0.5Hf0.5Ni0.8Pd0.2
Sn0.99Sb0.01 compound powders were mixed with ZrO2 nanopar-
ticles and annealed for 3 days. Sintering was performed at 1073 K
for 25 min. A Zr0.5Hf0.5Ni0.8Pd0.2Sn0.99Sb0.01 matrix with ne grain
microstructure was obtained. ZrO2 nanoparticles (20 nm) were
found mainly at the grain boundaries of the matrix with a small
amount of nanoinclusions within the grains. It was found that the
nanoparticles of ZrO2 had a considerable effect on the thermal
conductivity and on the electrical transport properties. The
Seebeck coefcient and the electrical conductivity of the nano-
composites was enhanced as compared to those of the matrix alloy.
Thus a considerable improvement in the thermoelectric gure of
merit was obtained.
2.17.6. Fe-magnetic alloys
Nanocrystalline bulk Fe88Nb2Nd2B5 and Fe76Co10Nb2Nd7B5
magnets were made by consolidating amorphous powders using
an electric pulse current sintering method between 673 and 923 K
(rate of 1.7 K/s) for 480 s, under a pressure of 636 MPa, with
subsequent annealing at 1023 K [93,958]. The X-ray diffraction
patterns showed that peaks of bbc Fe, Nd2Fe14B and Fe2B or Fe3B
phases were present in both the sintered and annealed samples of
amorphous Fe88Nb2Nd5B5 consolidated at 873 and 923 K. It should
be noted that the bulk alloys remained amorphous at sintering
temperature of 673 and 773 K. In addition, it was found that when
sintering amorphous and crystalline Fe88Nb2Nd5B5 powders at
873 K for 480 s, the amorphous phases densied at lower
temperature as compared with the crystalline one. In this respect,
it was reported that amorphous powders were easily deformed
near crystallization temperature because of the presence of Fe
(softening phenomenon). It was also found that the relative density
of the sintered compacts from amorphous powders increased as
the sintering temperature was augmented and it reached the value
of 7.7  103 kg/m3, i.e. relative density above 99% at 873 K.
However, density of the bulk alloy obtained by consolidating
crystalline powders, under the same conditions, had a lower value
of 6.6  103 kg/m3. Hard magnetic properties (remanence
enhancement and high reversibility in the recoil JH curve) were
also observed for nanocrystalline bulk alloy Fe88Nb2Nd2B5.
The bulk Fe(Al, Ga)(P, C, B, Si) alloys were produced by
consolidating the corresponding amorphous powders using
electric pulse sintering [959]. Bulk samples with high density
and better soft magnetic properties than those of FeSiB bulk
amorphous sample were obtained. The bulk glassy (Fe, Co,
Ni)70M10B20 (M = Zr, Hf) was also fabricated. Samples exhibited
large super-cooled liquid region at 72 and 82 K when M was Zr or
Hf, respectively. Further increase of super-cooled liquid region was
observed by replacing Zr or Hf with 2% of Nb or Ta. Fe70Al5-
Ga2P9.65C5.75B4.6Si3 alloy powders prepared by induction melting
were sintered by PECS at different temperature conditions ranging
from 693 to 713 K under a load of 590 MPa for 480 s [113]. Sintered
samples were 18 mm diameter and 1 mm thick. Crystallization
peaks appeared at 713 K. The maximum relative density for the
bulk Fe70Al5Ga2P9.65C5.75B4.6Si3 sample, which consisted only of
amorphous phase was 99% (which is superior to 94% for the bulk
Fe78Si9B13 alloy). Good soft magnetic properties of Fe70Al5-
Ga2P9.65C5.75B4.6Si3 alloy are related to its high structural homo-
geneity arising from its high deformability. Fe70Al5Ga2P9.65C5.75
B4.6Si3 was characterized by good soft magnetic properties as
compared to those of the bulk Fe78Si9B13 alloy prepared by the
same method.
SPS consolidation process was applied to Fe65Co10Ga5P12C4B4
glassy alloy which was prepared by the high pressure gas
atomization method and characterized by a large super-cooled
liquid region of 50 K before crystallization [960962]. To
determine the optimum sintering condition of Fe65Co10Ga5P12C4B4
glassy powders, the sintering was rstly performed under a xed
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
applied pressure of 80 MPa at three different temperatures (723,
743, 763 K) ranging from crystallization temperature (Tx) to the
glass-transition temperature (Tg). It was found that sample
densied at 723 K was completely amorphous. The sample
sintered at 743 K was characterized by a mixed structure of
crystalline and amorphous phases, while by further increasing
sintering temperature to 763 K, only crystalline phases were
detected. Therefore, bulk glassy alloy without crystallinity was
prepared by sintering powders of Fe65Co10Ga5P12C4B4 at 723 K. The
complete sintering of the sample was not achieved due to the low
applied pressure. Relative density was found to be about 95%. Thus,
in order to obtain glassy structure with higher density, subsequent
sintering was performed under high pressure of 200300 MPa, at
the glassy transition temperature of 723 K, for 600 s. The density of
the sample increased with the increase of the applied pressure. In
particular, a large size bulk glassy magnetic core (20 mm in
diameter and 5 mm in thickness) was obtained by SPS at 723 K
under a pressure of 300 MPa (cf. Fig. 130). The relative density was
99.7%. In addition, the multicomponent Fe-based bulk glassy core
was characterized by good soft magnetic properties (saturation
magnetization of 1.20 T, coercive force of 6 A/m and maximum
permeability of 8900) due to the high density (99.7%) achieved and
the maintenance of a single glassy structure.
The possibility of producing bulk amorphous NdFeB magnets
by SPS was studied by several authors. For instance, an anisotropic
magnet based on Nd15.5Dy1.0Fe72.7Co3.0B6.8Al1.0 alloy has been
prepared by SPS (SPS 3.20-MK-V; Sumitomo Coal Mining) and
compared with a magnet of the same composition processed by
conventional sintering methods [963967]. Magnetic properties,
microstructure and composition was investigated. Magnets
electrochemical properties in electrolytes and corrosion behavior
in oxidizing environment were also examined. It was found that
densication was improved as the sintering temperature was
Fig. 130. Changes of the density and relative density as a function of applied
pressure for Fe65Co10Ga5P12C4B4 magnetic cores. The data of the sample obtained
by sintering under the pressure of 80 MPa are also shown for comparison. Adapted
from Shen et al. [962].
241
increased (740860 8C, 3040 MPa, holding time 5 min). Corre-
spondingly, magnetic properties rst rose and then fell as the
temperature reached its maximum value. Regarding this aspect, it
was seen that a proper heat treatment after SPS enhanced the
magnetic properties of the compact. In fact, after SPS the Nd-rich
phase was present at the grain boundary of the ne and uniform
Nd2Fe14B main phase, but the Nd-rich phase was not uniformly
distributed and bulk Nd-rich phase clusters were present. After
proper heating treatment, the Nd-rich phase decreased and was
dispersed at the grain boundaries of the Nd2Fe14B main phase. In
addition, no scattered pores were present in the microstructure.
SPS experiments were also conducted under different pressures
(3050 MPa, 780 8C, holding time 5 minutes). Results were
compared to those obtained by conventional sintering method.
It was observed that density increased with increasing applied
pressure, while the magnetic remanence decreased abnormally. In
addition, the coercive force remained constant thus indicating that
it is not sensitive to pressure. It was also shown that NdFeB magnet
sintered by SPS has excellent dimensional precision. Furthermore,
the corresponding electrochemical properties and corrosion
resistance are better than those related to a conventionally
sintered magnets, due to the more uniform and ner micro-
structure obtained using SPS. In particular, the microstructure of
the anisotropic magnet sintered by SPS showed that Nd2Fe14B
grain size was ne and uniform, and that the Nd-rich phase was
agglomerated in the triple junctions and not along Nd2Fe14B grain
boundaries. Therefore, the pathways for corrosion propagation
were restricted and the intergranular corrosion process through
Nd-rich phase was suppressed. It was also observed that an
increase of compressive pressure can restrain the grain growth
remarkably and, then, can lead to better magnetic properties and
higher density for the magnets at the same temperature level.
The effect of sintering temperature and applied pressure on Nd
FeB bulk nanocomposites magnets produced by SPS was also
investigated [968,969]. Amorphous Nd4Fe77.5B18.5 melt spun
ribbons were consolidated by SPS at temperatures in the range
773973 K for 300 s and then held at the sintering temperature for
300 s by applying a pulsed current of 800 A at intervals of 2.4 ms.
Pressure was varied between 30 and 70 MPa. The density of the
resulting bulk materials increased as the sintering temperature
was augmented, and it was found to be equal to 7.29 g/cm3 (96%)
for the specimens consolidated at 973 K. The bulk materials were
amorphous when sintered at 773 K and were characterized by low
coercivity as expected for amorphous NdFeB materials. The
structure and magnetic properties of Nd4Fe77.5B18.5 bulk nano-
composite magnets obtained by SPS were found to be dependent
on both the sintering temperature and the applied pressure. Clear
diffraction peaks were present in the bulk materials consolidated
at 873 and 973 K, respectively. When sintered at 873 K between 30
and 70 MPa, the bulk materials consisted of nanocomposite
materials with a soft magnetic Fe3B phase and hard magnetic
Nd2Fe14B phase, together with small amount of a-Fe. Fe3B
diffraction peaks became smaller as the sintering temperature
was 973 K and clear diffraction peaks of a-Fe were found, while no
Nd2Fe14B peaks were observed. In addition, the bulk nanocompo-
sites obtained at 873 K exhibited high coercivity and smooth
hysteresis curves. It was found that an increase of the applied
pressure resulted in an increase of remanence value, due to the
higher density and larger amount of the hard magnetic Nd2Fe14B
phase. Similar results, in terms of magnetic properties and
microstructure, were obtained when considering amorphous
NdFeCoGaB and NdFeTiCB alloys [970,971].
A detailed examination of the microstructure, crystallization
process, volume ratio of the hard/soft phases and magnetic
properties was performed for the system NdxFe85xCo8V1B6 (with x
242 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

ranging from 7 to 11) consolidated by SPS (SPS-2040, Izumi

Technology Co. Ltd., Kawasaki, Japan), starting from rapidly
quenched amorphous ribbons [972,973]. Sintering was performed
under different temperature and pressure conditions. Better
results in terms of magnetic properties were obtained when x
was equal to 10, by performing sintering at 650 8C for 3 min under
a pressure of 980 MPa. The bulk exchange spring magnets
densied without crystal growth. There was no composition
segregation in the grain boundary region and mechanical strength
was equal to that of the interior of the powder grains. The magnets
displayed magnetic properties equal to those obtained by
annealing the starting ribbon powders.
Regarding the case of NdFeCoVbulk exchange spring
magnets having a low content of Nd, it was seen that the
saturation magnetization values were uniform and not dependent
on changes in the grain size [973,974]. Additionally, specic
resistance of the sample nearly coincided with the value
interpolated from the specic resistance of an ordinary sintered
pure Fe bulk compact and a sintered NdFeB magnets.
Bulk anisotropic NdFeB magnets were synthesized and hot
deformed using SPS (SPS-3.20-MK-V, Sumitomo Coal Mining,
Japan) [975]. Microstructure and magnetic properties were
investigated as a function of sintering temperature. It was found
that with the increase of sintering temperature, density of the
magnets increased from 7.42 to 7.60 g/cm3 as shown in Fig. 131.
Magnets consolidated at 650 8C (30 MPa, 180 s holding time)
possessed optimal magnetic properties (cf. Fig. 131). Hot pressed
and hot deformed magnets were characterized by different
microstructure. In the former ones, Nd2Fe14B grains were
randomly oriented and separated by a thin layer of Nd-rich phase,
while, after deformation, they resulted well aligned and Nd-rich
phase redistributed from grain boundaries to triple junctions of
Nd2Fe14B grains. The hot pressed magnets exhibited better
Fig. 131. Density (a) and magnetic properties (bd) of NdFeB SPSed magnets as a
remanence as compared with the starting melt spun powders.
function of sintering temperature (P = 30 MPa): Br = remanence; Hci = coercive
On the other hand, the coercive force fell slightly, due to grain force; BH = energy product. Adapted from Yue et al. [975].
growth of Nd2Fe14B phase. After hot deformation, remanence
greatly increased and coercive force decreased simultaneously, as a
consequence of a remarkable change in the microstructure. ture caused the crystallization and formation of Fe2B phase. The as
Nd2Fe14B/aFe isotropic bulk nanocomposite magnets were sintered samples exhibited soft magnetic properties, which
prepared by SPS using melt spun powders with a nominal became hard after annealing treatment.
composition of NdxFe94xB6 with x = 6, 8, 10 [976]. It was found SPS was also applied to prepare layer structural (Gd5Si2Ge2)x(G-
that higher sintering temperature improved the densication of d)y(Gd5Si1.85Ge2.15)z composite magnetic refrigerant materials
the magnets, while their magnetic properties deteriorated due to [979]. The magnetocaloric effect (MCE) of the magnets was
the exaggerated crystal growth. It was observed that an increase of evaluated by measuring their adiabatic temperature change (DTad)
compressive pressure led to better magnetic properties and higher and the applicability of these layer structural composites for room
density for the SPS magnets. An increase in Nd content amount temperature refrigeration technique was also taken into account. It
resulted in a gradual increase of coercivity and a reduction of the was found that proper x:y:z ratio improved both the value and the
remanence. Better results were obtained with the composition constancy of DTad. The solid solution materials in the boundaries
Nd8Fe86B6 (for x = 8), under the optimal sintering conditions. among the components, which are generated during the SPS
The SPS technology was used for the consolidation of process, were proven to have little effect on the MCE of the
Nd3.5Dy1.0Fe73Co3Si1B18.5 [977]. Several combination of tempera- composites. The value of DTad of all the composites exhibited a
ture, pressure and holding time were employed (680800 8C, 70 more constant tendency, which is suitable for practical application
75 MPa, 1030 min). It was found that higher sintering tempera- in room temperature refrigeration, when compared to those of the
ture can improve the consolidation, whereas it deteriorates the three components.
magnetic properties due to the appearance of a-Fe and grain Ni2MnGa alloys, synthesized from arc-melted ingots, were
growth. Although sintering at lower temperature can preserve consolidated by SPS at 80 MPa and 1173 K for 600 s [80,980]. The
magnetic properties, full consolidation cannot be achieved, even relative density of the as sintered alloy was 99.6%. After
under high applied pressure. Finer starting powders show similar densication, the samples were annealed at 1073 k for 864 ks.
behavior of the coarser ones. After heat treatment, the martensitic transformation temperatures
Consolidation of Fe67Co9.5Nd3Dy0.5B20 glassy powders has been were determined. Mechanical properties were also evaluated and
tested by SPS at around the transition temperature in order to yield stress, fracture strength and plastic deformation resulted
synthesize a hard magnetic bulk material with nanocomposite higher than to those ones of the arc-melted alloy.
structure [978]. The glassy powders were consolidated into bulk Consolidation of Fe35Pt35P30 and Fe50Pt50 was performed by SPS
form with relative density of 99.1% at 788 K for 420 s and a glassy after mechanical milling of the starting alloys [981]. SPS conditions
single-phase was maintained. The increase in sintering tempera- were as follows: load 3.53.8 kN (sample diameter 10 mm),
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
sintering temperature 773973 K, and sintering time 5 min. The
density of the Fe35Pt35P30 samples processed at 873 and 973 K was
higher than 95%, while it was 74% at 773 K. Furthermore, the
microstructures showed FePt phase with grain size in the range 80
150 nm depending on adopted conditions. The presence of nano-
sized (2040 nm) PtP2 inclusions was also observed (cf. Fig. 132).
Isotropic Mn1+xBi (0.0  x  0.5) were fabricated from mechani-
cally alloyed powders using SPS (SPS 515S, Izumi Tech) [982].
Sintering was carried out at 230 8C and 30 MPa. It took 1 min to
increase temperature and no holding time was considered. Heat
treatment after SPS was instead performed. Mechanically alloyed
powders consisted of MnBi, Mn and Bi phases, while for sintered
samples MnBi and Bi phases were detected. It was found that
annealing increased MnBi peak intensities at the cost of other
phases. This effect became stronger as x increased and only MnBi
phase was detected at x = 0.5.
2.17.7. Ba6C60
An SPS apparatus was adopted for the fabrication of bulk Ba6C60
fulleride using powder prepared by solid-state reaction from Ba
and C60 (fullerene) as raw materials [983]. Consolidation was
carried out under Argon atmosphere at 1873 K for 12 min, 500 K/
min heating rate, and 50 MPa mechanical pressure. The obtained
sample was 84% dense and the electrical resistivity, Seebeck
coefcient, thermal conductivity and Hall effect measurements
indicated that the obtained compound was metallic. In addition,
the lattice thermal conductivity for Ba6C60 fulleride at room
temperature was comparable to the value of amorphous SiO2.
2.17.8. Boron icosahedra compounds
In the framework of the preparation of REB17CN and REB22C2N
(RE = rare earth elements) characterized by thermoelectric proper-
Fig. 132. TEM bright eld micrographs of spark plasma sintered Fe35Pt35P30 magnets: (a) 773 K; (b) 873 K and (c) 973 K. Adapted from Gopalan et al. [981].
243
ties of n-type, the hot pressing technique was only able to give
samples with low density and extremely low power factors. Thus,
with the aim of improving the related properties, the spark plasma
sintering of HoB17CN and YB22C2N was recently investigated [984].
It was found that the SPS technique was able to produce samples
with density of about 75% of the theoretical value which is much
higher than about 50% obtained by the conventional hot pressing
method. Although no details on the SPS operating conditions were
reported in the paper, when the properties of SPS-prepared
HoB17CN and YB22C2N were compared with hot-pressed samples, a
large improvement in electrical conductivity was obtained, being
the resistivity decreased of about two orders of magnitude (cf.
Fig. 133). In addition, the power factor was found largely increased
from 31 to 106 times for the measured samples, as compared to
conventional hot-pressed samples
2.17.9. Carbonitrides
The fabrication of titanium carbonitrides TiC1xNx (x = 0.01.0)
and tantalum carbonitrides TaC1xNx (x = 0.00.95) was investi-
gated using the SPS technique starting from TiC, TiN, TaC, and TaN
without additional sintering aids [985,986]. A Dr. Sinter 2050
device was used in vacuum at 17001800 8C for 10 min, 100 8C/
min heating rate and applied pressure in the range 50100 MPa.
The results showed that the SPS technique allowed the rapid
synthesis of both the highly dense TiC1xNx and TaC1xNx solid
solutions. In particular, it was found that the highest densities were
obtained for low x-values.
The SPS method was also successfully used for the synthesis of
BCN nanocrystalline particles using amorphous BC2N as
precursor prepared by mechanical alloying from a mixture of
graphite and hexagonal BN [987]. The SPS process was investigated
in the temperature range of 12001900 8C, 300 8C/min heating rate
244 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 134. Apparent density of the LiTi2(PO4)3 (LTP)-based solid electrolytes sintered
by SPS or conventional sintering (CS). Adapted from Chang et al. [989].
Fig. 133. Temperature dependence of resistivity of conventionally hot pressed HP-
HoB17CN (lled triangles), HP-YB22C2N (lled circles), HP-ErB22C2N (lled squares),
spark plasma sintered SPS-YB22C2N (open circles), and SPS-HoB17CN (open shown to improve specimen densication when compared to
triangles). Adapted from Mori et al. [984].
conventional sintering, being the maximum density obtained of
about 90% (x = 0.5). The Li+ ion conductivity increased with sample
and 30 MPa mechanical pressure. It was showed that the BCN density and the highest conductivity of 1.1  104 S/cm was found
nanocrystalline particles with grain size less than 50 nm can be in the Li1.5Al0.5Hf1.5(PO4)3 SPS specimen, which was comparable to
synthesized at 1600 8C, while at 1900 8C, the BC2N precursor was the best value reported in the literature.
decomposed into graphite and hexagonal-BN.
2.17.11. Zn-doped CuAlS2
2.17.10. LiHf2(PO4)3 and LiTi2(PO4)3-based The preparation of p-type transparent CuAl1xZnxS2 bulk
The fabrication of LiTi2(PO4)3 (LTP)-based solid electrolytes by materials (x = 00.10) was investigated by SPS using the corre-
SPS was investigated starting from powders prepared by hydro- sponding powders synthesized by solid-state reaction of elemental
thermal synthesis [988]. Sintering was performed on a SPS-515S Cu, Al, Zn and S reactants [991]. The consolidation process was
apparatus in the temperature range 6001200 8C for 310 min, performed in Argon atmosphere at 1073 K for 4 min under a
150 8C/min heating rate and 39 MPa mechanical pressure. Product pressure of 60 MPa. It was found that with Zn doping, the electrical
density was found to increase with sintering temperature up to conductivity of the SPS material was enhanced, comparable to
about 81% of the theoretical value, which was much higher than the best p-type transparent conducting material reported in the
that (53%) of conventionally sintered pellets. In addition, the literature.
conductivity of the SPS specimens was typically about 106 S/cm at
50 8C, two orders of magnitude higher than that of conventional 2.17.12. ZnS-family phosphors
sintered powders, mainly due to corresponding increase in the The fabrication of ZnOZn, ZnOGa, ZnSSeAg phosphors
pellet density. Moreover, stacked pellets LiTi2(PO4)3/LiCoO2 with ceramics to be used as neutron detectors at high counting rates
clear interface were successfully prepared by SPS, which may open was investigated using an SPS apparatus [992]. The SPS process
the possibility of manufacturing all solid-state lithium batteries.
More recently, LiTi2(PO4)3-based solid electrolytes, i.e. LiTi2
(PO4)3, Li1.3Al0.3Ti1.7(PO4)3 (LATP), and Li1.3Al0.3Ti1.7(PO4)2.9(VO4)0.1
(LATPV), were also sintered by the SPS methods using powders
obtained from a solid-state reaction method [989]. The consolida-
tion process was conducted in the temperature range 9001100 8C
for 10 min, 100 8C/min heating rate and 30 MPa mechanical
pressure. It was found that the SPS process remarkably improved
pellets densication as compared to conventional sintering tech-
niques (cf. Fig. 134). In particular, the obtained ceramic products
were 9597% dense regardless the substituted ions (Al3+ and P5+).
LATP and LATPV exhibited ionic conductivity an order of magnitude
higher than LTP in SPS samples of similar densities (cf. Fig. 135). In
particular, the LATPV sample sintered at 1100 8C had the highest
conductivity (2.6  104 S/cm).
This preparation route was also applied by the same authors to
obtain Al substituted Li1+xAlxHf2x(PO4)3 (x = 0.00.5) solid elec-
trolytes [990]. The SPS process was conducted at 1100 8C for
10 min, 100 8C/min heating rate and by applying 30 MPa uniaxial Fig. 135. Ionic conductivity at 25 8C of the LiTi2(PO4)3 (LTP)-based solid electrolytes
pressure. Analogously to the previous investigation, SPS was sintered by SPS or conventional sintering (CS). Adapted from Chang et al. [989].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
was conducted under vacuum at 750 8C for 0.5 h. It was found that
the ZnO:Zn only having the fast component of lifetime (lumines-
cent peak of 395 nm) was successfully obtained. The obtained
material exhibited the fastest lifetime of 4 ns but its detection
efciency for thermal neutrons was evaluated to be one-eighths as
compared with a standard ZnS:Ag/6LiF detection sheet. Thus the
obtained ZnO:Zn ceramic material obtained by SPS may be suitable
for neutron imaging although the detection efciency is low.
2.17.13. Sn24P19.3BrxI8x
Sn24P19.3BrxI8x (x = 0, 2, 3,5, 7, 8) and Sn24P19.3Cl0.5I7.5 solid
solutions were sintered by SPS at 573 K and 500 MPa for 1 h under
argon atmosphere [993]. Electrical transport measurements were
performed on the resulting dense samples. It was observed that
both solid solutions were diamagnetic semiconductors. The values
of the band gap for Sn24P19.3BrxI8x (x = 08) was found to vary
from 0.03 to 0.14 eV and appeared to be a linear function of the
halogen atom ratio.
3. Modeling
From the analysis of the various systems presented so far, it
clearly appears that RS represents the mostly used technique to
perform the desired synthesis/sintering process. Thus, in what
follows, modeling considerations related to this process will be
presented and discussed.
Since RS process is a thermo-electro-mechanical system, the
corresponding modeling deals with a complex coupling of thermal,
electric and mechanic phenomena involving powders inside the
corresponding apparatus where several elements characterized by
different geometries and material properties may be found. In
general, the latter ones display a non-linear dependence from
temperature and pressure. This aspect makes modeling even more
challenging, because non-linearities accompanied by model
uncertainties and difculties to obtain reliable measurements
may cause masking effects that may be macroscopically mis-
interpreted.
Traditionally, the description of the mechanical behavior of RS
has been completely neglected. Thus, the analysis is limited to
solid (full-dense) or pre-sintered compact specimen instead of
sintering powders. However, the results obtained this way are
generally not extendable to RS of powder compacts, since, in this
case, it is likely that the mechanics of sintering and densication is
tightly coupled to the corresponding thermal and electric
phenomena. Moreover, even when limiting the analysis to a
thermo-electric perspective suitable for compact samples, too
many simplifying assumptions are typically assumed when
developing the model, thus leading to unsuccessful results from
the quantitative point of view. Indeed, simulation runs do not
completely correspond to the actual operative conditions experi-
mentally adopted, thus permitting only a qualitative description of
the system behavior. This is clearly evidenced by noting that,
usually, model results and experimental data are not directly
Fig. 136. Integration domain and boundary conditions of the model proposed by Raichenko and Chernikova [994].
245
compared, or, when this is done, the comparison is typically
limited to temperature proles. Most of the time, electric variables,
such as measured voltage or current, are not used for comparisons,
while the ability of the model to quantitatively track these
variables, along with the temperature levels involved, would make
it more reliable. The reason for such approach seems that
temperature distribution is considered the main cause of hetero-
geneity in nal sintered product, so that all other variables and
their effects on system behavior are minimized or completely
neglected, usually without any plausible justication. Additionally,
model reliability is not tested through prediction runs or, at least,
this information is typically not specied at all.
The review of RS modeling literature in chronological order
starts with Raichenko and Chernikova [994] and Raichenko et al.
[77], who quantitatively described heat transfer and generation
(joule effect) in an electrode(punch)specimenelectrode(punch)
system without a die. In particular, the following 1D (axial)
thermal balances, i.e. for steel (50S2G or 20KhN3A) electrode/
(punch) and for electric conductor powder (VK16 or VK8VK hard
alloys) specimen, respectively, coupled through continuity bound-
ary conditions at interface contacts (see Fig. 136), are taken into
account:

@T @2 T s pecimen powder
ri C p;i ki 2 rel;i j2 ; i (3.1)
@t @z electrode steel
In this model, heat is uniformly generated as proportional to the
corresponding electric resistivity (rel,i) and the square of the same
density current (j) that ows in series through the electrode(-
punch)specimenelectrode(punch) system. Axial symmetry is
assumed, thus considering half of the real domain of integration.
Cooling at extreme ends of electrode(punch) due to contact with a
high thermal capacity of the rest of the RS system is represented by
assigning a constant temperature equal to the initial one (T0).
Constant current density and constant thermophysical para-
meters (density ri, thermal capacity Cp,i, thermal conductivity ki,
and electric resistivity rel,i) are assumed to obtain the model
solution analytically. The effect of actual changes of thermo-
physical parameters with temperature, while recognized and
provided in the paper, is taken into account by solving the model
starting with different initial temperatures and selecting a
representative mean value. Besides, ongoing sintering of powder,
is modeled through the determination of effective thermophysical
parameters, obtained by correcting their corresponding solid (full-
dense) values with a constant level of specimen porosity (u) as
reported in the following equations:
r powder rsolid  1  u (3.2)
C p; powder C p;solid  1  u (3.3)
3
k powder ksolid  1  u (3.4)
2
1
3
rel; powder rel;solid  1  u (3.5)
2
246 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 137. Time dependence of the temperature T1 in the centre of a specimen of
VK8VK hard alloy (pore free, u = 0; j = 429  104 A m2 (13) and j = 784 
104 A m2 (10 30 )). Adapted from Raichenko and Chernikova [994].
Fig. 137 shows the comparison between experimental data and
modeling results in terms of temperature temporal prole taken at
the specimen center (z = 0 in Fig. 136) for the system VK8VK
powder specimen and 20KhN3A steel electrode (with u = 0), at two
different operative conditions, i.e. constant current density equal
to 429 and 784 A/cm2. At this point it is worth noting the absence
of details on the experimental procedure adopted when obtaining
the data. Only the information needed to compare them to the
model (i.e. current density, forcing function of joule effect) is
provided. Pulses and pressure are not even mentioned. The difcult
to appreciate likelihood of model simplifying assumptions is clear.
This consideration, actually, applies to most of the modeling papers
reviewed in what follows.
The experimentally measured curves 1 and 10 in Fig. 137
correspond to 429 and 784 A/cm2, while the corresponding model
results are reported for both operative conditions, being the
thermophysical parameters evaluated at 20 8C (curves 2 and 20 )
and 500 8C (curves 3 and 30 ), respectively. As it can be seen,
matching is not satisfactory. On the other hand, the model predicts
a relatively at temperature prole along system axis inside
electric conductor powder specimen, while a higher temperature
Fig. 138. Integration domain and boundary conditions of the model proposed by Yoneya and Ikeshoji [995].
gradient is simulated through the electrode(punch) as due to
cooled ends effect and a lower thermal conductivity.
More than 10 years later, Yoneya and Ikeshojy [995] addressed
the current density and the consequent joule heat distribution
between the specimen and the die by modeling the system
depicted in Fig. 138 (i.e. sample, die and portion of plungers inside
die). Specically, thermal balances (as Eq. (3.1) where joule heat is
expressed in terms of voltage gradient) are coupled to the
following current density balances (i.e. Kirchoff law with
distributed parameters) in a 2D cylindrical coordinate system:
1 @1=rel;i r @=@r @1=rel;i @=@z
0;
r

@r @z
s pecimen
i (3.6)
gra phitic die
where w represents the electric potential (current density vector is
proportional to voltage gradient according to Ohms law,
j 1=rel r
). Boundary conditions (see Fig. 138) take into
account radiation heat losses from outer surface of the die, and
effective heat conduction removal (h) in axial direction from
plunger to the electrodes which are not modeled. Convection heat
losses from outer surface of the die are neglected since PDS
apparatus chamber is operated under vacuum. Boundary conditions
between specimen, die and plungers are not explicitly provided, but
it seems that continuity for both temperature and voltage (i.e. equal
voltage and current density between both contacting sides) is
assumed. The model, where thermophysical parameters for solid
graphite or copper powder specimen into a graphitic die are taken
into account, is solved by proposing a numerical technique based on
the method of fundamental solutions, suitable for capturing in a more
simple way voltage and temperature spatial gradients discontinuity
at different materials junctions.
In Figs. 139 and 140 modeling results in terms of voltage and
current density axial proles (i.e. r = 0 in Fig. 138) under a uniform
temperature distribution of 303 K for graphite solid and copper
powder sample, when the system underwent 1 V voltage drop, are
reported. In particular, the isotropic thermophysical properties of
copper powder are determined for a constant porosity value.
A comparison with the conventional differential method by
Successive Over-Relaxation (SOR) is shown for appreciating
the numerical solution accuracy. Even if no comparison with
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 139. Calculated voltage proles in the z-direction at r = 0 for the case of graphite (a) and copper powder (b) specimen. Comparison with the results obtained by the
differential method (SOR). Adapted from Yoneya and Ikeshoji [995].
experimental data is given, it can be concluded that electric current
ows through sample instead of the surrounding graphitic die
when copper powders are used instead of solid graphite as a result
of an higher electric conductivity. Since an equal voltage drop is
applied for both samples, current densities are indeed higher when
copper is used (cf. Fig. 140). Correspondingly, axial voltage drop is
concentrated through graphite plungers when a copper powder
specimen (almost equipotential) is inserted into graphitic die (see
Fig. 139b), while it is almost uniformly distributed along whole
system if a graphitic sample is used (see Fig. 139a).
The authors reached also another conclusion that, due to its
lowest cross-section area, heat generation is concentrated on
plungers, as clearly shown in Figs. 141 and 142, where theoretical
potential, joule heat and temperature distribution contour plots
are reported for graphite solid and copper powder at time 500 s
(i.e. at reached steady state), when applying a voltage drop of 0.8
and 0.6 V to the system, correspondingly. As a result, temperature
is almost uniform in the sample for both cases, even if temperature
gradient is lower when copper powders are used.
A reverse conclusion was reached by Yucheng and Zhengyi
[996] when simulating TiB2/BN composite solid inserted into a
graphitic die as schematically depicted in Fig. 143. It is worth
noting that this material shows an electric resistivity almost equal
to that of graphite, while thermal conductivity is lower. Moreover,
system dimensions are larger than those ones used in the previous
Fig. 140. Calculated current density proles in the z-direction for the case of graphite (a) and copper powder (b) specimen. Comparison with the results obtained by the
differential method (SOR). Adapted from Yoneya and Ikeshoji [995].
247
paper (cf. Figs. 138 and 143). Only thermal balances for the
different materials in 2D cylindrical coordinate system are taken
into account. Constant thermophysical parameters are assumed in
order to obtain the steady-state analytical solution through an
original derivation which is based on radial as well as axial
symmetry. In particular, the solution of the original 2D (r and z
coordinate) mathematical problem is obtained as the product of
the solution of two 1D problems, as shown in Fig. 143. Radial
dependency is obtained by coupling thermal conduction and joule
heat generation inside two innitely long coaxial cylinders with
radiuses equal to those of real system, while axial dependency
results from considering sandwiched slabs of innite surface area
and heights equal to those of real system. Continuity boundary
conditions at contact surfaces are applied, being radiation heat
losses from lateral outer surface of external cylinder mimicking
lateral outer surface of die. A constant temperature value of
exposed surfaces of slabs (i.e. ambient temperature) which
simulates axial cooling from plungers to rams is assumed.
Fig. 144 reports the steady-state temperature difference from
sample centre along radial direction as predicted by the model,
while Fig. 145 shows the experimentally determined temporal
proles of temperature measured by two thermocouples posi-
tioned at sample center and, radially apart, at plunger/die contact
interface. Unfortunately, the operative conditions applied when
making these experimental data and those used as inputs for
248 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 141. Contour plots of potential (a), joule heat (b) and temperature (c) for the case of graphite solid specimen (t = 500 s; V = 0.8 V). Adapted from Yoneya and Ikeshoji [995].

Fig. 142. Contour plots of potential (a), joule heat (b) and temperature (c) for the case of copper powder specimen (t = 500 s; V = 0.6 V). Adapted from Yoneya and Ikeshoji
[995].

running the simulations (i.e. electric current densities and to 350 8C inside sample and 100 8C inside the die, being the TiB2/BN
corresponding heat generation) are not provided in the paper, sample hotter than graphite. Experimental measurements inside
neither are the thermophysical data and sample height. In any sample attains a relatively higher temperature difference equal
case, the model predicts a high radial temperature difference equal to 450 8C, and inner thermocouple always measures an higher

Fig. 143. Integration domain and boundary conditions of the model proposed by Yucheng and Zhengyi [996].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 144. Calculated steady-state temperature difference from sample centre along
radial direction. Adapted from Yucheng and Zhengyi [996].
temperature level. Thus, a qualitative agreement between experi-
mental data and model results is reported. On the other hand,
authors point out that during experimental run steady state is not
reached yet, as clearly shown in Fig. 145.
A relatively high temperature gradient in radial direction is also
modeled by Keum et al. [997] when the SPS of an electric insulator
(Al2O3) powder compact is considered. In particular, 1D (radial)
thermal balance with conduction and joule heat generation for the
sample of 2 cm diameter is solved via Finite Element Method (FEM)
for obtaining the temperature distribution. The surrounding
graphitic die is taken into account for determining the necessary
boundary condition of thermal balance inside the sample. In
particular, the temperature value at sample/die interface is
assigned. This value is determined by evaluating the joule heat
developed by the portion of current owing inside the die as a
function of its electric conductivity and its cross-section size, in
comparison with those ones of the alumina sample (i.e. sample and
die are implicitly considered as electric resistances in parallel
combination). However, it is worth noting that thermophysical
parameters and system geometry are not provided, and boundary
conditions are not clearly stated. On the basis of the so calculated
temperature distribution, grain growth of sintering powder is
mathematically described via Monte Carlo simulations by moving
grain boundaries and peak points of a ne cell structure. In
Figs. 146 and 147 the calculated radial temperature proles inside
alumina sample at two different steady states (i.e. when the
boundary temperature at sample/die contact is 1450 and 1650 8C,
correspondingly) are reported. Sample center is always at a lower
temperature than sample outer surface (maximum difference is
77 8C), since, according to their resistivities, electric current mainly
ows through graphitic die. Thus alumina sample is basically
Fig. 145. Temporal proles of temperature measured by two thermocouples
positioned at sample centre and at interface contact with the die. Adapted from
Yucheng and Zhengyi [996].
249
Fig. 146. Temperature distribution of Al2O3 at sintering temperature 1450 8C.
Adapted from Keum et al. [997].
heated by thermal conduction from the die. This aspect reects on
the calculated grain growth distribution which changes when
temperature is augmented, as depicted in Figs. 148 and 149, where
a qualitative comparison in terms of grain size between model
results and experimental data (SEM photographs) is provided.
The parallel combination between electric resistances of inner
sample and surrounding die which determines the distribution of
owing current density is taken into account by Heian et al. [998].
In this work the SPS, where a high exothermic reaction synthesis of
MoSi2/SiC composite starting from the mixture of Mo, Si and C
elemental powders occurs, is taken into account. 2D cylindrical
coordinate thermal balances for the sintering/synthesizing powder
sample and graphitic die shown in Fig. 150 are coupled with the
corresponding current density balances for properly evaluating
joule heat distribution. It is worth noting that plungers are not
simulated. The thermal balance inside powder compact is
characterized by an additional source term related to the enthalpy
released during the highly exothermic reaction between starting
powders. The rate of the corresponding heat generation is taken
into account by coupling materials balances of reacting species
with pseudo-homogeneous second-order kinetics and Arrhenius
type dependence of kinetic constants. Mixing rules are applied for
Fig. 147. Temperature distribution of Al2O3 at sintering temperature 1650 8C.
Adapted from Keum et al. [997].
250 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 148. Comparison of grain growth of Al2O3 between SEM and simulation at the sintering temperature 1450 8C. Adapted from Keum et al. [997].

Fig. 149. Comparison of grain growth of Al2O3 between SEM and simulation at the sintering temperature 1650 8C. Adapted from Keum et al. [997].

determining sample thermophysical parameters (specic heat, composition and electric conductivity of graphite, i.e. on the
thermal and electric conductivities) as a function of temperature, relative values of electric resistances for sample and die in parallel
which are based on fully dense thermophysical properties of combination, which determine where electric current ows and
reacting species, weighted by composition that changes as joule heat is generated. It is worth noting that these modeling
combustion reaction progresses. However, porosity variations
due to sintering under mechanical load are not taken into account.
Boundary conditions for thermal balances consider radiation and
convective losses from all exposed surfaces of die. In particular,
different effective heat transfer coefcients and emissivities are
taken into account to express heat losses from top and bottom or
from lateral surfaces of the die. This choice is made in order to
simulate the presence of contact resistances at top and bottom
surfaces of the die depicted in Fig. 150. Boundary condition at
contact surfaces between sample and die is not provided while
continuity one seems to be applied. Boundary conditions for
current density balances are stated as usual, i.e. connement of
electric current into conducting materials and applying a voltage
drop between the top and bottom equipotential surfaces of the die.
Comparison with experimental data is not given, while the model,
solved numerically via nite differences (FD), clearly predicts
volume or wavelike combustion reaction (inward from die to
sample or, conversely, outward in opposite direction) depending
on sample size (ranging from 2 to 8 cm in diameter), initial powder Fig. 150. Integration domain of the model proposed by Heian et al. [998].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
results are obtained under the application of 1540 V voltage drop
along graphitic die, which is a relatively high value in SPS
conventional experimental runs.
All the relevant qualitative results reached by modeling
activities described so far (i.e. hot spots in plungers, electric
current and related joule effect distribution eld as a function of
electric resistances of sample and die in parallel combination) are
conrmed by Matsugi et al. [999]. Here, the Spark Sintering
behavior of pre-sintered Ti powders (electric conductive material)
and alumina powders (electric insulator material) are compared
with model results obtained by considering the SPS system
schematically depicted in Fig. 151. Apart from considering a more
complex spatial domain of integration closer to the real system
with respect to the other ones used so far, for the rst time in the
modeling literature pulses of electric current (rectangularly
shaped, with 100 ms duration) and mechanical load actually
applied during Spark Sintering experimental runs are mentioned
and taken into account, respectively. The proposed model
considers the usual thermal balance, along with heat conduction
and joule effect, coupled to current density conservation equation
for pre-sintered powder sample, graphitic die and plungers. The
changing of the relative density in pre-sintered powder sample is
taken into account through the evaluation of effective thermo-
physical properties. These are determined taking advantage of the
corresponding full-dense thermophysical material properties as
well as empirical functions (third order polynomials) of relative
density (D). The latter one is considered as a function of
temperature (T) and applied nominal pressure (P) through the
following expression:
DT; P Dm aP bT  T 0 c (3.7)
where Dm is the initial relative density of pre-sintered powder
sample and T0 is the initial temperature of the system, while a, b,
and c are adjustable parameters. Their values are tted by
comparison of Eq. (3.7) and experimentally determined relative
density. This latter one is evaluated by measuring longitudinal
Fig. 151. Integration domain of the model proposed by Matsugi et al. [999].
251
displacements between electrodes and assuming a uniform
temperature and pressure distribution inside sample.
Thermal and electric contact resistances are taken into account as
a function of local temperature and are referred to a specic contact
surface (horizontal and vertical) between the different elements of
Spark Sintering apparatus (i.e. die/compact, punch/compact, punch/
die and graphite-spacer/punch) depicted in Fig. 151. As a result,
the obtained contact conductances range in the intervals 5  103 to
7  106 S/m2 and 3  102 to 2  105 W/(m2 K).
The comparisons between experimental data and model results
reported in the original paper are shown in Figs. 152 and 153. In
these gures, temperature contour plot for titanium and alumina
compacts at steady state under the application of 37.5 MPa and
constant current equal to 290 and 700 A, correspondingly, are
compared with the temperature values experimentally measured
by thermocouples at six different positions (two in plungers, three
in die, and one in sample center). As it can be seen in Fig. 152, the
matching for the case of titanium sample (maximum deviation is
90 8C, corresponding to almost 10% error) is better than for alumina
case. It is evident that current ows through the die when an
insulator (alumina) is used, so that temperature reaches lower
values inside sample than inside the die (10 8C difference). Thus, it
can be concluded that sample is basically heated by conduction
from the surrounding die. On the other hand, the opposite
direction of heat ux is observed for titanium (conductor) sample,
which results hotter than die (30 8C difference). Thus, temperature
gradient are larger in the case of the conducting sample. Both cases
show hot spots in plungers as a consequence of their lowest cross-
section area.
With the aim of reducing heterogeneity in nal sintered
product of complex shape by reducing heterogeneity of tempera-
ture eld distribution inside the sample, the same authors [1000]
applied the previous model to Spark Sintering of pre-sintered Ti
powder with a punchdie-two step system schematically depicted
in Fig. 154. After a pre-sintering stage (15 min) with pulsed current
(rectangular pulses of 100 A and duration 100 ms, 1 ON and 1 OFF)
and constant mechanical load equal to 7 kN (i.e. 10 MPa on top
252 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 152. Comparison between experimental data and model results in terms of
temperature distribution (Kelvin scale) of Ti compact at t = 3600 s subjected to
37.5 MPa and 390 A. The measurements by six thermocouples at positions P1, P2, D1,
D2, D3 and C1 are indicated in brackets. Adapted from Matsugi et al. [999].
plunger and 38 MPa on bottom plunger), a second step (1 h) of
constant continuous current of 900 A, while applying the same
mechanical load, is performed and modeled. In Figs. 155 and 156
the comparison between experimental data and modeling results
in terms of temperature contour plot at 3 and 10 min, corres-
pondingly, is given. Temperatures experimentally measured by
thermocouples at eight different positions (two in plungers, three
in die, and three in sample axis) are indicated in brackets. Matching
is very good (maximum difference is 3%). As clearly shown,
temperature reaches its maximum value inside lower plunger (i.e.
at the smallest cross-section area), and titanium sample is always
hotter than surrounding die in radial direction.
The heating by thermal conduction from surrounding die of an
insulator-like material sample is evidenced once again by Wang
et al. [1001] when analyzing SPS behavior of BN powder. The
modeling of powder densication is addressed by assuming that
SPS process consists of three stages up to the shrinkage occurrence,
as depicted in Fig. 157. In the rst stage, temperature rises with
negligible shrinkage; then, in the second one, density rises quickly
due to shrinkage being the temperature almost constant; nally, a
stage of holding temperature, where density of sample keeps a
constant value too, follows. Only the rst stage is considered in the
modeling activity performed in this paper, thus justifying the use
of a constant spatial domain of integration (as depicted in Fig. 158).
Accordingly, only the temperature dependence of the thermo-
physical parameters of powder material (unfortunately, not
provided in the paper) is taken into account, being the applied
mechanical load and consequent shrinkage during sintering not
Fig. 153. Comparison between experimental data and model results in terms of
temperature distribution (Kelvin scale) of Al2O3 compact at t = 3600 s subjected to
37.5 MPa and 700 A. The measurements by six thermocouples at positions P1, P2, D1,
D2, D3 and C1 are indicated in brackets. Adapted from Matsugi et al. [999].
considered. The usual 2D cylindrical coordinate thermal and
current density balances for graphitic die and plungers, and for
powder compact are solved by Ansys (FEM). However, the relevant
equations are not given neither boundary conditions for current
density except for the voltage drop assigned between plungers
ends. Boundary conditions for thermal balances, i.e. radiation
losses from all exposed surfaces (neglecting natural convection
due to vacuum conditions guaranteed inside SPS chamber during
processing), assigned temperature (initial value) at plungers
ends mimicking a perfect cooling system in SPS apparatus, and
continuity condition at every contact surface are specied.
Fig. 159 shows model results (at 3 V voltage drop between
plungers ends) in terms of temperature contour plot distribution
at four different times, for a quarter of domain (the assumed
cylindrical symmetry guarantees a specular behavior in the rest
of the system). It is seen that, the intensive heat generation in
plungers regulate heat ux direction inside sample and die,
especially when the heating process begins. However, as a
consequence of a relatively higher electric resistivity of BN powder
than graphite, it is clearly shown that sample is colder than die at
earlier times. This is due to the preferential owing path of electric
current through the less resistive die, thus joule heat effect is here
more pronounced than inside powder sample. On the other hand,
the radial gradient of the temperature is reversed at longer times,
as a consequence of the radiation losses from outer surfaces of the
die, which become relevant as temperature rises.
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 253

Fig. 154. Integration domain of the model proposed by Matsugi et al. [1000].

Consequently, temperature radial prole inside powder sample
may present a minimum (wavy shape) as clearly shown in
Fig. 160. In general, temperature difference in radial direction
inside sample is lower than inside die (about 10 8C vs. 40 8C).
Qualitative comparison with experimentally measured tempera-
tures at different positions inside the sample conrms these
modeling results. However, it should be noted that the experimental
runs are performed with operative conditions different from those
ones used during simulations, i.e. temperature is controlled by
adjusting electric power input while a constant voltage drop is
adopted when solving the model.
It is concluded that, in order to minimize nal sintered
product heterogeneity in terms of relative density distribution,

Fig. 155. Comparison between experimental data and model results in terms of Fig. 156. Comparison between experimental data and model results in terms of
temperature distribution (Kelvin scale) of Ti compact at t = 180 s subjected to 7 kN temperature distribution (Kelvin scale) of Ti compact at t = 600 s subjected to 7 kN
and 900 A. The measurements by eight thermocouples at positions P1, P2, D1, D2, D3, and 900 A. The measurements by eight thermocouples at positions P1, P2, D1, D2, D3,
C1, C2 and C3 are indicated in brackets. Adapted from Matsugi et al. [1000]. C1, C2 and C3 are indicated in brackets. Adapted from Matsugi et al. [1000].
254 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 157. Schematic illustration of the sintering process. Adapted from Wang et al.
[1001].
temperature gradient inside sample may be kept small by
lowering heating rate.
The same authors [1002] applied the developed model to an
electric conductor-like material sample, namely TiB2/BN powder.
The system geometry used is that one reported in Fig. 158. In this
case, electric current ows through sample which results hotter
than die (as shown in Fig. 161c), while, in axial direction, an
intensive joule heat generation rises plungers temperatures till
reaching the highest values in the whole system (cf. Fig. 161b).
Thus, sample is heated axially by thermal conduction from
plungers, while loosing heat to the die in radial direction. High
radial temperature differences are predicted inside sample
(about 150 8C). However, it is worth noting that the voltage
drop between rams applied as input to the developed model is
not provided, neither comparisons with experimental data. The
temperature gradients increase as temperature rises with time
Fig. 158. Integration domain of the model proposed by Wang et al. [1001].
as shown in Fig. 161d. Again, it is concluded that by lowering
heating rates, the transient spatial temperature differences
inside sample are reduced, thus minimizing nal sintered
product heterogeneity.
An approach similar to that one adopted by Matsugi et al.
[999] is followed by Chang et al. [1003] when simulating the
ElectroconsolidationTM process. ElectroconsolidationTM is a pro-
cess suitable for densifying complex-shaped preformed materials
to near-net shape by using electrically conductive particulate
solids as a pressure transmitting medium. As schematically
depicted in Fig. 162, the densication of preformed materials is
obtained by passing an electric current through a bed of particulate
graphite that surrounds the preform and, simultaneously, trans-
mitting pressure by means of a double-acting hydraulic press.
Basically, the surrounding graphite powder, heated up by joule
effect, permits preform densication by raising its temperature
through thermal conduction and acting as a pressure transmitting
medium. A 2D cylindrical coordinates model, developed with
respect to the system geometry depicted in Fig. 163, consists of
three modules. The rst one determines the density and electric
resistivity of graphite particulate medium as a function of the
mechanical pressure applied. This module basically consists of two
empirical algebraic equations which are determined by tting the
experimental data represented in Fig. 164, which are obtained by
using a large diameter die in order to minimize the effect of
powder-die wall friction. Using such a module along with the
temperature dependent electric resistivity of full-dense (solid)
graphite, the corresponding graphitic powder value is obtained as a
function of pressure and temperature rel; powder gra phite . In the
second module, on the basis of the results obtained in the rst
module, the software Elecktra (FEM) is used for determining the
resistive heating, voltage and current distribution eld inside the
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 255

Fig. 159. (ad) Temperature contour plots of SPS of BN powder subjected to 3 V at four different processing times. Adapted from Wang et al. [1001].

Basically, the employed software solves the current density

balances with Ohmic behavior, while Maps provides the solution of
thermal balances taking into account joule effect and thermal
conduction. In particular, the necessary thermal conductivity of
particulate graphite is obtained on the basis of the electric
resistivity determined by the rst module through the following
empirical relationship:

ksolid gra phite T

k powder gra phite T; P (3.8)
rel; powder gra phite T; P

Convection and radiation heat losses from the exposed surfaces

Fig. 160. Calculated radial temperature proles for SPS of BN powder. Adapted from
Wang et al. [1001].
whole system. Finally, the resistive heating distribution eld based
on Elektra results is given to the third module where the software
Maps (FD) is adopted for the calculation of the corresponding
temperature distribution eld.
are considered as boundary conditions, while a constant tem-
perature equal to 50 8C is set at plungers ends, thus considering
perfect cooling from a very large thermal capacity reservoir. In
particular, effective heat transfer coefcients for convection and
radiation losses from exposed surfaces to the air or at plungers/die
interfaces are considered, thus mimicking thermal contact
resistances.
The innovative aspect of the developed model is that friction
between powder and internal die wall is taken into account in

Fig. 161. Calculated temperature distribution for TiB2/BN powder system. System geometry and relevant positions (a); axial prole (b); radial proles (c) and temporal
proles (d). Adapted from Wang et al. [1002].
256 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 162. Schematic diagram of Electroconsolidation1 apparatus. Adapted from
Chang et al. [1003].
order to determine the axial pressure distribution inside the
particulate graphite medium. This way, the temperature- and
pressure-dependent thermophysical parameters calculated above
change not only due to the temperature distribution eld
calculated by Maps, but also according to the pressure distribution
in axial direction assumed. This approach is different from that one
proposed by Matsugi et al. [999] where a single value of pressure
(i.e. nominal pressure) is used, although for a pre-sintered
Fig. 163. Integration domain of the model proposed by Chang et al. [1003].
compact. By neglecting friction between powder and preform,
the pressure distribution is determined through integration of the
following axial momentum equation (cf. Fig. 165):
dPa Pa
2m (3.9)
dz R
where Pa is an axial pressure averaged over cross-section at z
position, R is die internal diameter, m = hl is the friction index
(being h the coefcient of friction, and l the Janssen constant). This
equation is obtained by assuming that Coulomb law is applied for
contact friction (Pf = hPr, where Pr is the radial pressure due to die
wall and Pf the frictional force due to shear) as well as radial
pressure is proportional to axial one (Pr = lPa).
The friction index which actually changes during compaction, is
assumed to be constant for simplicity. Axial and radial pressures
(Pa and Pr) are used to determine the actual compaction pressure
acting on the graphite particulate medium at axial position z. The
density and the electric resistivity of graphitic powder are
determined by the rst module of the proposed model on the
basis of the compaction pressure.
In Fig. 166a the successful comparisons between model results
and the temporal proles measured by thermocouple at two
different positions inside particulate graphite medium are
reported. As schematically shown in Fig. 166c, the system here
considered, without the preform, is subjected to the voltage
temporal prole reported in Fig. 166b and to a nominal pressure of
136 MPa. According to the authors, in general the temperature
eld distribution is particularly sensitive to the absence or
presence of electric contacts at powder/die and plunger/die
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 257

Fig. 164. Effect of applied pressure on graphite particulate medium used in Electroconsolidation1 apparatus. Adapted from Chang et al. [1003].

Fig. 165. Forces on an element of graphitic particulate medium inside the die. Adapted from Chang et al. [1003].

interfaces. The model results reported in Fig. 167 show the peratures. This is basically due to its higher (porosity-dependent)
corresponding radial temperature proles at different instants, electric resistivity, even if full-dense graphite is a relatively good
during heating and cooling stages. As it may be seen, graphite electric conductor. Moreover, relatively high radial temperature
powder looses heat to the die and reaches always higher tem- differences (about 100 8C) inside powder are predicted.

Fig. 166. Comparisons between experimental data and model results in terms of temporal proles of temperature taken at two positions inside Electroconsolidation1
apparatus (a). Temporal prole of applied voltage drop between rams ends (b). system geometry and relevant positions considered (c). Adapted from Chang et al. [1003].
258 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 167. Calculated radial proles of temperature at different instants for the system considered in Fig. 166 (a). System geometry and relevant positions considered (b).
Adapted from Chang et al. [1003].
The relevance of contact resistances in SPS process is eviden-
ced by Zavaliangos et al. [1004] when simulating the system
schematically depicted in Fig. 168 (Model 1050-Sumitomo),
where a solid graphitic cylinder is inserted into the die. The usual
2D cylindrical coordinate system of coupled thermal and electric
problems is numerically solved via Abaqus (FEM). In particular,
radiation heat losses from all exposed surfaces are taken into
account except on rams ends, where a constant temperature
equal to 25 8C is set. Thermophysical parameters are provided.
Moreover, a proportional feedback controller based on outer die
surface temperature is modeled for the determination of the
voltage drop applied between rams ends (see Fig. 168). This
controller mimics the actual proportional integral derivative (PID)
one present in real SPS apparatuses, which sets the electric power
input to the system when temperature controlled runs are
experimentally performed.
Boundary conditions between contacting surfaces (hori-
zontal and vertical) appearing in Fig. 168 are mathematically
described by means of constant contact conductances. Indeed,
across a perfect interface, the temperature and the electric
potential are continuous functions. However, when two real
surfaces are considered, geometrical irregularities and surface
deposits prevent perfect contact. Consequently, both tem-
perature and electric potential are discontinuous. Thus, a nite
temperature (Du) or voltage difference (Dw) should be
considered at the interface as shown in Fig. 169, being
the thermal ux and electric current density across it expressed
as follows:
q c hg  u1  u2
j s g  1  2
where hg and sg are the thermal and electric gap conductances,
respectively. In addition to the localized drop of temperature, the
heat ux is also discontinuous at the interface as joule heat is
generated by electric contact resistance:
q ec j  1  2 s g  1  2 2
As a result, the heat ux at the contacting surfaces of parts (1)
and (2) in Fig. 169, can be written as:
1
q 1 q c  12q ec hg  u1  u2  s g  1  2 2 (3.13)
2
1
q 2 q c 12q ec hg  u1  u2 s g  1  2 2 (3.14)
2
where joule heat due to electric contact resistance is assumed to be
evenly divided between the two contacting surfaces.
Fitting of contact conductances (hg and sg) is performed by
comparing model results with experimental data referred to the
system reported in Fig. 168 under the application of 15 MPa at a
heating rate of 15 8C/min. The constant values obtained are
reported in Table 4.
Clearly, vertical contact resistances are higher than horizontal
ones, from the electric as well as the thermal point of view. This
difference is ascribed to the mechanical load directly applied on
the horizontal contacts, which makes them closer to perfect
contact condition.
The innovative aspect of this paper is represented by the
discrimination between horizontal and vertical contact resistances
that is not considered by Matsugi et al. [999,1000]. The importance
of contact resistances is shown in Fig. 170. Here, the difference
between experimentally measured temperatures at sample center
and at outer surface of die is reported as a function of the latter one.
The corresponding model results, with and without taking into
account thermal contact resistances, are also reported. It is
noteworthy that increasing temperature differences up to more
than 200 8C are experimentally found, being sample center at
(3.10)
higher temperature than outer die, even if the two SPS elements
(3.11) are made of the same electric conductor material.
Table 4
Thermal and electric contact conductances determined by Zavaliangos et al. [1004].
Contact conductance Horizontal Vertical
2 7
Electric (S/m ) 1.25  10 7.5  106
(3.12) Thermal (W/(m2 K)) 2.4  103 1.32  103
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 259

Fig. 168. Integration domain of the model proposed by Zavaliangos et al. [1004].

In Fig. 171 the relative contribution of the possible heating loss
routes as a function of surface die temperature are reported.
Indeed, temperature evolution in plungers/sample/die assembly is
characterized by the interplay of joule heat generation and heat
transfer. Heat is removed from the assembly via thermal
conduction towards the loading train and, eventually, the
water-cooled electrodes (not modeled) and via radiation to the
wall of the SPS chamber. Referring to Fig. 171, at low temperatures
most of the heat is lost by conduction q c to the loading train,
while the role of radiation q rps q dt ds
r q r becomes more
important at higher temperatures, as expected. However, heat
removed by conduction to loading train represents always a
relevant portion of total heat losses, ranging from 40 to 80%. It is
worth noting that these conclusions have been obtained by
simulating cooling water system by setting a constant ambient
temperature at rams ends. Thus, the conclusion may be too
pessimistic, because the chosen boundary condition represents a
perfect cooling system.
In any case, the heat removed by conduction to loading train
seems to be a relevant portion of the total heat removed.
Contact resistances are analyzed also by Vanmeensel et al. [39],
when simulating the system schematically depicted in Fig. 172
(Model HP D 25/1-FCT, Germany), where a solid cylinder specimen
is inserted into the die. The system presents two boreholes as
depicted in Fig. 172: the upper one is used for temperature
measurement near the sample by pyrometer, while the lower one
260 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 169. Temperature or voltage drops at an imperfect interface with apparent contact area SA due to thermal contact resistance or electrical contact resistance as heat, q c , or
electric current ux, J, ows across the interface, respectively. Joule heat, q ec , is also generated and evenly distributed into two parts. q 1 and q 2 are heat ux in parts 1 and 2,
respectively. Adapted from Zavaliangos et al. [1004].

is used for xation and positioning of the whole assembly as well expressions:
as for symmetry reasons. Balance equations considered are the r
same as those ones reported by Zavaliangos et al. [1004], with 2
IRMS I (3.15)
radiation heat losses from lateral surfaces. However, an effective 3 peak
convective heat transfer to simulate axial cooling directly from r
2
spacers ends is taken into account. Experimental runs are V RMS  V peak (3.16)
3
performed by controlling temperature measured at bottom of
upper borehole (closest as possible to the sample center), while the where Ipeak and Vpeak represent the peak values of the correspond-
developed model is solved via Abaqus (FEM) imposing a total ing pulsed signals experimentally measured as independent
current owing through the assembly. It is worth noting that, in variables which are reported in Fig. 173.
order to properly evaluate joule effect when pulsed DC is used as in Here, a pulse sequence of 10 ms ON and 5 ms OFF (which means
Model HP D 25/1 (FCT), the RMS (root mean squared) values of that 10 ms is the duration of direct pulses, followed by 5 ms period
current and voltage are accounted for through the following of no pulses) is adopted.

Fig. 170. Comparison between experimental data and model results in terms of temperature difference at sample centre and die surface. Adapted from Zavaliangos et al.
[1004].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 261

Fig. 171. The relative contribution of various mechanisms of heat losses vs. the controlled temperature. Adapted from Zavaliangos et al. [1004].

Fig. 172. Integration domain of the model proposed by Vanmeensel et al. [39].

Fig. 173. Typical on-part of a 10/5 ms on/off pulsed current signal provide by a FCT System apparatus. Adapted from Vanmeensel et al. [39].
262 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 174. Dummy geometries used to establish the inuence of horizontal and vertical contact resistances. Thick horizontal lines indicate the presence of horizontal graphite
papers while thick vertical lines indicate the presence of the vertical graphite papers. Adapted from Vanmeensel et al. [39].

Thermal and electric resistances at contacts between the
elements of the dieplungersample set-up are evaluated experi-
mentally by comparing thermal and electric response of three
different graphite set-ups characterized by increasing complexity,
thus allowing to establish the inuence of horizontal as well as
vertical contacts resistances. The dummy geometries used are
schematically depicted in Fig. 174, where graphite sheets with
anisotropic thermophysical properties are inserted at horizontal
and vertical contacts.
In particular, using the full dummy geometry (F), where no
contact is present, the electric resistivity of the solid graphite,
rel;solid gra phite provided by the supplier, is experimentally veried
by comparison of model results with experimental data, while tting
the effective heat transfer coefcient at spacers ends (800 W/
(m2 K)). Fig. 175 shows the successful comparison between
experimental data and model results obtained when simulating
FAST behavior of F dummy geometry. The experimental current
temporal prole represents the model input, while temperature at
sample center, voltage and power are model outputs.
Consequently, by subtracting the experimentally determined
electric resistance of F geometry from that one of SPP geometry
(cf. Fig. 174) at various steady states, the electric horizontal
contact resistance between plungers and spacers is evaluated as a
function of temperature. This contact resistance is used for
determining the electric resistivity of the graphite foil
rhorizontal
el;gra phite foil sandwiched at horizontal contacts between spacers
and plungers, and modeled by means of the thin-lm approxima-
tion. The corresponding thermal conductivity of the sandwiched
graphite foil khorizontal
gra phite foil is determined through the following
empirical expression:
rel;solid gra phite
khorizontal
gra phite foil T m  ksolid gra phite T  (3.17)
rhorizontal
el;gra phite foil
T
where the value of the proportional constant m is 2.85, as tted
through comparison of model results with experimental data of
SPP dummy geometry. Basically, this empirical relation states that,
at any temperature, the ratio between thermal and electric
conductivities of graphite foil sandwiched at horizontal contacts
is proportional to the corresponding ratio of solid graphite.
Finally, thermal and electric resistivities of graphite foil in
vertical contacts between plungers and die are determined as

Fig. 175. Comparison between simulated and experimentally measured temperature (a); input current (b); voltage (c) and power (d) temporal proles for F dummy
geometry. Adapted from Vanmeensel et al. [39].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
follows:
vertical horizontal
r el;gra phite foil T ael  r el;gra phite foil T
1 system geometry considered in the paper. On the other hand, in the
kvertical
gra phite foil T ather 
khorizontal
gra phite foil
T
where the values of the proportional constants ael and ather result
to be both equal to 7 from the tting procedure where model
results are compared with experimental data of GRA dummy
geometry (cf. Fig. 174). Thus, vertical, thermal and electric contact
resistances are higher than horizontal ones, in accordance with
Zavaliangos et al. [1004] (cf. Table 4). However, in this paper the
temperature dependence of contact resistances is determined. On
the other hand, the effect of the applied mechanical load is not
simulated through the proposed model, even if pre-set mechanical
load temporal changes are used (from 5 to 28 MPa) during the
experimental runs used for tting procedure.
The effect of contact resistances is shown in Fig. 176, where
experimentally determined and simulated radial temperature
differences between sample centre and external surface of the die
are compared as a function of time. Apart from the good matching
between model results and experimental data, the effect and
contribution of vertical contact resistances may be clearly seen.
The reported temperature differences, indeed, increases from 100
to 200 8C when F and SPP geometries are compared to GRA one.
This relatively high variation is due to the combined effect of
vertical thermal contact resistances and vertical electric ones,
which are able to conne owing current into plungers and sample
in series combination, thus enhancing joule heat by reducing cross-
section area.
Once contact resistances are evaluated by means of solid
graphitic samples, the model is runned for the case of FAST of
electric full-dense conductor (TiN) and insulator (ZrO2) specimen,
respectively. Even if no comparison with experimental data is
given to test model reliability, it is clearly shown that radial
temperature difference inside sample is larger (80 8C) in the case of
conducting material than when the insulator specimen (25 8C) is
used. According to the authors, this result mainly depends on the
distribution of the current density and, consequently, of the joule
heating as a result of the parallel combination of sample and
surrounding die. However, the rates of conductive heat transfer
between the two elements and heat loss by radiation from outer
surface of the die play a signicant role. These combined effects
depend on relative sizes of the different elements, as pointed out
p . The latter one, on the other hand, is related to the
p D  Vm
Fig. 176. Simulated and experimentally measured temperature differences
between central and external pyrometer, focusing on the die, for the different
graphite dummy geometries. The shown values indicate an average value of three
measurements with their respective standard deviations. Adapted from
Vanmeensel et al. [39].
263
by authors. Thus, it is concluded that measured temperature at die
outer surface seems representative of the sintering temperature
(3.18) of specimen when an insulator material is used, at least for the
(3.19) case of conductor-like material, the real sintering temperature of
the sample is signicantly different from the temperature
measured at outer surface of the die. In this latter case, the
reliability of temperature measurement may be reached by
covering external surface of the die with a porous graphite
insulation, thus minimizing radiative heat losses and, simulta-
neously, optimizing FAST process from an economical perspective.
The same authors [510,774] applied the developed model to the
FAST of ZrO2TiN powder composite with varying composition
(from 65/35 to 10/90 vol.%). Mixture rules are adopted for
evaluation of the thermophysical properties of the sintering
powder mixture.
In particular, from the knowledge of electric (s) and thermal (k)
conductivities of full-dense ZrO2 and TiN as a function of
temperature, the PolderVan-Santen (PVS) mixture rule is applied
to obtain the thermophysical parameters of full-dense ZrO2TiN
composite as follows:

1
kmix  2km  k p 3V p k p  km
4 q
 2
k p  2km 3V p k p  km 8km k p (3.20)

1
s mix  2s m  s p 3V p s p  s m
4 q
 
s p  2s m 3V p s p  s m 2 8s m s p (3.21)
It is assumed that the mixture is made of a continuous matrix
phase (m), and a solute secondary phase (p), homogeneously
dispersed therein and characterized by spherically shaped uniform
particles. Vp represents the percentage volume of the secondary
phase in the mixture, which, in the case study, is ZrO2 or
alternatively TiN, according to the nominal composition of ZrO2
TiN. This way, temperature and composition dependence of the
thermophysical parameters for full-dense ZrO2TiN composite is
taken into account, as reported in Fig. 177.
In order to properly take into account the effect of ongoing
densication-sintering of ZrO2TiN composite powders with
different residual porosity, the PVS mixture rule is applied by
incorporating porosity as a third phase with zero conductivity. This
way, the equations reported above are still valid and applied while
using a reduced (by porosity) volume percentage of secondary
phase, V
relative density (D) of the sintering powder compact through the
following equation:
V
(3.22)
where Vm is the volume fraction of matrix phase in a partially
sintered compact.
The heat capacity of the sintering powder is determined by
directly multiplying the temperature and composition dependent
heat capacity of full-dense material with the relative density.
The relative density of the sintering powder compact (D)
changes with time during FAST process depending on composition.
It is experimentally determined by Archimedes method as
reported in Fig. 178, along with the adopted operative conditions
(heating rate and pressure cycle) reported in the inset. From the
experimental data reported in Fig. 178, the relative density of the
sintering powder compact (D) is determined as a function of
temperature, assuming that a uniform temperature distribution is
attained inside the sample.
264 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Thus, thermal and electric conductivities of ZrO2TiN sintering

Fig. 177. Calculated thermal (a) and electrical (b) conductivity of fully dense ZrO2
TiN composites with varying content as a function of temperature. Adapted from
Vanmeensel et al. [774].
powder composite are fully determined as function of temperature
and composition or, alternatively as function of relative density of
the powder compact and composition, as shown in Fig. 179. The
calculated values indicate that all materials with a TiN content
<70 vol.% experience a sudden increase in electric conductivity,
and percolation takes place. This means that, during FAST,
the sample suddenly changes from insulator- to conducting-like
electric behavior, as relative density increases during sintering. As
a consequence, current and joule heat generation concentrate
inside the sample instead of the surrounding die.
In Fig. 180 the electric conductivity and the relative density as
function of temperature for ZrO2TiN sintering powder composite
with a composition equal to 60/40 vol.% are reported. As it may be
seen, percolation takes place at this composition when tempera-
ture reaches a value between 1200 and 1300 8C. Consequently, the
developed model correctly predicts that current density concen-
trates inside the die when the sample temperature reaches
1050 8C, as clearly shown in Fig. 181a. On the other hand, when the
sample reaches a temperature equal to 1500 8C, the current ows
also inside specimen (cf. Fig. 182a). Moreover, by comparing
Figs. 181b and c and 182b and c, it is apparent that, when at earlier
sintering times ZrO2TiN powder composite behaves as an electric
insulator, the sample center reaches lower temperatures than the
surrounding die. The latter one heats up the sample via thermal
conduction. On the other hand, at longer sintering times the
sample center displays higher temperature levels than die, due to
joule heating inside it and radiative heat losses from the exposed
surface of the die. In this latter case, high temperature differences
in radial direction are attained inside the sample (about 150 8C)
and the die (about 400 8C).
The comparison between model results and experimental data
is given in Fig. 183, where the temperature of the pyrometer
focused on the surface of the die as a function of the temperature of
the pyrometer focused on the sample center is reported. Correctly,
when percolation takes place between 1200 and 1300 8C, the
plotted function goes below the bisector line and the model agrees
with the experimental measurements.

Fig. 178. Densication behaviour of selected ZrO2-TiN composites with varying TiN content (35, 50, 80 and 90 vol.% TiN). As a reference the densication behaviour of pure
2YZrO2 (grey full-line) and TiN (black-full line) is shown as well. The inset shows the predened temperature and pressure cycle throughout the sintering cycle. Adapted
from Vanmeensel et al. [774].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 265

Fig. 179. Calculated thermal (a) and electric (b) conductivity of the ZrO2TiN composites with varying TiN content as a function of relative density. Adapted from Vanmeensel
et al. [774].

If one considers different compositions, the transition tem-
perature changes as indicated in Fig. 184a and summarized in
Table 5, where the satisfactory agreement between experimentally
determined transitions temperatures and the corresponding
modeled ones may be seen. However, Fig. 184b, where the com-
parison between model results and experimental data is shown,
reveals only a qualitative agreement. The temperature difference
between central and external pyrometers as a function of
composition (or, alternatively, as function of thermal conductivity
at 1500 8C of the full-dense ZrO2TiN composite which varies with
TiN content) predicted by the model is much lower than that one
experimentally measured.
According to this modeling approach, the distribution of
the relative density of the powder needs to be experimentally

Fig. 180. The evolution of the calculated electric conductivity and the measured relative density of a sintering ZrO2TiN (60/40) powder compact, plotted as function of the
sintering temperature. Adapted from Vanmeensel et al. [510].
266 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 181. Current density distribution (a); temperature distribution inside sample
(b) and inside the system (c), for the SPS of ZrO2TiN composites (60/40) at a
controlling temperature of 1050 8C after applying a pressure of 28 MPa. Adapted
from Vanmeensel et al. [510].
determined as a function of temperature distribution eld (cf.
Fig. 178), along with an averaged pressure (stress) inside the
sample.
The SPS of a full-dense electric conducting (copper) specimen is
compared by Anselmi-Tamburini et al. [37] with a full-dense
electric insulator (alumina) sample, by considering the system
domain of integration represented in Fig. 185. As it can be seen,
Fig. 182. Current density distribution (a); temperature distribution inside sample
(b) and inside the system (c), for the SPS of ZrO2TiN (60/40) composite at a
controlling temperature of 1500 8C after applying a pressure of 56 MPa. Adapted
from Vanmeensel et al. [510].
stainless steel electrodes (rams) are incorporated in the model for
the rst time, since, according to the authors, if they are neglected,
the boundary conditions of axial cooling and the consequent
temperature distribution change dramatically. The mathematical
equations used, i.e. the usual enthalpy and current density
conservation equations in cylindrical coordinates applied to every
single system element depicted in Fig. 185, are solved in full 3D
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 267

version via CFD-Ace (FEM). Temperature dependence of thermo-

physical properties for all materials are considered.
Radiation heat losses from the exposed surfaces are taken into
account along with the assignment of a constant ambient
temperature and voltage drop or total owing current at rams
ends surfaces, while neglecting contact resistances at interfaces
between the different elements. The results related to the dis-
tribution of owing current density when insulator or conducting
samples are alternatively used are similar to those ones obtained in
the RS literature. The innovative aspect of the paper consists in that
the behavior of the Sumitomo SPS DC pulse generator is analyzed
and revealed for the rst time by means of an oscilloscope. In
Fig. 183. Comparison between the experimentally determined and simulated
temperature difference between the central pyrometer (CP) and the external
Fig. 186 the complex temporal prole of the voltage measured
pyrometer (EP) in case a ZrO2TiN (60/40) composite powder compact is placed between the rams ends for the case of the so-called 8/2 (ON/OFF)
inside the die. Adapted from Vanmeensel et al. [510]. sequence is reported. This specic sequence allows one to generate
eight direct voltage pulses of xed 3 ms (ON) followed by two
pulses of 3 ms with zero voltage (OFF). This corresponds to a low
frequency signal (<100 Hz, as described by the Fourier analysis of
the pulse pattern) which is not able to generate a relevant skin
effect when considering the electric conductivities and sizes of the
different elements used in the SPS apparatus. Thus, at least with
the 8/2 pulse sequence, the electric current is not forced by
electromagnetic induction to be concentrated on external surfaces
but is distributed along cross-section areas according to the
relative electric conductances in series or parallel combination.
This consideration justies the simplifying assumption of the
developed model to consider materials characterized only by
ohmic behavior so that the density current conservation equations
considered so far reasonably represents the process taking place.
In Fig. 187 the simulated dependence of the fraction of the total
current carried by the sample when its electric conductivity at
room temperature covers eighteen orders of magnitude, thus
ranging from the electric conductivity of alumina to that one of
copper, is reported. In particular, the dependence is shown for two
sample heights (namely 3 and 10 mm), while keeping constant the
rest of system geometry. Virtually no current is carried by a sample
with a conductivity less than about 103 S/m. It is interesting to note
that in the case of a sample height equal to 10 mm almost all
current is carried by a conducting (copper) sample. This is due to
the relative resistances of the two current paths, i.e. through the
sample and the surrounding die, respectively. Since copper is a
better conductor than the graphite of the die, if sample height is
augmented the resistance of the rst path increases only margin-
ally as compared to the second one.
In order to justify the choice of neglecting contact resistances in
Fig. 184. Comparison of the central pyrometer (CP) and the external pyrometer the proposed model the following considerations were made. The
(EP) temperature measurements during sintering experiments using ZrO2TiN electric resistance at room temperature (measured by a four-point
composite powder compacts with different TiN (a). Calculated radial temperature method on a 3 mm sample) across the die with the plungers in
gradient and measured difference between CP and EP temperature as a function of
place for the cases of alumina and copper, respectively is reported
the thermal conductivity of the fully dense ZrO2TiN composite materials (b).
Adapted from Vanmeensel et al. [774]. in Fig. 188 as a function of the applied mechanical pressure. At
pressure levels less than about 50 MPa, the resistance is lower for
the case where copper is inside the die, while at higher pressures
the resistance is the same for both cases. Both values decrease with
Table 5
Comparison of predicted and measured transition temperature for the percolation
increasing pressure, and appear to reach an asymptotic value.
of ZrO2TiN composite powder system. Adapted from Vanmeensel et al. [774]. Theoretically the overall resistance for die and plungers, as
evaluated on the basis of room temperature resistivity of the
Vol. % TiN Transition Transition
graphite, while excluding contact resistance, is around
temperature (8C) temperature (8C)
calculated measured 1.5  103 V. As the applied pressure is increased, the resistance
approaches this theoretical value for both samples. This suggests
35 1430 13501400
that contact resistance has a stronger role than the resistivity of the
40 1244 12501300
50 1145 11501200 samples. It is then concluded that contact resistances can be safely
60 1052 10501100 neglected as long as the experimental observations are obtained at
70 910 10001050 high pressure levels (i.e. about 100 MPa).
80 No clear transition 850900
Experimental data and modeling results are reported in
90 No clear transition 750800
Fig. 189, where the temporal prole of the temperatures at sample
268 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 185. Integration domain of the model proposed by Anselmi-Tamburini et al. [37].

center and surface of the die are compared when the system is sintering and densication (i.e. stressstrain mechanics) which
subjected to a 400 s constant current step of 1000 A for the case of takes into account grain boundary diffusion, power-law creep
alumina sample. As it can be seen, model results underestimate the driven by externally applied load, sintering stress due to surface
experimental data by 200 8C, while sample center results at lower tension and steady-state electromigration is developed. Speci-
temperature than die surface, being the opposite situation found cally, the electromigration represents the contribution of the
experimentally.
A constitutive model applicable to SPS of powder compacts
of conducting materials (aluminum), and capable of taking into
account an effect related to the owing of electric current different
from joule heating has been recently proposed by Olevsky
and Froyen [1005]. In particular, a constitutive law for powder

Fig. 187. Dependence of the fraction of the total current owing through the sample
Fig. 186. Typical voltage pulse pattern of a 8:2 (on:off) in the SPS. Adapted from on its electric conductivity. Sample thickness: 3 and 10 mm; applied voltage = 5 V.
Anselmi-Tamburini et al. [37]. Adapted from Anselmi-Tamburini et al. [37].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 188. Experimentally determined room-temperature resistance of the die
measured at different applied pressures for non-conducting (alumina) and
conducting (copper) samples. Sample thickness = 3 mm for both cases. Adapted
from Anselmi-Tamburini et al. [37].
Fig. 189. Temperature proles of the center of the non-conducting (alumina)
sample and the corresponding position on the external surface of the die: (a)
calculated and (b) experimentally measured (constant current of 1000 A
maintained for 400 s and then turned off). Adapted from Anselmi-Tamburini
et al. [37].
269
electric eld to the diffusive mass transfer taking place during the
sintering of powder compacts. On the other hand, the electron
wind, related to the drift of atoms by momentum transfer, is
neglected.
According to NernstEinstein equation, matter ux J caused by
grain boundary diffusion is driven by stress and electromigration
as follows:
J C E  E C s  r
s (3.23)
where E is the electric eld and r s is the gradient of stresses
normal to grain boundary, while CE and Cs are temperature-
dependent parameters related to mass diffusivity on grain
boundary.
The electric eld is considered an input of the developed model,
being evaluated as E V=, where V is the applied voltage drop
along a characteristic length of the grain, . On the other hand, r s
is determined by solving the equilibrium mechanical problem,
which allows one to simulate the stress eld distribution due to the
surface tension (free-sintering) and the sintering under external
load for a powder compact of simple packed, rectangular grains
with elliptical pores. Then, by linking the strain rate e to the matter
ux J in orthogonal direction, the following expression represent-
ing the shrinkage kinetics due to grain boundary diffusion e gb is
obtained:
e gb e Egb e stgb e load
gb (3.24)
where electromigration, surface tension and external load terms
represent the corresponding three contributions.
However, the total shrinkage rate e is the result of the shrinkage
rate due to grain boundary diffusion and power-law creep
mechanism as follows:
e e gb e cree p (3.25)
The shrinkage rate due to power-law creep e cree p is evaluated
on the basis of the continuum theory of sintering, where the
dependences of normalized shear and bulk viscosity modules on
porosity u along with the effective sintering are assessed.
According to authors analysis, the contribution of external load
to grain boundary diffusion shrinkage kinetic e load
gb is negligible.
Consequently, the inuence of external load is limited to the
power-law creep phenomenon. In particular, the densication map
for the case of aluminum powder reported in Fig. 190 shows that
electromigration e Egb plays a signicant role when small
porosities and ultra-ne powders are considered. For conventional,
micron-size powders, power-law creep is the dominant mechan-
ism of shrinkage kinetics.
By considering that, in a 2D axial coordinate system (x and y),
porosity rate is related to strain rate by the following expression:
u 1  u  e x e y (3.26)
and assuming that during SPS process pressing of powder compact
takes place in a rigid surrounding die (i.e. e y 0), the following
relationship for densication kinetics is obtained:
 
u 1  u  e Egb;x e stgb;x e load
gb;x e cree p;x (3.27)
This latter equation is numerically solved to obtain temporal
prole of porosity during SPS of aluminum powders, when the
experimentally measured temporal prole of temperature is
provided, along with the applied voltage gradient and constant
pressure.
The comparison with experimental data is provided in Fig. 191
for the case of aluminum powders compact subjected to 500 V/m
electric eld under a pressure of 23.5 MPa, and the corresponding
270 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 190. Densication map for aluminum powder. Adapted from Olevsky and
Froyen [1005].
temperature temporal prole experimentally measured and
reported in the same gure. As it can be seen, the model
adequately describes shrinkage kinetics of powder compacts.
However, as recognized by the authors, the proposed constitutive
law should be coupled to the thermal and electric problems in
order to avoid the experimental measurement of temperature
prole and voltage gradient for modeling purposes.
Along the lines of inquiry followed by Anselmi-Tamburini et al.
[37], recently Wang et al. [128] analyze the ECAS behavior taking
place when using a full-dense electric conducting (copper)
specimen or a full-dense electric insulator (alumina) sample in
the system whose geometry is represented in Fig. 192. In this case,
copper electrodes of height equal to 2 cm are considered. In
particular, the ECAS apparatus is equipped with a DC generator
which does not provide pulses, while mechanical load is applied on
top rams being bottom rams end blocked in a xed vertical
position. The innovative aspect of the proposed model is that, for
the rst time, the usual enthalpy and current density conservation
equations are coupled to the stressstrain mechanical equilibrium
ones. In particular, the 2D cylindrical coordinates FEM minimiza-
tion of the total mechanical potential energy related to elastic
and thermal expansion is solved in order to determine stress
Fig. 191. Porosity kinetics during SPS of aluminum powder. Comparison of the
proposed model with experimental data. Adapted from Olevsky and Froyen [1005].
distribution eld inside the system resulting from mechanical as
well as thermal loads. Boundary conditions of the thermal and
electric equations are the same ones adopted by Anselmi-
Tamburini et al. [37], i.e. radiation heat losses from all exposed
surfaces are taken into account along with the assignment of a
constant ambient temperature and voltage drop or total owing
current at rams ends surfaces, while neglecting contact resistances
at interface between the different elements. It is worth noting that
the experimental runs are conducted by applying a constant
pressure of 140 MPa, so that contact resistances may be neglected
according to Fig. 188.
For what concerns the boundary conditions of the mechanical
problem, while friction forces are explicitly neglected, a uniform
pressure of 140 MPa is applied on top rams end and zero vertical
displacement is set for bottom rams end, thus reecting the actual
operative conditions adopted during experimental runs. In
addition, the vertical displacement at the middle points of the
die outer surface is set equal to zero. As noted by the authors, even
if this boundary condition does not exactly reect the actual
experimental conditions, it is considered an appropriate approx-
imation since its effect is negligible in the crucial plungerdie
sample portion.
The comparison between experimental data and model results
in terms of temporal prole of temperature at the middle point of
the die when, for the case of alumina sample, an input electric
current step of 500 or 1000 A is imposed to the system, is shown in
Fig. 193. As it can be seen, matching is very good during heating as
well as during cooling stages.
Simulation runs show that, when using a conducting sample,
temperature is generally lower than for the case of an insulator
specimen, while, at steady state, the temperature difference inside
the sample is higher if copper is used instead of alumina. Fig. 194a
and b show the radial displacement distribution eld at steady
state when applying a current of 1000 A and a pressure of 140 MPa
to the system for the case of alumina and copper sample,
respectively. The corresponding distribution eld of radial and
axial components of the stress due to thermal and Poisson-type
expansion are shown in Fig. 195 for the case of alumina (cf.
Fig. 195ac) and copper (cf. Fig. 195bd), respectively. Apart from
the concentration of the radial stress gradient where plungers
come into contact with the spacers, large differences, at positions
close to the sample, are observed when comparing the two cases of
copper and alumina specimen. In particular, inside copper sample
the radial and axial stresses are not uniformly distributed, in axial
as well as in radial directions. This behavior, is due to the relatively
high coefcient of thermal expansion of copper, which causes the
pushing of the Cu sample against the internal walls of the die. The
stresses inside the sample are lower at positions close to the die/
sample interface.
Under steady-state conditions the temperature differences
inside sample in radial direction are modest (max difference is 2 8C,
corresponding to 1% variation), while the stress ones result to be
relatively higher (max difference is 50 MPa, corresponding to 33%
variation). It was then concluded that, the nal sintered product
heterogeneity is due to the stress distribution more than the
temperature one. Consequently, the nominal sintering pressure
(i.e. that one obtained by the mechanical load applied over the
cross-section area of plungers), as well as the sintering tempera-
ture measured by a pyrometer on outer surface of die, may not be
proper indications of the operative conditions experimentally
adopted.
In the papers reviewed above, quantitative comparisons with
experimental data are limited and, typically, model reliability is
not tested by comparing experimental data with model predic-
tions. Moreover, the agreement between the operative conditions
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Fig. 192. Integration domain of the model proposed by Wang et al. [128].
Fig. 193. Comparison between experimental data and model results in terms of
temporal prole of temperature taken at the middle point of the die for the case of
alumina sample. Adapted from Wang et al. [128].
271
as well as the apparatus system geometry and the corresponding
representation used for the simulation runs is typically missing. In
particular, temperature controlled runs are usually considered.
This aspect complicates modeling activity, since additional
adjustable parameters for the mathematical description of the
control system need to be introduced. As a consequence, quan-
titative comparisons with experimental data are typically provided
in terms of temperature, without considering voltage or current
and displacement experimentally evaluated.
On the other hand, a reliable model of ECAS processes can be
obtained by separately analyzing an increasing complex system
behavior in the framework of a step by step procedure, where
physico-chemical phenomena, previously excluded, are gradually
introduced along with their unknown model parameters. This
approach allows one to independently t the complete set of
unknown parameters of the comprehensive ECAS model, thus
avoiding the masking effect given by the various phenomena
involved in the whole process.
The rst step towards this ideal approach is carried out by
Cincotti et al. [45] when addressing the mathematical description
of SPS behavior of graphitic elements inserted between the two
stainless steel rams used in the model 515S apparatus (Sumitomo),
272 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 194. Steady-state contour plots at 1000 A current input: (a) radial displacements of sample-die area of alumina sample (705 8C at center of the sample) and (b) radial
displacements of sample-die area of copper sample (692 8C at center of the sample). Adapted from Wang et al. [128].

schematically represented in Fig. 196. In particular, on the basis of
previous results reported in the literature, the geometry of the
graphitic elements considered in this paper is chosen by accurately
avoiding the presence of vertical interfaces between them thus
limiting the corresponding mathematical model to the presence of
horizontal contact resistances.
The developed 2D model in cylindrical coordinates consists
of the usual enthalpy conservation equation which accounts for
joule heat generation, coupled to density current balances
expressed in term of the RMS portion of the electric potential,
and the mechanic equilibrium equations due to elastic behavior
and thermal expansion already introduced by Wang et al. [128].

Fig. 195. Steady-state contour plots at 1000 A current input: (a) radial stress of sample-die area of alumina sample (705 8C at center of the sample); (b) radial stress of
sample-die area of copper sample (692 8C at center of the sample); (c) vertical stress of sample-die area of alumina sample (705 8C at center of the sample) and (d) vertical
stress of sample-die area of copper sample (692 8C at center of the sample). Adapted from Wang et al. [128].
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 273

Fig. 196. Schematic representation of SPS apparatus, model 515S Sumitomo (not to scale). Adapted from Cincotti et al. [45].

Thermophysical properties of graphite and stainless steel are taken elements are experimentally found to be negligible. Accordingly,
into account and provided in the paper when modeling different the continuity condition for the resistive portion of the RMS
graphitic elements inserted between the two rams as schemati- electric potential and current density is applied. In particular, by
cally represented in Fig. 197, where the system domain of simultaneously tting experimental data in terms of temporal
integration for the case of a monolithic graphitic element, proles of RMS portion of electric potential and temperature,
mimicking plungers positioned in place within the die, is shown. thermal and electric contact conductances are determined as a
It is worth noting that, according to the real geometry of the function of temperature and applied mechanical pressure through
apparatus depicted in Fig. 196, stainless steel rams and the the following relationships:
corresponding water cooling system are modeled with different
bT
lengths. This choice does not allow to consider only one quarter of P
C T T; P aT kHarm (3.28)
the integration domain, due to the lack of symmetry in axial HHarm
direction. The developed model is solved via Comsol Multyphysics
bE
P
software (FEM). The boundary conditions related to the thermal C E T; P aE s el;Harm (3.29)
HHarm
problem consist of radiation losses from all exposed surfaces, a
constant ambient temperature at rams ends and forced convective where the parameters kHarm and sel,Harm take the temperature
losses from rams along the contact interface with the cooling dependence of contact conductances into account. These are
water. In particular, in order to maintain symmetry in radial expressed as follows using the harmonic mean of the individual
direction, an hypothetical geometry of water cooling circuit thermal and electric conductivities of graphite (G) and stainless
mimicking the real one (cf. Figs. 196 and 197) is calculated by steel (SS):
assuming an equal heat ow rate loss and joule heat generation
inside rams, while determining the real heat transfer coefcient by 2kG Tkss T
kHarm T (3.30)
means of typical correlations for forced convection in closed ducts. kG T kss T
Horizontal thermal contact resistances, stated as in Zavaliangos 2s el;G Ts el;ss T
et al. [1004], are however considered only between stainless steel s el;Harm T (3.31)
s el;G T s el;ss T
rams and graphitic spacers. As evidenced by proper experimental
runs, horizontal thermal contact resistances between graphitic Basically, the use of the harmonic mean is a consequence of the
elements are found to be negligible. Thus, accordingly, the series combination between the two interfacing materials which
continuity condition in terms of temperature and conductive heat characterize the real contact. Analogously, the parameter HHarm is
ux is applied. Regarding boundary conditions for the electric the harmonic mean between graphite and stainless steel hard-
problem, since current controlled experimental runs are per- nesses:
formed, the RMS portion of voltage drop between the two rams
2HG Hss
ends is determined by assigning the RMS value of the total electric HHarm (3.32)
HG Hss
current owing through the system, i.e. an integral equation of the
gradient of RMS portion of electric potential is applied. Analo- The adjustable parameters aT, bT, aE, and bE, which depend on
gously to the thermal problem, horizontal electric contact surface roughness and plastic behavior at contact interface
resistances, stated as in Zavaliangos et al. [1004], are considered between graphite and stainless steel elements, are obtained
only between stainless steel rams and graphitic spacers, because following a proper tting procedure and are reported in Table 6
also horizontal electric contact resistances between graphitic along with the 95% condence band and correlation coefcients.
274 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

Fig. 197. Integration domain of the model proposed by Cincotti et al. [45].

The corresponding values of the electric and thermal con-
ductances obtained in the range of temperature and mechanical
load investigated in this work are 0.25 to 1.7  106 V1/m2 and
0.007 to 2  103 W/(m2 K), respectively, to be directly compared to
those one reported in Table 4.
It is worth noting that the experimental data used for the tting
procedure are obtained by considering a system consisting of only
one graphitic element (8 cm OD) between the two rams subjected
to a RMS current of 1200 A with varying mechanical loads (3
50 kN corresponding to 0.610 MPa).
The need to specify the RMS values of the electric variables for a
correct evaluation of the joule heat distribution is evidenced by
the comprehensive analysis of the apparatus behavior performed
from the electro-magnetic perspective. By taking advantage of an
Hall effect transducer and a voltage isolation amplier, as
schematically depicted in Fig. 196, the independent measuring
of the pulsed current and voltage drop between the two rams,
respectively are obtained. From these instantaneous measure-
R tt
ments, the corresponding average I 1=t t It dt and V
R tt q
R tt
1=t t Vtdt and RMS IRMS 1=t t I2 t dt and
q
R tt
V RMS 1=t t V 2 t dt) values are readily calculated. It is
found that a magnetic self-inductive character due to pulsing may
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
Table 6
Fitted parameters of contact conductances along with 95% condential band, and
correlation coefcient R. Adapted from Cincotti et al. [45].
Parameter Value  error
aT 22810  4.6 m 1
bT 1.08  0.23
aE 64  1.38 m1
bE 0.35  0.05
arise depending on current level, pulse cycle and system
geometry. However, as already noted by Anselmi-Tamburini
et al. [37], this low frequencies (<100 MHz) pulsing is not able to
induce a skin effect on electric current path through the system. In
addition, it is found that the 515S SPS machine by Sumitomo is
equipped with a measuring system that provides the average
value of the current owing in the system and the average value of
voltage drop between rams. In particular, depending on the pulse
cycle adopted and the level of current owing inside the system,
the RMS value of the current may be more than two times higher
than the corresponding average value, as clearly reported in
Fig. 198. Macroscopically, from circuit theory perspective this
behavior is described by a non-ideal inductor, i.e. a resistance (R)
inductance (L) series combination for which the following
relationship holds:
dI
V V R V L RI L
dt
being V and I the instantaneous voltage and electric current,
respectively.
This result is not really surprising, since, in principle, the SPS
systems involve time varying electromagnetic elds. However, in
this case the assumption of the current density conservation,
typically adopted in the literature, is not valid. Thus, in order to
properly take into account the magnetic induction and the
corresponding joule heat distribution, a more complex version
of Maxwells equations should be considered. Moreover, the whole
model should be solved in the time scale of the generated electric
pulses (fractions of millisecond), while temperature and displace-
ment change in a much larger time scale (i.e. seconds at least).
Clearly, such a mathematical description would be characterized
by a high degree of stiffness and time-consuming solution.
Fortunately, a macroscopic non-ideal inductor may be represented,
from a distributed parameter modeling approach, by the super-
Fig. 198. Instantaneous, average and RMS electric current temporal proles when a 12/2 pulse cycle is adopted (a) and effect of pulse cycle on IRMS =I vs. IRMS (b). Adapted from
Cincotti et al. [45].
275
position of two models: a steady-state magnetic model outside the
conductor (i.e. outside the element assembly of the SPS apparatus)
which takes into account the inductive character of the system, and
R a steady-state conduction model inside the conductor, which takes
0.9368 into account the resistive character of the system.
However, the latter one is mathematically equivalent to the
0.9609
usual current density balance expressed in terms of electric
potential, except that, accordingly, it is able to determine only the
resistive portion of the electric potential. On the other hand, the
measurable voltage drop between rams refers to the resistive as
well as the inductive contributions. This problem is solved by
means of a Fourier series development which evidences that the
experimental counterpart of the modeled resistive portion of the
RMS voltage can be obtained as w = RIRMS, where resistance (R)
is determined from the measured average voltage and electric
current R V=I.
Regarding the boundary conditions of the mechanical problem,
an uniformly distributed load is assigned at the bottom surface of
lower ram, while a blocked displacement is imposed at the top
surface of upper ram in the radial as well as in the vertical
direction. All the exposed surfaces are free, meaning that a zero
radial and shear component of stress is imposed. Friction forces in
horizontal contacts are neglected thus applying the continuity
condition on stress axial component and vertical displacement
between the two contacting sides of the interface.
From a mathematical perspective, the proposed model is not
(3.33) fully coupled with temperature and electric current distribution.
Indeed, once thermal and electric current balances are solved,
temperature distribution represents the input for the mechanical
problem that allows one to determine the stressstrain distribu-
tion and the displacement temporal prole. Actually, the implicit
assumption adopted (i.e. the spatial domain of integration does not
change substantially due to thermal expansion and mechanical
load), is however reasonable for the SPS system without powders
considered. Indeed, the order of magnitude of the resulting
negative displacement due to thermal expansion is equal to
103 m while apparatus height is 1 m. Of course, it is also implicitly
assumed that contribution to thermal expansion as well as
mechanical load is equally distributed between the different
elements, comprising stainless steel electrodes. On the other hand,
such assumption may be not valid when modeling SPS system
behavior in presence of powder samples, where a positive
displacement with order of magnitude of about 3 to 5  103 m
is basically localized in the shrinking powder specimen. Modeling
276 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287
with moving boundaries should be considered in this case,
especially if spatialtemporal proles of nal product density is
simulated.
Fig. 199 reports the comparisons between experimental data
and model results in terms of temporal proles of temperature at
two different positions, RMS portion of voltage, and displacement
obtained when submitting the system assembly depicted in
Fig. 199. Comparison between experimental data and model predictions in terms of
temporal proles of temperature (a); resistive portion of RMS voltage (b) and
displacement (c), when the system is submitted to a RMS electric current step of
980 A for 10 min, with a load of 3.5 kN. Temperature is taken at two different
locations, i.e. center of lower small spacer (r = 0, z = 31.5 cm) and inside the die
(r = 1.1 cm, z = 32.25 cm). Adapted from Cincotti et al. [45].
Fig. 200. Axial proles of temperature and resistive portion of RMS voltage
(r = 3 cm; t = 20 min) when the system depicted is submitted to a RMS electric
current step of 1200 A for 20 min, with a load of 50 kN. Adapted from Cincotti
et al. [45].
Fig. 197 to a RMS electric current step of 980 A for 10 min with a
load of 3.5 kN (corresponding to an average pressure of 21 MPa on
plungers cross-section area). As can be seen, during heating as well
as during cooling stages the agreement is good, especially if one
considers that these are model prediction runs, i.e. do not coincide
with those used when tting the adjustable parameters related to
the thermal and contact resistances (cf. Table 6). In particular,
model prediction without considering contact resistances are
reported as well. It is evident the need to include them in a
modeling activity of SPS process with quantitative purposes. This
conclusion is corroborated by the simulation run reported in
Fig. 200, where axial temperature and RMS portion of electric
potential proles at steady state are reported for the system
assembly subjected to a RMS current of 1200 A and a mechanical
load of 50 kN (corresponding to 10 MPa). Due to the relatively low
electric resistance of the graphitic elements, the voltage drop is
mainly concentrated at contact interface with the stainless steel
rams. Thermal contact resistances are only apparently less evident,
due to the joule heat contribution to the discontinuous conductive
heat ux at contact interface. Even if, for the main part of their
length, stainless steel rams are at ambient temperature, the small
portion at higher temperatures, closer to graphitic elements,
contributes signicantly to the measured displacement. This is due
to the coefcient of thermal expansion of stainless steel, which is
three times higher than the corresponding one of graphite. Thus,
care on modeling the water cooling system inside full length rams
seems mandatory when aiming to simulate displacement mea-
sured at bottom end of lower ram.
4. Conclusions
Synthesis and/or simultaneous consolidation of materials by
ECAS is the subject of this review article. More than a thousand
papers published during the past decades are taken into account. It
is seen that the vast majority of publications on ECAS processes
describe successfully attempts to synthesize and/or consolidate a
tremendous amount of materials. Consequently, the correspond-
ing experimental conditions and procedures, formation mechan-
isms, properties, and functionality of a wide spectrum of dense
materials fabricated by ECAS techniques are presented. Theoretical
 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287 277

analysis based on the modeling of the mostly used RS process, Table 7

Effects of ECAS techniques with respect to pressure assisted conventional ones, i.e.
i.e., SPS, is also proposed.
HP or HIP.
It is clearly shown that ECAS techniques give the possibility to
fabricate advanced ceramics, metal-based and composite materi- Effect System Reference
als and to develop high-technology parts with tailored properties Shorter sintering time Si3N4 [79]
that cannot be obtained taking advantage of conventional sintering Si3N4/SiC composites [738]
techniques. Thus, the comparison of electric current activated Al2O3Y3Al5O12 [492]
Fe0.91 Mn0.09 Si2 [400]
sintering over conventional methods represents an emerging
HA-20 vol.% 316L [825]
theme. Specically, the possible effects of ECAS techniques with Si2N2O3CaOAl2O3 [557]
respect to pressure assisted conventional ones, i.e. HP or HIP, are ZrB2ZrCSiC [85,798]
summarized in Table 7, by considering only those references where Y2O3ZrO2ZrB2 [86]
the same starting powders to be reacted and/or consolidated were Cr2AlC [317]
Porous stainless steel [204]
used. It is reported for example that higher density are achieved at
lower sintering temperature in shorter sintering time. Smaller Lower temperature Si3N4 [79]
grain sizes are typically obtained with a consequent direct effect Al2O3Y3Al5O12 [492]
HA powders [809]
on nearly all properties investigated on the fabricated dense Si2N2O3CaOAl2O3 [557]
materials. Nb/Nb5Si3 [674]
It should be however noted that some of the explanations ZrB2MoSi2 [85,792]
provided to justify the typically claimed advantages with respect Y2O3ZrO2ZrB2 [86]
to conventional sintering techniques seems to be not convincing Lower pressure Y2O3ZrO2ZrB2 [86]
from the scientic point of view since suitable experimental
Finer microstructure Si3N4 [79]
evidence is not reported. Al2O3Y3Al5O12 [492]
Consequently, several considerations of general type somehow WC6.29Co [608]
related to the ones above can be made. One of these issues is ZrB2SiCZrC [791]
represented by the sintering temperature. While the evaluation of More homogeneous microstructure Nb/Nb5Si3 [674]
this quantity may be easily obtained in sintering furnaces, in ECAS
Higher density Ti5Si3 [89]
processes the one corresponding to the die surface is typically
measured. However, the latter one clearly does not represent the Higher densication rate HfB2SiC [85]
sample sintering temperature. In addition, there might be radial Improved mechanical properties Ta [223]
temperature gradients inside the sample which make the SWCNT [897]
denition of the sintering temperature even more complicated. Cr2AlC [317]
Care should then be taken when attributing specic values of Higher apparent activation energy Si3N4 [371]
sintering temperatures during ECAS processes. Similar considera- for a-to-b phase transformation
tions can be made when taking into account the so called nominal
Shorter sintering and coating time BN ceramic [876]
pressure, i.e. the mechanical pressure applied to the plunger. In layer/metal substrate
fact, it is shown that signicant pressure gradient may be found
Improved properties (various) WC6.29Co [608]
along the sample cross-section. In addition, mean values of current
and voltages typically provided are not appropriate when current Improved electrical properties AlNSiC [745]
pulses are present. In fact, it is demonstrated that only the Boron icosahedra [984]
compounds
corresponding RMS values allow one to correctly evaluate the
contribution of Joule effect. Furthermore, it is clearly shown that Improved bioactivity HA powders [809]
contact resistances should be taken into account, when modeling
RS processes. Sample dimensions indeed play a signicant role to
identify the actual current path and consequently the Joule effect presence is unlikely since voltage levels used during resistive
distribution. In fact, as the sample dimensions are augmented, skin sintering processes are too low. Unfortunately, it is quite difcult
effects phenomena, which strongly affect current distribution, may to design experiments where the intrinsic effect of the electric
take place. In addition, since heat losses and heat generation by current is separated from the other experimental parameters. For
Joule effect in the die/sample are proportional to the corresponding this reason, we did not try to rationalize the possible electric eld
surface and volume, respectively, it clearly follows that tempera- and current effects on consolidation processes. Recent attempts in
ture distribution inside the sample may be strongly affected by its this direction may be found elsewhere [43].
dimensions. Following the considerations above and the rapid increase in
It should be noted that the only phenomenon which is ex- the utilization of ECAS processes, as clearly shown in this review
perimentally proved to be driven by the current owing through paper, we have the opportunity to summarize in what follows
the plunger/die/sample ensemble is Joule effect. While other potential subjects for future investigations which will contribute
phenomena, i.e. spark occurrence, plasma formation, removal of signicantly to the growing to this exciting eld of materials
oxides (breakdown of oxides lms) and adsorbed gases from the science and technology. Investigation aimed at providing a
particle surfaces with a resulting cleaning effect, high localized comprehensive understanding of the fundamental role of the
temperature at the contact area between particles, enhanced current and its waveform in synthesis reaction and consolidation
diffusion of materials at forming particle necks, may take place processes need to be carried out. Specically, results that
simultaneously with the joule effect, they are not experimentally unambiguously show the role of the current in mass transport
demonstrated and some of them can be masked since Joule effect is enhancement occurring during ECAS processes are necessary. The
most probably the dominant one. For example, the presence of possibility of tailoring new structures and functions of materials
sparks are typically invoked to explain certain mechanisms through the exploitation of ECAS processes needs to be addressed
of densication and/or product formation. However, while no by taking into consideration crystallographic properties and
experimental evidence of sparks is reported in the literature, their processing factors. In fact, the design of products and processes
278 R. Orru` et al. / Materials Science and Engineering R 63 (2009) 127287

that can satisfy social needs in diverse sectors calls for the Field assisted densication
development of new materials that are tailored up to the molecular High Energy High Rate (HEHR) consolidation
level to satisfy specic performance requirements. Along with Impulse plasma sintering
traditional, albeit necessary, synthesis/consolidation, character- Instrumented electric discharge consolidation
ization and testing efforts and high-throughput experimentation, Instrumented pulse discharging consolidation
modeling plays an increasingly important role in this develop- Instrumented pulse electro discharge consolidation
ment. Specically, modeling of ECAS processes, based on the Plasma activated sintering (PAS)
molecular and continuum engineering approaches, should invari- Plasma assisted sintering (PAS)
ably account for thermal, electrical and mechanical behavior at the Plasma pressure compaction (P2C) or (PPC)
same time. By taking advantage of state-of-the-art mathematical Plasma sintering
and numerical techniques and harnesses the power of present days Pulse current activated sintering (PCAS)
computers, ECAS models should enable the understanding and Pulse current hot quasi-isostatic pressing (PCHIP)
control of the eld/current effect and related phenomena. The nal Pulse current hot pressing (PCHP)
goal will be to establish quantitative relations between structure, Pulse current pressure sintering (PCPS)
properties, processing, and performance of materials fabricated by Pulse current sintering (PCS)
ECAS processes, which are valuable in product and process design. Pulse discharge sintering (PDS)
Besides, the investigation of the intrinsic effect of electric current Pulse electric current pressure sintering (PECPS)
when bonding submillimeter diameter particles may represent a Pulse electric current sintering (PECS)
useful tool to understand which phenomenon is responsible Pulse electric discharge consolidation
during the sintering. Finally, it is worth mentioning that another Pulse high current (PHC) heating sintering
obstacle to meet in order to leave the development stage of ECAS Pulse plasma sintering (PPS)
processes is the manufacturing of large-sized objects with high Resistance heated hot pressing
exibility and cost effectiveness. It is believed that the scientic Resistance sintering (RS)
community, with its synthetic, problem-oriented thinking, and Resistance sintering under pressure
thorough training in the fundamentals of mathematical, physical, Resistance sintering under ultra-high pressure (RSHUP)
chemical and materials sciences have contributed and will Resistive sintering
contribute signicantly to the advances and growing of ECAS Spark discharge sintering
processes understanding and applications. Spark isostatic pressing (SIP)
Spark plasma activated sintering
Spark plasma sintering (SPS)
Acknowledgements
Spark pressure sintering
Spark sintering
The nancial support of Sardegna Ricerche, Italy and IM
(Innovative Materials) Srl, Italy, is gratefully acknowledged.

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