Nanocrystalline materials
c. Suryanarayana
The current status of research and development on
the structure and properties of nanocrystalline
materials is reviewed. Nanocrystalline materials
are polycrystalline materials with grain sizes of up
to about 100 nm. Because of the extremely small
dimensions, a large volume fraction of the atoms is
located at the grain boundaries, and this confers
special attributes to these materials.
Nanocrystalline materials can be prepared by inert
gas condensation, mechanical alloying, plasma
deposition, spray conversion processing, and many
other methods. These are briefly reviewed. A clear
picture of the structure of nanocrystalline materials
is only now emerging. Whereas the earlier workers
had concluded that the structure of grain
boundaries in nanocrystalline materials was quite
different from that in coarse grained materials,
recent studies have shown unambiguously that the
structure of the grain boundaries is the same in
both nanocrystalline and coarse grained materials.
The properties of nanocrystalline materials are very
often superior to those of conventional
polycrystalline coarse grained materials.
Nanocrystalline materials exhibit increased
strength/hardness, enhanced diffusivity, improved
ductility/toughness, reduced density, reduced
elastic modulus, higher electrical resistivity,
increased specific heat, higher thermal expansion
coefficient, lower thermal conductivity, and
superior soft magnetic properties in comparison
with conventional coarse grained materials. New
concepts of nanocomposites and nanoglasses are
also being investigated with special emphasis on
ceramic composites to increase their strength and
toughness. There appears to be a great potential
for applications in the near future for
nanocrystalline materials. The extensive
investigations in recent years on structure-property
correlations in nanocrystalline materials have
begun to unravel the complexities of these
materials, and pave the way for successful
exploitation of alloy design principles to synthesise
better materials than hitherto available. IMR/271
© 1995 The Institute of Materials and ASM International.
The author is in the Institute for Materials and Advanced
Processes, University of Idaho, Moscow, 10, USA.
Introduction
Metallurgists and materials scientists have been con-
ducting research investigations for several centuries
to develop materials which are 'stronger, stiffer, and
lighter' than the existing materials and also capable
of use at elevated temperatures ('hotter'). The high
technology industries in the developed countries have
given an added fillip to these efforts. Several novel
and non-equilibrium processing methods have been
developed during the past few decades to improve
the performance of the existing materials; these
include rapid solidification from the liquid state,1,2
International
mechanical alloying," plasma processing.t'" and
vapour deposition," A central underlying theme in all
these methods is to energise the material to bring it
into a highly non-equilibrium (metastable) state (also
including a possible change of state from the solid
to liquid or gas) through melting, evaporation,
irradiation, application of pressure, storing of
mechanical energy, etc," The material is then brought
to another lower energy metastable state by quench-
ing or related processes when it can exist as a super-
saturated solid solution, metastable crystalline or
quasicrystalline phase, or even in a glassy state,
affording ample opportunities to modify the crystal
structures and/or microstructures. These processes
have led to considerable improvement in the prop-
erties of a number of alloy systems and, consequently,
some industrial applications; these have been
described and fully documented in the references
listed above.
A novel way of transforming a material to a
metastable state is to reduce its grain size to very
small values of a few nanometres when the proportion
of atoms in the grain boundaries is equivalent to or
higher than those inside the grains. This type of
metastability can be classified as morphological meta
(or 'in') stability in the scheme of Turnbull." Materials
with such small grain sizes are now referred to as
nanocrystalline materials (and also as nanocrystals,
nanostructures, nanophase materials, or nanometre
sized crystalline solids), and have been shown to have
properties much improved over those exhibited by
conventional grain sized (> 10 urn) polycrystalline
materials. It is the combination of unique com-
positions and novel microstructures that leads to
the extraordinary potential of the nanocrystalline
materials.
There has been a continued increase in the number
of research investigations in recent years on the
synthesis/processing, characterisation, properties, and
potential applications of these novel materials. A new
journal entitled Nanostructured Materials, * was
started in 1992. In addition to several national confer-
ences and also as part of other symposia, a series of
international conferences is planned exclusively to
discuss the developments in nanostructured materials.
The first of these international conferences was held
in Cancun, Mexico, in September 1992 and the second
one was recently held in Stuttgart, Germany, in
October 1994.
The purpose of the present article is to present a
very broad overview of the structure and properties
of nanocrystalline materials. Potential applications of
these novel materials are also highlighted. This field
has been reviewed earlier with emphasis on some
selected topics.8-24 However, there is no comprehen-
sive review related to the materials aspects; this review
is an attempt to fill that gap.
* Published by Pergamon Press.
Materials Reviews 1995 Vol. 40 No.2 41
42 Suryanarayana Nanocrystalline materials
1 Schematic of the four types of nanocrystalline
materials (after Ref. 23)
Classification
Nanocrystalline materials are single phase or multi-
phase polycrystals, the crystal size of which is of the
order of a few (typically 1-100) nanometres in at
least one dimension. Thus, they can be basically
equiaxed in nature and will be termed nanostructure
crystallites (three-dimensional (3D) nanostructures),
or they can consist of a lamellar structure, and will
be termed a layered nanostructure (one-dimensional
(lD) nanostructure), or they can be filamentary in
nature (two-dimensional (2D) nanostructurej.l"
Additionally, Siegel/" considers zero-dimensional
atom clusters and cluster assemblies. Table llists this
classification and Fig. 1 illustrates the four types
of nanostructures schematically. The magnitudes of
length and width are much greater than thickness in
the layered nanocrystals, and length is substantially
larger than width or diameter in filamentary nano-
crystals. The nanocrystalline materials may contain
crystalline, quasicrystalline, or amorphous phases and
can be metals, ceramics, or composites.
Among the above, maximum attention has been
paid to the synthesis, consolidation, and characteris-
ation of the 3D-nanostructured crystallites followed
by the ID-Iayered nanostructures. While the former
are expected to find applications based on their
high strength, improved formability, and a good
combination of soft magnetic properties, the latter
are intended for electronic applications. Relatively
few investigations have been carried out on the
2D-filamentary nanostructures and it is only recently
Table 1 Classification of nanocrystalline materials
Typical method(s)
Dimensionality Designation of synthesis
Three dimensional Crystallites Gas condensation
(equiaxed) Mechanical alloying
Two dimensional Filamentary Chemical vapour deposition
One dimensional Layered Vapour deposition
(lamellar) Electrodepositi on
Zero dimensional Clusters Sol-gel method
International Materials Reviews 1995 Vol. 40
2 Schematic representation of equiaxed
nanocrystalline metal distinguishing between
atoms associated with the individual grains (.)
and those constituting grain boundary
network (0) (after Ref. 11)
that zero-dimensional clusters are being investigated
to 'tailor' the optical properties.
Characteristics
A schematic representation of a hard sphere model
of an equiaxed nanocrystalline metal is shown in
Fig. 2. Two types of atoms can be distinguished:
crystal atoms with nearest neighbour configuration
corresponding to the lattice and boundary atoms with
a variety of interatomic spacings, differing from
boundary to boundary. A nanocrystalline metal
contains typically a high number of interfaces
(-- 6 X 1025 m -3 for a 10 nm grain size) with random
orientation relationships, and consequently, a sub-
stantial fraction of atoms lie in the interfaces.
Assuming that grains have the shape of spheres or
cubes, the volume fraction of nanocrystalline mater-
ials associated with the boundaries can be calculated."
as
C = 311/d
where 11 is the average grain boundary thickness and
d the average grain diameter. Thus, the volume frac-
tion of atoms in the grain boundaries can be as much
as 50% for 5 nm grains and decrease to about 30%
for 10 nm grains and 30/0for 100 nm grains.
In recent years, it has become apparent that it is
the total intercrystalline region (consisting of grain
boundaries and triple junctions, i.e. intersection lines
of three or more adjoining crystals) which is important
since at very small grain sizes triple junctions become
an important component of the microstructure. Since
neither of the above grain shapes (spheres or cubes)
is reasonable nor are they suitable for deriving triple
junction volume fractions, Palumbo et al.26 consid-
ered the grains to have the regular 14-sided tetra-
kaidecahedron shapes, with the hexagonal faces
representing the grain boundaries, and edges corres-
ponding to triple junctions. Assuming the maximum
diameter of an inscribed sphere as the grain size d
and the intercrystalline component as an outer 'skin'
of the tetrakaidecahedron with a thickness of 11/2, the
No.2

intercrystalline region
z conditions. Since then a number of techniques have
a
i=
o
-c
ff: 0.1
w
~ fine grain sized polycrystalline materials can be used
=>
--l
~ triple junction
0.01 '--_--'-_--'-----'----L-.l.-.L...l.-L-.l.-------:..:.:....--L_-L--l--L--l-L~
1 10
GRAIN SIZE,
3 Effect of grain size on calculated volume
fractions for intercrystalline regions, grain
boundaries, and triple junctions, assuming grain
boundary thickness of 1 nm (after Ref. ?7)
intercrystalline volume fraction
as
Vic = 1 - [(d - ~)/d]3
The grain boundary component
~b = [3~(d - ~)2]/d3
and therefore, the volume fraction
triple junctions V;j is then given by
V;j = Vic - ~b
All of the above equations are valid for d > ~. Figure 3
shows the variation of Vic, ~b' and V;j as a function
of the grain size d and suggests that these values can
be as much as 70-800/0 at very small grain sizes of
2-3 nm (Ref. 27).
From the foregoing, it is clear that nanocrystalline
metals can be considered to consist of two structural
components - the numerous, small crystallites with
long range order and different crystallographic orien-
tations constituting the 'crystalline component' and a
network of intercrystalline regions, the structure of
which differs from region to region, called the 'inter-
facial' component. This interfacial component has an
average atomic density which is 10-300/0 less than
the crystal density depending on the type of chemical
bonding between the atoms. Further, the boundaries
exhibit a broad spectrum of interatomic spacings and
if these are averaged, there would be neither long nor
short range order. This has led Gleiter to coin the
nanocrystals as 'a new form of maUer'. Both these
characteristics of the interfacial component (reduced
density and wide distribution of interatomic spacings)
have been confirmed by experimental observations
using high resolution electron microscopy, grazing
incidence diffraction of X-rays, small angle X-ray
scattering, extended X-ray absorption fine structure
(EXAFS), and other techniques.I'r'"
Synthesis
Increased activity on the synthesis of nanocrystalline
materials in recent years dates back to the pioneering
investigations of H. Gleiter of the University of
Saarlandes in Germany in 1981.28 He synthesised
Suryanarayana Nanocrystalline materials 43
ultrafine nanometre sized metallic particles using an
inert gas condensation technique and consolidated
them in situ into small discs under ultrahigh vacuum
been developed in which the starting material can be
either in the solid, liquid, or gaseous states (Table 2).
In principle, any method capable of producing very
to produce nanocrystalline materials. If a phase trans-
formation is involved, e.g. liquid to solid or vapour
to solid, then steps have to be taken to increase the
nucleation rate and decrease the growth rate during
formation of the product phase. The methods which
100
nm have been commonly employed to synthesise these
materials include inert gas condensation.Pr" mechan-
ical alloying.'? spray conversion processing." sputter-
ing,32 physical vapour deposition (PVD),6 chemical
vapour processing." electrodeposition.i'v'" coprecipi-
tation,35,36 sol-gel process.?" sliding wear." spark
erosion." plasma processing.t?'?' laser ablation."
has been calculated hydrothermal pyrolysis." thermophoretic forced
flux systern.?" and quenching the melt under high
pressure." The grain size, morphology, and texture
can be varied by suitably modifying/controlling the
has been assessed as process variables in each of these methods.
Controlled crystallisation of the amorphous phases
produced by any of the above methods (e.g. mechan-
associated with ical alloying, vapour deposition, electrodeposition) or
by rapid solidification from the liquid state can also
be used to produce nanocrystalline materials. In fact,
the most common method to produce nanocrystalline
magnetic materials has been to obtain an amorphous
phase by rapidly solidifying the melt of appropriate
composition and then crystallising the glassy phase
at a relatively low temperature. These materials -
referred to as FINEMET - were first investigated by
Yoshizawa et al.46 and this method has now become
an established practice to study the structure and
properties of nanocrystalline magnetic materials.i?':"
This simple method has been commonly employed to
study the the magnetic properties of nanocrystalline
materials because it can produce (a) porosity free
samples, (b) samples with different grain sizes by
controlling the processing parameters, and (c) large
quantities of material. Furthermore, since no artificial
consolidation process is involved (as in inert gas
condensation, mechanical alloying, or plasma pro-
cessing, where fine powders are involved), the
interfaces are clean and the product is dense. There
have also been several basic investigations during the
past 2-3 years to define the conditions under which
Table 2 Methods to synthesise nanocrystalline
materials
Starting phase Techniques
Vapour Inert gas condensation
Sputtering
Plasma processing
Vapour deposition
(physical and chemical)
Liquid Electrodeposition
Rapid solidification
Solid Mechanical alloying/milling
Sliding wear
Spark erosion
International Materials Reviews 1995 Vol. 40 No.2
44 Suryanarayana Nanocrystalline materials

ultrafine microstructures form starting from the glassy illiqUid nitrogen

phases.49-51 r-------4
Even though all of the above methods have been [scraper
used with different levels of success to produce nano-

.' ..·..._'-"J", .
crystalline phases in a variety of materials, gas con-
densation, mechanical alloying, crystallisation of
amorphous alloys, chemical precipitation, and spray
conversion processing techniques have been most
. .,. -- .... main vacuum

C
chamber
commonly employed to produce 3D equiaxed nano-
.v ' .. ':-.:' .'.
crystallites while vapour deposition, sputtering, and A B
electrodeposition techniques have been used to syn- ~
evaporatlon
thesise the 1D-Iayered nanocrystals; the sol-gel pro- sources
cess has been commonly used to generate clusters.
Among all the techniques mentioned above, the gas
vacuum pumps --
condensation (or its modifications), mechanical
alloying, and spray conversion processing techniques fixed piston
have been most commonly employed to produce large low pressure
quantities of nanocrystalline materials. SbdE:I--I--anvii compaction unit

Gas condensation technique

sleeve
In this method, a metal or a mixture of metals is high pressure
evaporated inside an ultrahigh vacuum (UHV) compaction unit
piston -~~~~~~.
chamber filled with helium gas. As a result of
interatomic collisions with the helium atoms in the
chamber, the evaporated metal atoms lose their kin- 4 Schernatic representation of gas condensation
chamber for synthesis of nanocrystalline
etic energy and condense in the form of small crystals
materials (after Ref. 13)
of loose powder which accumulate, because of convec-
tive flow, on a vertical liquid nitrogen filled cold
finger. The powder is stripped off the cold finger by metastable solid solubilities; presumably related to
moving an annular Teflon ring down the length of solute segregation at the nanocrystalline grain
the tube into a compaction device. The scraping and boundaries.
compaction processes also are carried out under UHV
conditions to maintain cleanness of the particle sur- Spray conversion processing
faces (and subsequent interfaces) and also to minimise
WC-Co nanocrystalline composites have been pro-
the amount of any trapped gases (Fig.4).13 High
duced on a commercial basis using this method'"
densities of as compacted samples have been meas-
starting from aqueous solution precursors such as am-
ured with values of about 75-90% of bulk density
monium metatungstate [(NH4)6(H2 W12040)4H20]
for metal samples.
and CoCI2, Co(CH3COOh, or Co(N03h. The solu-
A full description of the technique, the variety of
tion mixture is converted into an aerosol and rapidly
evaporation methods, and the effect of the process
spray dried to give extremely fine mixtures of tungsten
variables on the size, size distribution, and consti-
and cobalt complex compounds. This precursor
tution of the powder particles can be found, for
powder is reduced with hydrogen and reacted with
example, in Refs. 11 and 15.
carbon monoxide in a fluidised bed reactor to yield
nanophase cobalt-tungsten carbide powder. The
Mechanical alloying tungsten particles are 20-40 nm in size. A typical
This process consists of repeated welding, fracturing, powder particle consists of a hollow porous 75 urn
and rewelding of powder particles in a dry high dia. sphere containing hundreds of millions of WC
energy ball charge.3,52 In this process, mixtures of grains in a cobalt matrix. To prevent grain growth of
elemental or prealloyed powders are subjected to tungsten, additions of inhibitors such as VC and
grinding under a protective atmosphere in equipment Cr3 C2 are made as binders during the sintering steps.
capable of high energy compressive impact forces Recently, vanadium was introduced into the starting
such as attrition mills, vibrating ball mills, and shaker solution itself to achieve a more uniform distribution
mills. A majority of the work on nanocrystalline in the powder mixture. The process parameters are
materials has been carried out in highly energetic being further optimised and since the process is fully
small shaker mills. A very recent comprehensive integrated, online control is also being planned,
review'" describes the process of mechanical alloying Widespread application of nanocrystalline mater-
and the characteristics and properties of the nanocrys- ials requires production of the powder in tonnage
talline materials obtained. It has been shown that quantities and also efficient methods of consolidating
nanometre sized grains can be obtained in almost the powders into bulk shapes.P Since the gas conden-
any material after sufficient milling time. The grain sation process is carried out completely under UHV
sizes were found to decrease with milling time down conditions, the cost of production is high. However,
to a minimum value which appeared to scale inversely the powder produced is very clean and the cleanness
with the melting temperature. Further, mechanical between the particles can be maintained even after
alloying of immiscible metals resulted in very large compaction. Mechanical alloying, on the other hand,

International Materials Reviews 1995 Vol. 40 No,2


is a proven commercial process to produce oxide
dispersion strengthened, Ni- and Fe-base superalloy
powders'f and can be easily adapted to produce
nanocrystalline powders on a commercial scale. This
should prove a relatively inexpensive method. But,
contamination of the powder during milling (because
of the fine size of the powder, atmosphere, and
addition of process control agents to prevent excessive
welding of powder particles among themselves and
to the container walls) could prove a serious limitation
of the process. Plasma processing can be another
viable commercial process for making nanocrystalline
powders.
Two companies in the USA have started producing
nanocrystalline powders on a commercial scale.
Nanophase Technologies (Darien (near Chicago), IL)
markets metal (e.g. Ag, AI, Au, Cu, Ni) and ceramic
(e.g. titanium dioxide, aluminium oxide, iron oxide,
chromium oxide, zirconia, yttria, silica, cerium oxide,
and manganese oxide) powders produced by a modi-
fied inert gas condensation method. They plan to
produce about 9000-18000 kg/year to be available
in 1995 (Ref. 55). Even though they sell nanocrys-
talline Ti02 powder now at $IIO/kg, the company
expects that the price will soon come down to about
$22-44/kg in view of the increased demand.
Nanodyne, Inc. (New Brunswick, NJ) produces
WC-Co composite powders by the spray conversion
process. They produce about 90000 kg/year of the
ultrafine grain WC-Co (the WC grain sizes are
20-40 nm, which are 10-20 times smaller than those
available in the finest conventional micro grain pow-
ders) composite and sell it for about $77/kg. Although
conventional tungsten tool materials cost about
$44/kg, the nanocrystalline materials could deliver up
to four times the service life.
ULTRAM (Olten, Switzerland) using the evapor-
ation condensation method, and PSI Ltd (Polegate,
East Sussex, UK) using the PVD technique, also
produce large quantities of powders and sell them in
the open market. A former Soviet Union (FSU)
company, Server (Talinn, Latvia) has advertised metal
powders available in gram to kilogram quantities
produced by an exploding wire technique.
Structure
In order to understand the interrelationship between
structure and properties, nanocrystalline materials
need to be characterised on both atomic and nano-
metre scales. The microstructural features of import-
ance include (a) grain size, distribution, and
morphology, (b) the nature and morphology of grain
boundaries and interphase interfaces, (c)the perfection
and nature of intragrain defects, (d) composition
profiles across grains and interfaces, and (e) identi-
fication of residual trapped species from processing.
In the case of layered nanostructures, the features of
importance are (a) the thickness and coherency of
interfaces, (b) composition profiles across interfaces,
and (c) the nature of defects.
There is a gamut of experimental techniques that
can yield structural information on nanocrystalline
materials. These include 'direct' microscopic tech-
niques such as transmission electron microscopy
Suryanarayana Nanocrystalline materials 45
5 High resolution electron micrograph of
nanocrystalline Cu sample produced by gas
condensation technique (after Ref. 58)
(TEM), scanning tunnelling microscopy (STM), field
ion microscopy (FIM), and the less direct electron,
X-ray, and neutron diffraction techniques. Indirect
spectroscopic tools, such as EXAFS, nuclear magnetic
resonance, Raman and Mossbauer spectroscopies,
and positron annihilation spectroscopy, have also
been used. Other useful tools employed include
differential scanning calorimetry (DSC), mass spec-
troscopy, X-ray fluorescence, atomic absorption spec-
troscopy, Auger electron spectroscopy, and hydrogen
absorption.
Owing to the ultrafine scale of these materials,
traditional characterisation tools such as TEM and
X-ray and neutron diffraction are both necessary and
useful to understand the structure of nanocrystalline
materials. However, for microchemical analysis on
the requisite fine scale, further advances in the state
of the art of instrumental capabilities will be necessary
to obtain the desired lateral scale resolution. Only
atom probe FIM or STM seem to offer the required
lateral scale resolution for such chemical mapping
at present.
Gleiter and co-workers9•11•56 and others"? have
used a number of the above techniques to study the
structure of nanocrystalline materials and interpreted
most of their results in terms of a two component
microstructure - perfect long range ordered atomic
arrangement in the grains and a random interfacial
component. The possibility was raised that the struc-
ture of the grain boundaries in nanocrystalline mater-
ials might have unique characteristics owing to the
constraints imposed on the grain boundary atoms by
their synthesis via cluster consolidation. In recent
years, however, there has been some confusion regard-
ing the structure of the grain boundaries in nanocrys-
talline materials and also whether it is different from
that in conventional coarse grained polycrystalline
materials. The present situation on this aspect is
briefly reviewed.
The microstructure of nanocrystalline metals has
been investigated by high resolution TEM. These
studies indicated that nanocrystalline metals consist
of small crystallites of different crystallographic orien-
tations separated by grain boundaries. Figure 5 shows
a high resolution transmission electron micrograph
International Materials Reviews 1995 Vol. 40 No.2
 46 Suryanarayana Nanocrystalline materials
recorded from a nanocrystalline Cu specimen syn-
thesised by the gas condensation method. 58 From
such micrographs (as well as from field ion micro-
graphs and by small angle X-ray or neutron scattering
data), grain sizes and their distributions have been
determined. The grains exhibit typically narrow log-
normal size distributions, i.e. they exhibit a single
peak when the frequency is plotted on a linear scale
against the log of the particle size.
The following features may be noted from high
resolution electron micrographs of nanocrystalline
materials:
1. Most of the ultrafine grains are equiaxed and
exhibit fringe contrast. The grains are randomly ori-
ented with respect to one another and there is no
apparent preferred orientation, irrespective of the
method of preparation.
2. The fringes abruptly stop in each grain at the
grain boundary, 59 indicating that there is little or no
atomic disorder perpendicular to the imaged planes.
3. The grain boundary planes are basically flat but
exhibit some local faccting.'" probably to bring the
planes from both grains into registry.
4. Neither voids nor dislocations have been
observed in many investigations, even though posi-
tron annihilation spectroscopy.i'''?' and precise den-
sitometry and porosimetry'v'v" measurements have
clearly indicated the presence of porosity in nanocrys-
talline metals. Nieman et ai.,58 however, reported
observation of abundant twinning and low index,
faceted crystal regions, while Wunderlich et ai.64
reported detection of isolated dislocations or dipoles.
Li et ai.59 reported observation of grain boundary
dislocations, fivefold twins, and edge and 60°
dislocations.
High resolution TEM investigations have been
carried out on nanocrystalline Pd (Refs. 59, 60, 64),
440C martensitic steel (Fe-17Cr*),65 Fe-Mo-Si-B
crystals, 59 and Ti-AI compacts." Wunderlich et ai.64
noted that the grain boundaries in nanocrystalline
Pd appeared to be different from conventional coarse
grained Pd, and with a smaller grain boundary thick-
ness of 0,4-0,6 nm as against the accepted value of
1 nm. A qualitative difference in the contrast in a
vicinity of > 0·6 nm at general grain boundaries (com-
pared with conventional polycrystalline material) was
observed. This was attributed to the high energy
states of the grain boundaries in nanocrystalline
. materials, a situation not observed in conventional
materials. They also noted that in the nanometre
sized crystals ordering of the grain boundary structure
to minimise the interfacial energy does not take place
since the curvature of the grain boundary has a much
different effect on the energy.
Based on Raman spectroscopy studies on nanocrys-
talline Ti02 (Refs. 67-69) and high resolution TEM
combined with image simulations on nanocrystalline
Pd (Refs. 60, 70), it was suggested that the grain
boundary structures in nanocrystalline materials are
no different from those observed in conventional
coarse grained polycrystalline materials." By com-
puter simulation methods it was shown that the
nanocrystalline grain boundaries contain short range
* All compositions are in weight- % unless stated otherwise.
International Materials Reviews 1995 Vol. 40
ordered structural units representative of the bulk
material suggesting that the atoms in nanocrystalline
materials have sufficient mobility to rearrange them-
selves into low energy configurations. Further, since
the densities of nanophase materials consolidated
from equiaxed clusters extend beyond the 780/0 limit
for close packing of identical spheres, Siegef" con-
cluded that an extrusionlike deformation of the clus-
ters occurred during the consolidation process (but
no preferred orientation was observed). This could
occur because of a combination of local deformation
and diffusional processes that allow low energy con-
figurations to result. Recent STM observations on
nanocrystalline Ag and Pd also confirm this hypo-
thesis. Complementing the above results from Raman
spectroscopy and small angle neutron scattering
experiments, Siegel and Thomas 70 concluded that the
grain boundaries in nanocrystalline materials and
conventional coarse grained polycrystalline materials
have similar structures. Similar conclusions were
reached based on observations in nanocrystalline Cu
and 440C martensitic steel produced by sliding wear.'"
Fe alloys produced by high energy ball milling," and
(Fe,Moh8Si9B13 nanocrystals prepared by crystallis-
ation of an amorphous ribbon." Thus, these data did
not reveal any evidence for grain boundary disorder
of the type and extent suggested by earlier studies.'!
The results of high resolution TEM have to be
interpreted with care.'! First, electron microscopic
characterisation of nanocrystalline materials has been
done under less than DHV conditions, making the
influence of impurities an important consideration.
Further, the influence of the high energy electron
beam on the shape and stability of the nanostructures
is yet to be defined. Second, since very thin specimens
(usually the thickness is less than the crystal diameter)
are required for ultrahigh resolution TEM, the 3D
crystal arrangement of a bulk nanocrystalline speci-
men gets transformed into a 2D arrangement. This
process may change the boundary structure as it
alters the forces between neighbouring crystals and
induces new forces due to the energy of the free
surface. In fact, thin foil specimen preparation may
modify the internal stresses and hence the free energy
of the entire system. Recent results using STM and
atomic force microscopy have shown that the struc-
ture of nanocrystalline materials is significantly affec-
ted." For example, it was shown that the grain
boundaries in nanocrystalline materials are highly
mobile far below the melting point and results in
structural rearrangement. Further, because of the high
diffusivity in nanocrystalline materials, atoms may
diffuse from the free surface of a thin specimen into
the grain boundaries at ambient temperatures within
a time much shorter than the time for specimen
preparation, leading to changes in the boundary
structure.
It has recently been shown that the method of
preparation and the time-temperature history of
nanocrystalline materials have a significant effect on
their structure and properties. For example, Tong
et al." and Wurschum et ai.75 have shown that the
structure of the grain boundary strongly depends on
the crystal size and external pressures. The pressure
effect in nanocrystalline materials seems to be of
No.2
 Suryanarayana Nanocrystalline materials 47

0,3
general significance because coarse grained crystalline
and glassy solids are far less sensitive to pressure ~
0 0,2
effects. In other words, the P~ V term in Gibbs free ctf
<l
energy may play an important role in nanocrystalline 0.1

materials. 0
Atomistic simulation results on nanocrystalline Fe
suggest that the structure of the boundary component eft. -0,1
.s
is different from that of the amorphous or gaseous <l
-0,2 Ni3P
substances." Recent Mossbauer spectroscopy results (a)
on nanocrystalline ZnO also suggest that the bound- -0,3
ary atoms exhibit a non-recoil free y-absorption, i.e. 0 20 40 60 80 100
they behave like almost free, isolated atoms."? AVERAGE GRAIN SIZE, nm
From the above it is ·apparent that the question of 0,3
whether the structure of the grain boundaries in
nanocrystals is different from the coarse grained crys-
tals is not answered clearly. However, it is clear that
• •
0.2
nanocrystalline materials are not just polycrystals with ~
0

a reduced grain size. Once the crystal size and bound- :>
<l
ary dimensions become comparable with certain
length scales new physical effects are to be expected. 0.1

Direct evidence for an accurate structure of the

grain boundary is difficult to obtain in view of the
relaxation at surfaces; additional results from FIM
and STM may shed new light. Additionally, it would
be useful to compare the structure of the grain
boundaries in the same material using the same
characterisation technique, but produced by different
methods to resolve some of the conflicting data
available in the literature.
The structure of the grains (crystallites) in nanocrys-
talline materials has been normally accepted to be
the same as in a coarse grained material and hence
there have not been many investigations on this
aspect. Lu and co-workers 78,79 used X-ray diffrac-
tion and Mossbauer spectroscopy techniques and
observed some interesting results in nanocrystalline
Ni3P and Fe2B phases obtained by crystallisation of
the Ni-P and Fe-Mo-Si-B amorphous alloys. Both
the phases have tetragonal structures and their a para-
meters increased and the c parameters decreased with
a decrease in grain size (about 0·2%) (Fig. 6), while
the unit cell volume increased with respect to the
(b)
0
0 0.1 0.2
1/d, nrn"
6 a variation of Aa and Ac with average grain size
of Ni3P and Fe2B phases and b variation of AV
versus 1/dfor Ni3P and Fe2B phases
porosity present in the samples. Additionally, grain
boundary Zener drag and triple junction drag have
been found to be significant in retarding grain
growth." In some instances, abnormal grain growth
has been observed.82,83
Significant grain growth (doubling of the crystal
size in 24 h) was observed in several single phase
nanocrystalline materials at ambient temperature or
below only when the equilibrium melting temperature
Tm was lower than about 600°C (Ref. 9). Grain growth
was retarded for higher Tm metals, e.g. for Cu up to
100°C, for Pd up to 250°C (Ref. 9), and for Ti-Mg
I"V

equilibrium values for coarse grained materials. The up to 450°C (Ref. 84).
isomer shift and half-line width measurements con- The kinetics of normal grain growth under iso-
firmed these results. These lattice distortions have thermal annealing conditions can be represented by
been explained on the basis of a supersaturation of the equation
the constituent elements or vacancies.I"
d2-d6=Kt
Grain growth where d is the grain size at time t, do the mean initial
Grain growth occurs in polycrystalline materials to grain size (at t = 0), and K a constant. Theoretical
decrease the interfacial energy and hence the total predictions also agree with the above trend. The
energy of the system. Since nanocrystalline materials above equation is obeyed only at temperatures
have a highly disordered large interfacial component close to the melting point. Assuming that d» do, the
(and therefore they are in a high energy state), the empirical equation
driving force for grain growth is high. However,
contrary to the expectations, experimental obser-
d = K'tl/n
vations suggest that grain growth in nanocrystalline where K' is another constant and n the grain growth
materials, prepared by almost any method, is very exponent, better represents the grain growth behav-
small (and almost negligible) up to a reasonably high iour in metals at lower temperatures. n has been
temperature. found to have values ranging between 2 and 3.
The inherent stability of the nanocrystalline grains The activation energy for grain growth Q, can be
has been explained on the basis of structural factors calculated from the equation
such as narrow grain size distribution, equiaxed grain
K'=Kbexp(-Q/RT)
morphology, low energy grain boundary structures,
relatively flat grain boundary configurations, and where Kb is a pre-exponential constant, and R is the
International Materials Reviews 1995 Vol. 40 No.2
48 Suryanarayana Nanocrystalline materials

gas constant. The processes and mechanisms con- 100

trolling grain growth in crystalline solids were recently
reviewed." 90
Grain growth studies in nanocrystalline materials
80 1273K
are difficult since the grain size cannot be accurately
determined.t":"? In spite of this, some grain growth
70 •
0- 1173K
studies have been carried out using TEM, DSC, X-ray
diffraction, and Raman spectroscopy techniques.
Grain growth studies in nanocrystalline materials
were conducted by observing the grain size in the as
E
c
ui
N
00
60

50
,- _/0 »-:

synthesised material and observing its change as a

function of time at different temperatures, using direct
z
«
a:
<.!J
40 /
0
------- ... 1073K

microscopic observations, 86,88,89 or estimated from

X-ray diffraction peak broadening values.?? Chen and 30
~~~A e------ e- 1048K

Spaepen'" .have shown that DSC techniques can be

used to determine the parameters that characterise
the grain growth process in nanocrystalline materials.
The heat released during the growth of the nanometre
sized grains is large enough (because of the high
density of interfaces) to be detected by present day
calorimeters. It is estimated that the heat energy
released can be as much as 339 mJ for a grain size of
S nm, while it decreases to 0·7 mJ for a S urn grain
size."?
Crystallisation of amorphous alloys obtained by
rapid solidification techniques often results in the
formation of nanocrystalline grains at relatively low
temperatures." Grain growth studies after crystallis-
ation of these glasses was observed and studied by
many authors.47.48,81,90,93 Grain growth studies have
also been performed on nanocrystalline materials
produced by sliding wear." inert gas conden-
sation,82,86 electrodeposition." electron gun evapor-
ation.?" mechanical alloying,95,96 and chemical vapour
deposition.??
Crystallisation of metallic glasses takes place gener-
ally in two stages, though polymorphic crystallisation
converts the glassy phase directly into a crystalline
phase of the same composition." A stable tetragonal
(Fe,Co)Zr2 phase forms directly from the ternary
Fe-Co-Zr amorphous phase, while in the binary
Fe-Zr alloys, the amorphous phase first transforms
to a metastable fcc FeZr2 phase which later trans-
forms to the equilibrium tetragonal FeZr2 phase.
Grain growth studies were performed for both the
stable and metastable phases and it was found that
the grain size increases with annealing time at temper-
ature." It has also been noted that grain growth
starts at a higher temperature in the nanocrystalline
sample with smaller grains'" and that grain growth
is rapid above a certain temperature and becomes
negligible for longer annealing times. Figure 7 shows
a plot of the grain size variation with annealing time
at different temperatures-in an A13Nb-S·STi alloy.?"
From an analysis of the kinetic data Spassov and
Koster'" calculated that the grain growth exponent n
has a value of 3 and that the activation energy for
grain growth of the FeZr2 phase in a wide temperature
range (of about 200 K) was 260 ± 2S kJ mol-1 for
both the binary and ternary alloys. Similarly,
activation energies of 162 ± 2 kJ mor ' for Al3Nb
(Ref. 89) and 201 ± 2 kJ mol-1 for A13Nb-S·STi
(Ref. 9S) were reported for grain growth. It may be
noted that the grain growth is retarded by Ti
additions. The value of n was calculated as 3 for the
20
le ______
4~
........
0 0 o- 1023K
_0
10
0
0 5 10 15 20 25
ANNEALING TIME, ks
7 Variation of mean grain size of Nb3AI-S·STi
phase as function of annealing time at different
temperatures (after Ref. 9S)
binary AI-Nb alloy, whereas it was estimated to be 4
for the ternary AI-Nb- Ti composition. By measuring
the value of n, Spassov and Koster'" concluded that
they were indeed observing crystallisation of an
amorphous phase rather than grain growth in an
extremely fine grained material.
In most of the studies involving nanocrystalline
materials, the value of n is different from the value
of 2 deduced from the parabolic relationship for grain
growth. Thus, in addition to Zener drag (where a
particle interacts with the grain boundary to reduce
the energy of the boundary-particle system and
restrain the boundary movement), other mechanisms
such as pinning of grain boundaries by pores or
inclusions also may be operative. The fact that
pores86,99 and impurity dopingl?" have considerable
effect on the grain growth characteristics was clearly
demonstrated in Ti02. For an initial grain size of
14 nm, when the porosity was about 2S%, the grain
size after annealing for 20 h at 700°C was 30 nm
(Ref. 99). When the porosity was reduced to about
10%, the grain size for a similar annealing treat-
ment was dramatically increased to SOO nm. The
same authors have also demonstrated that sintering
the same nanocrystalline material under pressure
(1 GPa), or with appropriate dopants such as Y, can
suppress the grain growth (Fig. 8).101
Pinning of grain boundaries in nanocrystals of a
Ni solid solution by the Ni3 P precipitates in a crystal-
lised Ni-P amorphous alloy'" and segregation of Si
to grain boundaries in a Ni-Si solid solution?" have
been found to be responsible for preventing grain
growth in nanocrystalline phases. LU81 studied the
thermal stability of 7-48 nm grains in a Ni-P alloy
and concluded that samples with smaller grain sizes
have enhanced thermal stabilities, suggesting that the
grain growth temperature and the activation energy
for growth in a nanocrystalline state are higher in
comparison with coarser grains. This is attributed to

International Materials Reviews 1995 Vol. 40 No.2


o • p=O
~ A p=1GPa
o • P=OTi98.2Y1.802
E
c
a:
w
tu 100
~ ~0
« activated sintering.l'" shock (explosive) consoli-
o Q)
z
<i:
a:
CJ
w U5
50
~ 50
a:
w density requires use of high temperatures. However,
~ because nanocrystalline materials resist grain growth,
o 500 1000
SINTERING TEMPERATURE, °C
8 Density (open symbols) and grain size (closed
symbols) of nanocrystalline Ti02 as function of
sintering temperature (after Ref. 101)
the configuration and energetic state of the interfaces
in the nanocrystalline materials.
Ganapathi et al.8s tried to fit their grain growth
data on nanocrystalline Cu produced by sliding wear
and observed an excellent fit for values of n of 2, 3,
or 4. Thus, they concluded that it is difficult to identify
a grain growth mechanism on the basis of the
exponent n alone, and that grain growth in nanocrys-
talline materials probably occurs in a manner similar
to that in conventional polycrystalline materials.
Abnormal grain growth has been observed at room
temperature or slightly above in some instances, e.g.
Cu, Ag, and Pd (Refs. 82, 83). Similar to the obser-
vation of Hahn et al.,99 Gertsman and Birringer'P
also noted that grain growth occurs preferentially in
the denser material. This anomalous grain growth
has been suggested to be due to (a) a certain non-
uniformity of the grain size distribution in the as
prepared samples (so that the larger grains act as
nuclei) and (b) impurity segregation. If the impurity
distribution is spatially non-uniform, enhanced grain
growth may occur in regions of lowest impurity
content. The reason why such abnormal grain growth
does not occur in coarse grained polycrystalline
materials has been attributed to the enhanced grain
boundary enthalpy (leading to high driving force)
and/or non-equilibrium grain boundary structure
(leading to increased mobility of grain boundaries) in
the nanocrystalline state.
It has also been recently noted that about 50% of
the excess enthalpy stored in nanocrystalline Pt is
released during heating without any measurable vari-
ation of grain size;102owing to relaxation of internal
strain and/or non-equilibrium grain boundary struc-
tures. The kinetics of relaxation and grain growth
have been found to be very sensitive to the sample
preparation method.l'" Samples with the same initial
grain size obtained by inert gas condensation and
ball milling show very different recovery behaviour,
Suryanarayana Nanocrystalline materials 49
which was explained in terms of the estimated grain
boundary energies and initial grain size distribution.
Grain growth can also occur in nanocrystalline
materials during consolidation of the powder. This
requires exposure of the powder to high tempera-
tures and pressures for extended periods of time.
co Consolidation of nanocrystalline powders has been
.Q achieved by electro discharge compaction.l'" plasma
£; dation.l?" hot isostatic pressing.l"? and Ceracon
~
0 processing. lOS Optimisation of the consolidation
>= parameters is important because retention of the
~
nanostructures requires use of low consolidation
z
w temperatures while the achieving of full (theoretical)
0
grain coarsening has not been a serious concern in
the consolidated materials. Figure 9 shows a series of
electron micrographs of a Ti-24AI-IINb (at.-%)
powders of 15 nm grain size produced by mechanical
alloying and consolidated by hot isostatic pressing at
800,900, and 975°C at a pressure of 207 MPa for 2 h.
It may be noted that the grain sizes are only 50 nm
at 800°C and 125 nm at 975°C. A similar situation
was obtained in the Ti-55 at.-o/oAIsamples mechan-
ically alloyed to an amorphous state and hot iso-
statically pressed at the above temperatures; in fact,
the grain sizes are finer in this case.lOS Recent results
on consolidation of nanocrystalline materials can be
found in Ref. 53.
Properties
Because of the very fine grain sizes, nanocrystalline
materials exhibit a variety of properties that are
different and often considerably improved in com-
parison with those of conventional coarse grained
polycrystalline materials. These include increased
strength/hardness, enhanced diffusivity, improved
ductility/toughness, reduced density, reduced elastic
modulus, higher electrical resistivity, increased specific
heat, higher thermal expansion coefficient, lower ther-
mal conductivity, and superior soft magnetic prop-
erties in comparison with conventional coarse grained
materials. All of these properties are being extensively
investigated to explore possible applications. In the
present article, the origin and consequences of some
of these properties are discussed.
Diffusion and sinterability
Since nanocrystalline materials contain a very large
fraction of atoms at the grain boundaries, the numer-
ous interfaces provide a high density of short circuit
diffusion paths. Consequently, they are expected to
exhibit an enhanced diffusivity in comparison with
single crystals or conventional coarse grained poly-
crystalline materials with the same chemical com-
position.l09-115This enhanced diffusivity can have a
significant effect on mechanical properties such as
creep and superplasticity, ability to dope efficiently
nanocrystalline materials with impurities at relatively
low temperatures, and synthesis of alloy phases in
immiscible metals and at temperatures much lower
than those usually required in other systems.
International Materials Reviews 1995 Vol. 40 No.2
50 Suryanarayana Nanocrystalline materials
9 Electron micrographs of mechanically alloyed Ti-24AI-11 Nb (at.-%) powders hot isostatically
(207 MPa, 2 h) (after Ref. 108)
The measured diffusivities .in nanocrystalline Cu
are about 14-20 orders of magnitude higher than
lattice diffusion and about 2-4 orders of magnitude
larger than grain boundary diffusion. For example,
the measured diffusivity at room temperature is
2·6 x 10- 20 m2 s -1 for 8 nm grain sized Cu samples
compared with 4·8 x 10-24 m2 S-l for grain boundary
diffusion and 4 x 10- 40 m2 s - 1 for lattice diffusion.I':'
Similarly enhanced diffusivities were also observed
for solute diffusion in other metals. However, it was
noted 116 that hydrogen segregation at grain bound-
aries in Pd had to be described by a spectrum of site
energies or segregation energies. This causes the
diffusion coefficient to become concentration depen-
dent, being lower than the single crystal value at low
hydrogen concentrations and higher for higher hydro-
gen concentrations. The enhanced self and impurity
diffusivities in nanocrystalline materials appear to be
strongly linked to the porosity present in the samples.
Averback et al.101 showed that diffusion coefficients
could be reduced to conventional values by sintering
the samples to full density. However, in the light of
the more recent results.I'" the difference in diffusion
coefficients seems to be caused by differences in
relaxation states rather than by porosity.
The increased diffusivity (and consequently the
reactivity) leads to increased solid solubility limits,
formation of intermetallic phases (at temperatures
much lower than those required for coarse grained
materials and sometimes new phases), and increased
sinterability of nanocrystalline powders.
Solid solubility limits are usually enhanced when
the material is in the nanocrystalline state. In extreme
cases, solid solutions can also form in alloy systems
which exhibit miscibility gaps both in the liquid and
solid states. Typical examples of this phenomenon are
the Ag-Fe (Refs. 117,118), Ti-Mg (Ref. 119), and
Cu-Fe (Ref. 120) systems. While the solid solubility
of Mg in Ti under equilibrium conditions is
<0·2 at.-%, it could be increased to 6 at.-% when Ti
grains are in the nanometre range. Similarly, the solid
solubility of Bi in Cu is < 10-4 at.-% under equi-
librium and this has been increased to 4 at.-% in the
International Materials Reviews 1995 Vol. 40
pressed
nanocrystalline state.111 A dramatic example is the
achievement of 17 at.-% (40 wt-%) solubility of Hg
in nanocrystalline Cu, against an equilibrium value
of < 1 at.-% (Ref. 121). The enhanced solid solubility
limits in these systems have been explained on the
basis of elastic strains at the interfaces; demonstrated
earlier to be the reason both theoretically and exper-
imentally for various alloys. Thus, nanostructure pro-
cessing appears to be a novel way of forming solid
solution alloys in systems in which alloying has not
been possible by any other technique.
The high diffusivity of nanocrystalline materials
results in alloying by diffusion along the grain bound-
aries resulting in the formation of stable and meta-
stable phases at relatively low temperatures. For
example, formation of the Pd3 Bi intermetallic has
been found to occur at 120°C, a temperature much
lower than normally observed.P" Similarly, nanocrys-
talline mixtures of Cu and Er crystallites formed
the equilibrium CuEr compound by compaction.F"
Li et al.123 detected two new polymorphs of erbium
oxide in the nanocrystalline state.
Another important consequence of the increased
diffusivity is that sintering of nanocrystalline powders
can occur at temperatures lower than those required
for sintering coarse grained polycrystalline powders.
Significant improvements in the sinterability and
mechanical properties (hardness and fracture charac-
teristics) have been obtained in nanocrystalline Ti02
(rutile) in comparison with conventionally synthesised
coarse grained rutile.61,99,124 For example, Ti02 with
a grain size of 12 nm could be sintered at ambient
pressures at temperatures 400-600 K lower than those
required for ball milled 1·3 urn powder (Fig. 10), and
without the need for any compacting or sintering aid,
such as polyvinyl alcohol, which is usually required.
Additionally, the fracture characteristics of sintered
nanocrystalline Ti02 appear to be significantly differ-
ent from those of sintered commercial powder. The
sintering temperature for trans granular fracture of
nanocrystalline Ti02 (12 nm grain size) has been
shown to be 200 K lower than that for sintered
commercial coarse grained (1·3 urn grain size) powder.
No.2
 Suryanarayana Nanocrystalline materials 51

c-.IE 1600
E

C\I
'E 200
z
~ --e- 14nm grain size
en
en --£1 50/J.m grain size
w
~ 100
en
-a- 8--0 --a --a --e

0.5 1.0 1.5 2.0 2.5

o~:::::==:::±=:::::±:=.2.:~~~:i:=..2--'---L-L--L---l-----.J
o 200 400 600 800 1000
TEMPERATURE) -c
10 Vickers microhardness of Ti02 (rutile)
measured at room temperature as function of
30 min sintering at successively increased
temperatures. Note that rutile with 12 nm
grain size sinters at temperatures 400-600 K
lower than coarse grained (1'3 Jim) rutile:
=
1 kgf mm -2 9'8 MN m -2 (after Ref. 61)
Further, the sintered nanocrystalline material had
smaller and fewer voids than the commercial mater-
ial.125 Reduced sintering temperatures for achieving
full density was also observed in nanocrystalline
titanium aluminide intermetallics'F'r'?" and thus it
may be a general phenomenon. It is not surprising
that nanocrystalline materials, with their ultrafine
grain sizes (and possibly clean particle surfaces and
high grain boundary purity), will sinter at much lower
temperatures than conventional coarse grained mater-
ials. However, it is interesting that they retain the
ultrafine grain size after sintering to full density.
Mechanical properties
The elastic constants of nanocrystalline materials
have been found to be reduced by 30% or less. These
results were interpreted as a result of the large free
volume of the interfacial component resulting from
the increased average interatomic spacings in the
boundary regions.!' The reduction in Young's modu-
lus values was interpreted by others63,126 to be the
result of the level of porosity and state of cracks in
the samples.
The most significant change resulting from a
reduction in the grain size to the nanometre level is
a 4-5 times increase in the strength and hardness
over the coarse grained material. This is also the least
understood and most controversial area. While the
0·20/0 yield strength of a 14 nm grain size Pd sample
was reported to be 250 MN m -2, that of a sample
with a 50 urn grain size was only 52 MN m - 2
(Fig. 11).62 Similar results were reported by others
in Pd (Refs. 127, 128) and other pure metals Cu
(Refs. 63,127,129), Ni (Refs. 129-131), Fe (Refs.
129, 132), Ti (Ref. 133), Ag (Ref. 58), intermetallic
compounds Nb3Sn (Ref. 134), Ni3AI (Ref. 135),
TiAl (Refs. 32, 108), Ti3AI (Ref. 108), Al3Nb (Ref.
136), Ni-P (Refs. 128, 137), Fe-B-Si (Ref. 138),
Fe-Mo-Si-B (Ref. 139), and Ti02 samples." A on the variation of hardness (there are very few
STRAIN, 0/0
1200 1400
11 Stress-strain curves for nanocrystalline
(14 nm) and coarse grained (50 Jim) Pd samples:
strain rate 2 x 10-5 S-1 (after Ref. 62)
reduction in hardness with decreasing grain size was,
however, reported for Cu and Pd samples by Chokshi
et al.140 and for Ni-P by Lu et al.141
The Hall-Petch relationship142,143 for conventional
coarse grained polycrystalline materials suggests
that the yield strength (or hardness) of a material in-
creases with a decreasing grain size according to the
rela ti onship
(J = (Jo + kHdn
where d is the grain size, (J the 0·2°A> yield strength
(or hardness), (Jo the lattice friction stress to move
individual dislocations (or the hardness of a single
crystal specimen, d ~ (0), n the grain size exponent
(generally -1/2), and kH a constant, called the Hall-
Petch intensity parameter. Accordingly, nanocrystal-
line materials are expected to show a much higher
yield strength than the coarse grained materials of
the same composition. However, it should be realised
that the above equation has certain limitations. First,
the strength value cannot increase indefinitely to
beyond the theoretical strength limit. Second, any
relaxation process taking place at the grain bound-
aries (because of the very fine grain size) could lead
to a decrease in strength and, thus, an inverse Hall-
Petch relationship (decrease in strength with a
decrease in grain size) could result below some criti-
cal grain size. Third, the Hall-Petch relationship
was derived on the basis of strengthening resulting
from dislocation pile-ups at physical obstacles. At
extremely fine grain sizes, e.g. in the nanometre
regime, the individual grains cannot support more
than one dislocation; and thus, the Hall-Petch
relationship may not be valid. Thus, it is logical to
expect that the mechanism of hardening/softening
observed in nanocrystalline materials may be funda-
mentally different from that observed in coarser
grained metals.
Recently, there has been an active debate in the
literature on the origin of the high strengths of
nanocrystalline materials, and attempts have been
made to modify the Hall-Petch relationship to explain
the observed results. Before these modifications are
discussed, it may be useful to summarise the results
International Materials Reviews 1995 Vol. 40 No.2
52 Suryanarayana Nanocrystalline materials
reports of yield strength measurements on materials
with a grain size of < 100 nm) with grain size.
1. Generally, the hardness increases with a decrease
in grain size.
2. At very small grain sizes, the hardness decreases
with a decrease in grain size, referred to as the inverse
Hall-Petch relationship.l'" The critical grain size at
which this reversal takes place is dependent on the
rnaterial. In some materials, the hardness increases
linearly with d-1/2 and then reaches a plateau at
small grain sizes.
3. The Hall-Petch slope kH is much smaller in the
nanometre range than is observed at more normal
grain sizes.
4. Annealing a sample to produce grain growth
resulted in hardness values greater than those of as
prepared samples with similar grain sizes.
Consider now the possible reasons for the deviation
from the Hall- Petch relationship in nanocrystalline
materials. The Hall-Petch relationship was derived
using the concept of dislocation pile-ups in individual
grains.r" However, since in very fine grained mater-
ials, e.g. nanocrystalline materials, pile-ups cannot
form when the grain size is less than a critical value
de (Ref. 146), weakening mechanisms (e.g.viscous type
flow) operate and lead to a decrease in hardness with
decreasing grain size, i.e. a negative value for the
slope kH (Ref. 147). The value of de can be calculated
by equating the repulsive force between the dislo-
cations and the applied stress using the relation
3Gb
d =----
e n(l- v)H
where G is the shear modulus, b the Burgers vector,
v the Poisson's ratio, and H the hardness.
The above model could explain the reversal in
hardness with grain size in nanocrystalline Cu and
Pd. The negative slope in Ni-P has been explained
on the basis of precipitation hardening due to the
formation of Ni3 P on thermal annealing. However,
this reasoning does not explain all of the results." A
more convincing explanation for the negative slope
can be offered by taking into account the volume
fraction of triple junctions,27,131,148since it has been
earlier reported 149that an increased triple junction
volume-fraction leads to softening and enhanced bulk
ductility in polycrystalline materials.
Many investigators now accept that there exists a
critical grain size in nanocrystalline materials above
which the Hall- Petch slope is positive and below
which it is negative; different reasons have been put
forward for its presence. According to Palumbo
et ai.,148 the transition from a positive to a negative
slope occurs when the triple junctions in the micro-
structure begin to comprise a significant volume
fraction of the bulk specimen value. Fougere
et ai.127,150 and Liu et ai.151 observed that the harden-
ing or softening of nanocrystalline materials can
depend on the method used to vary the grain size.
Annealing a sample to produce grain growth resulted
in hardness values greater than those of as prepared
samples with similar grain sizes. Lu and SUi,152on
the other hand, felt that thermal annealing of the as
prepared sample will relax the interfacial structure
leading to a reduction in interfacial excess energy
International Materials Reviews 1995 Vol. 40
and this could explain the abnormal Hall-Petch
behaviour.
Unlike the situation in equiaxed nanocrystalline
materials, the Hall-Petch type relationship appears
to be obeyed always with a positive slope in layered
nanocrystalline materials when the microhardness is
plotted as a function of the layer thickness. This
observation has been verified in vacuum deposited
AI-2-15'3Fe alloys with the Fe layer spacing vary-
ing between 0·2 and 2·9 nm (Ref. 6) and also in
Cu-15-60Fe alloys.P'' The layer thickness here is
defined as the sum of the individual layer thicknesses
of the constituent metals. However, it should be
remembered that hardnesses have been measured for
layer thicknesses of 24-2000 nm only, which are con-
siderably larger than the sizes at which a transition
in the Hall-Petch slope is expected to occur. It will
be interesting to produce layered nanocrystals with a
layer thickness of about 10 nm or less and see whether
the Hall- Petch slope is negative in this range.
Apart from the sign of the Hall- Petch slope, there
are also reports that the grain size exponent n can
have very different values (i.e. the traditional Hall-
Petch equation may not be valid at all). Christman 'P"
presents data for both coarse and nanograined
polycrystalline materials to show that the yield
strength or hardness variation with grain size can be
equally well explained assuming that n = -1, -1/2,
-1/3, and -1/4. Each of these values, obtained from
theoretical estimates, is based on different mechanisms
and/or modelling for dislocation-grain boundary
interaction mechanisms. Christrnanv" also suggests
that a correspondence could exist between the crystal
structure and n. Assuming that the dislocation pile-up
model is valid even in nanocrystalline materials,
Pande et ai.155 considered the effect of a smaller
number of dislocations in the pile-up and also the
effect of anisotropy and suggested that the grain size
exponent could be modified from the traditional value
of -1/2. Other investigators have modified the
normal Hall-Petch equation by modifying either the
grain size exponent and/or the slope of the plot k«.
Different values of kH have also been reported above
and below the critical grain size.128,156-158
Instead of a dislocation pile-up, another Hall-Petch
model assumes a characteristic dislocation network
density within the grains to transfer slip through the
otherwise impenetrable grain boundaries. Assuming
that the dislocation line tension is size scale depen-
dent, Scattergood and Koch 156identified the critical
grain size de with a transition from cutting to Orowan
bypassing of the network dislocations. They calcu-
lated the variation of hardness with grain size under
these two conditions and arrived at the following
relationshi ps
H = Ho + kHd-1/2 for d ~ de
and
H = kH _1_ [In(~)J d-1/2 for d < de
2na reff
where a is a dimensionless constant (= (J/Gb2, where
(J is applied shear stress, G the shear modulus, and
b the Burgers vector) and reff an effective cut-off
radius. Thus, a straight line with a slope m = kH/2na
No.2
 Suryanarayana Nanocrystalline materials 53

was obtained when the hardness was plotted against lead at room temperature. However, no superplas-
[In(d/rerr)]d-1/2. A good agreement was reported ticity has yet been observed in nanocrystalline mater-
between kHxPt and kn
t (= 2nam) for nanocrystalline ials at room temperature, which would yield strain
materials with a grain size d < de and gives an rate sensitivity values about an order of magnitude
adequate description of the grain size softening higher than the maximum so far observed. Never-
transition. theless, superplastic behaviour is expected to be exhib-
ited by these ultrafine grained materials at least at
Ductilisation of ceramics and intermetallics elevated tcmperatures.l'"
The enhanced strain rate sensitivity appears to
The fine grain sizes and the high rates of diffusivity
arise from a combination of several factors - grain
observed in nanocrystalline materials suggest that
boundary sliding, presence of porosity, ultrafine grain
considerable ductility can occur in these materials
size, and rapid short range diffusion. These can lead
even at room temperature. This follows from the
to enhanced formability of intermetallics, ceramics,
expression for strain rate (ds/dr), during diffusional
and semiconductors. It has been recently demon-
creep
strated that near net shape forming of nanocrystalline
de aQ ( B2f1Db) Ti02 can be achieved at 800-900°C with excellent
dt = d2kT B1Dy + -d- detail.165
The fine grain size and its effect on improved
where a is the applied stress, Q the atomic volume, forming characteristics is an advantage for many
d the grain size, k the Boltzmann cons tan t, T the structural materials. However, the ultrafine grain size
temperature, B1 and B2 constants, D; and Db, respect- may not be compatible with good elevated temper-
ively, the volume and grain boundary diffusion ature creep performance. A way out of this dilemma
coefficients, and f1 the grain boundary width. At low can be that the nanostructured grains can be used to
temperatures, where boundary diffusion dominates, enhance processing (forming) and the grain size of
de/dt can be rewritten'P? as the final product could be subsequently increased
de B2aQf1Db using a suitable heat treatment.
It should be realised that enhanced ductility (and
dt - d3kT
hence formability) is generally associated with low
Thus, the diffusional creep rate of a polycrystalline hardness (and strength) and the presence of sufficient
sample is increased by reducing the grain size and/or number of slip systems to satisfy the von Mises
by increasing the grain boundary diffusivity. The criterion for plasticity. Since nanocrystalline materials
grain size of nanocrystalline materials is reduced by are very hard (and strong), it is doubtful whether the
three orders of magnitude compared with conven- formability can be substantially improved (at least in
tional polycrystalline materials (from about 10 urn tension), especially in non-cubic intermetallic com-
to 10 nm), and the boundary diffusivity is higher pounds. This may, however, be possible if the mechan-
by three orders of magnitude. Accordingly, nanocrys- isms of deformation in nanocrystalline materials are
talline ceramic and intermetallic compounds are entirely different from those in conventional coarse
generally expected to exhibit a 12 orders of magni- grained polycrystalline materials. Irrespective of the
tude increase in diffusional creep. And this has, in reasons for the high strength of nanocrystalline mater-
fact, been observed'P? when nanocrystalline CaF2 ials, several investigations are being conducted to
and Ti02 deform plastically at room temper- optimise the strength and ductility of these materials.
ature. However, there have been very few reports of It has been noted that a uniform dispersion of about
the expected dramatically increased ductility in 20 vol.-% of a nanocrystalline phase in an amorphous
nanocrystalline intermetallic compounds. matrix increases the strength of the material signifi-
Jain and Christman'?' consolidated mechanically cantly while maintaining an adequate level of ductility
alloyed Fe-28AI-2Cr (at.-%) powder by shock wave in the composite (Fig. 12).166 This appears to be a
compaction and produced fully dense compacts with fruitful line of research investigation.
a grain size of rv 80 nm. These compacts were brittle Metals are usually soft, ductile, and tough while
in tension, with a failure strength of 0·65 GN m - 2, ceramics are strong, hard, and brittle. However,
comparable to the coarse grained intermetallic. through nanostructure processing, it appears to be
However, the compact exhibited superplastic-like flow possible to make metals hard and strong like ceramics
in compression at room temperature with true and ceramics can be made ductile like metals.
strains > 1·4.
Wang et ai.,162 conducted creep experiments on
nanocrystalline (28 nm) and coarse grained (257 nm) Electrical properties
Ni-20 at.-%P samples and noted that the creep rate Because of the increased volume fraction of atoms
at 280°C was 3·7 times higher for the nanocrystalline lying at the grain boundaries, the electrical resistivity
sample than the coarse grained one. Based on the of nanocrystalline materials is expected to be higher
analysis of the creep data, the authors concluded that than that in the corresponding coarse grained
creep in the two different samples originated from polycrystalline materials. Actual measurements of
different mechanisms. electrical resistivity on the nanocrystalline materials
Recent nanoindenter measurements on 12 nm Ti02 have been carried out only recently.
(Ref. 124) and 7 nm ZnO (Ref. 163) have demon- The electrical resistivity p of nanocrystalline mater-
strated that the strain rate sensitivity increases dra- ials has been found to be higher than that in both
matically to about 0·04, approximately 1/4 that for coarse grained polycrystalline metals and amorphous

International Materials Reviews 1995 Vol. 40 No.2

54 Suryanarayana Nanocrystalline materials

after fracture: ductile -... ~ brittle 0

100 f- 30nm
0
0
15
0
0
C\I 0
'E 1500 80 -
0
z 0
:;;E ~
0 0
0
I
I- 40nm
E 00
C!J 10 ~ 0 D D
Z
~ ~ 60- DD
W
(!J Q. [J
DD
~ 1000 Z [J

•• •• •
CJ) [J • 50nm
0
....J C
W CD
....J W
• •
enZ
5 40 - •• • • 90nm

•• ••••
W
I-

•
500

20 -
.- • ••
'--_-'--_--1..._---&. __ .1..--_-'--_--1...--1 0 I I I

300 350 400 450 500 550 600 50 100 150 200 250
TEMPERATURE, K
TESTING TEMPERATURE, K

12 Tensile strength and elongation as function of 13 Variation of electrical resistivity with

temperature for nanocrystalline Fe-Cu-Si-B
test temperature for AissNigCe2Fe1alloy with
alloys (after Ref. 167)
20 vol.-% of nanocrystalline a-AI dispersions;
strain rate 8'3 x 10-4 S-1 (after Ref. 166)

(iii) the residual resistivity at 0 K decreases with

alloys. Wang et al.167 and Liu et al.151,16S measured p an increasing grain size and this has been
at room temperature for an amorphous alloy of correlated with the variation of interfacial
(Fe99CulhsSi9B13 composition as 102 flO em; after volume fraction with the grain size169
crystallisation to a grain size of 30 nm, p was (iv) the temperature coefficient of electrical resis-
126 flO em. A similar behaviour was reported in Ni-P tivity has been found to decrease with a
alloys.169,170 The resistivity of nanocrystalline metals decreasing grain size.169
Cu, Pd, and Fe prepared by the gas condensation All of the above conclusions are consistent with the
method, and Ni by electrodeposition 171 was also theoretical analysis of scattering of electrons by grain
measured, showing values higher than those in the boundaries. If the crystal size is smaller than the
coarse grained material of similar compositions. electron mean free path, grain boundary scattering
Table 3 summarises the few available results on the dominates and hence the electrical resistivity as well
electrical resistivity of nanocrystalline materials. as the temperature coefficient are expected to increase.
From the variation of p with temperature and grain A negative temperature coefficient of resistivity is
size, the following conclusions can be drawn: frequently observed in amorphous alloys;173 this has
(i) the resistivity is proportional to tempera- not been reported in nanocrystalline materials even
ture for different grain sizes and in a wide though it has been predicted.l?"
temperature range167,169 It has been showrr'" that the ac conductivity of
(ii) at a -constant temperature, p increases with nanocrystalline Ti02 doped with about l%Pt is
decreasing grain size (Fig. 13). For example, reversible with temperature. This reversibility has
for the Fe-Cu-Si-B nanocrystalline alloy, p is been ascribed to the Pt doping in the band gap of
126 flO cm for a grain size of 30 nm and this wide band gap (3'2 eV) semiconductor. The easy
decreases to 44 flO em at 90 nm (Ref. 167) doping possibility of nanocrystalline electroceramics

Table 3 Electrical resistivity of nanocrystalline materials

Resistivity at Temperature coefficient Residual resistivity
Grain size, room temperature, of resistivity, at 0 K,
Material nm J..lQcm K-1 JlQcm Ref_

Ni-P 11 360 1-26 x 10-3 220 169

51 220 2-00 x 10-3 90
102 200 2'35 x 10-3 62
(FeggCuhsSig813 30 126 2'01 x 10-3 50 172
50 60 1-6 X 10-3 33-4
90 44 1-6 x 10-3 17
102 93-2
(FeggMo1 hsSig813 15 198 151
195
200 63

* Amorphous,
International Materials Reviews 1995 Vol. 40 No.2
 Suryanarayana Nanocrystalline materials 55

may lead to a wide range of interesting device 500/0 in some cases) and of even the amorphous
applications. material. While most of the investigators'P'v'"
The relations between conductivity and temper- reported a non-linear (parabolic) variation of specific
ature, composition, and compaction pressure were heat with temperature, Lu et al.182 reported a linear
recently studied175 for a series of nanocrystal- variation. Hellstern et al.181 also noted that the specific
line oxide samples - LaFe03, LaCo03, and heat increase at a constant temperature was linear
Lal-xSrxFel-yCOy03' The results show that though with the reciprocal crystal size.
the conductivity is lower, the slope of the conductivity The specific heat of a material is closely related to
temperature curve is higher for the nanocrystalline its vibrational and configurational entropy, which is
materials in comparison with the coarse grained significantly affected by the nearest neighbour con-
materials. figurations. Thus, the increase in specific heat of
The magnitude of the electrical resistivity (and nanocrystalline materials has been attributed to the
hence conductivity) in composites can be changed by small crystal size (and consequent large interfacial
altering the size of the electrically conducting com- component). If this is so, grain growth should reduce
ponent. For example, by changing the size of the Fe the specific heat of the nanocrystalline material. This
particles and the volume fraction occupied by iron, was, in fact, observed.180,181
the electrical properties can be varied in a continuous
fashion in an iron-silica system. By changing the
Thermal expansion
volume fraction alone, the electrical conductivity
could be increased by 14 orders of magnitude. Measured thermal expansion coefficients (J. of nano-
The phenomenon of giant magnetoresistance crystalline Cu, Pd, Fe-B-Si, and Ni-P alloys were
almost twice the value of single crystals.9,138,170,182
(G MR) (decrease of electrical resistance of materials
when exposed to a magnetic field) has been reported For example, (J. for nanocrystalline (8 nm) Cu has
in a number of multilayer systems.l?" Giant mag- been reported to be 31 x 10- 6 K - 1 in comparison
netoresistance has been recently observed in equiaxed with 16 x 10-6 K-l for Cu single crystals." Similar
(3D) nanocrystalline materials.V'>'?? Whereas the enhancements were observed in nanocrystalline Pd,
resistance drop is only 1-20/0 in conventional coarse Ni-P, Fe7sB13Si9, and Ti02 samples. The thermal
grained materials, the drop is as large as 50-800/0 in expansion coefficients of different materials in the
the case of a nanocrystalline material. Giant mag- nanocrystalline, amorphous, and coarse grained con-
netoresistance has been shown to occur in magnet- ditions are compared in Table 5. As the crystalline
ically inhomogeneous media containing non-aligned component for a nanocrystalline material contributes
ferromagnetic entities on a microscopic scale and insignificantly to the enhancement of (J., the average
(J. of the boundary component has been proposed
scales inversely with the average particle diameter.
to be about 60 x 10-6 K -1; agreeing with direct
mcasurernents.l'" Thus, by varying the interfacial
Specific heat volume (by changing the grain size), one can
Since the specific heat of a material is directly related 'tailor' the coefficient of thermal expansion to any
to the atomic structure, measurements of the specific predetermined value.
heat as a function of temperature of nanocrystalline
materials should reveal differences in comparison with Optical properties
glassy or crystalline materials of comparable chemical
Only a limited amount of information is available on
composition. Specific heat measurements have been
the optical properties of nanocrystalline materials.
made on nanocrystalline materials prepared by gas
In spite of this, the results are interesting and show
condensation, 180 mechanical alloying.l'" and crys-
that the optical transparency can be changed by
tallisation of amorphous alloys prepared by rapid
controlling the processing parameters.
solidification methods.l'"
Figure 14 shows two ceramic Y203 samples syn-
The specific heats of different nanocrystalline
thesised by the gas phase condensation technique.
materials with their coarse grained polycrystalline
Even though both the samples have approximately
counterparts, and also with the amorphous material
the same grain and pore size (8 nm), the sample on
of the same composition, wherever available, are
the right is transparent, while the one on the left is
compared in Table 4. It may be noted that the specific
opaque. The reason for the different transparencies is
heat in the nanocrystalline state is much higher than
that there is very little aggregation of pores between
that in the coarse grained material (by as much as
the nanocrystals in the specimen on the right; accord-
ingly, the pores (which are much smaller than the
Table 4 Comparison of specific .heats
(J mol"? K-1) of nanocrystalline, amor-
Table 5 Thermal expansion coefficients (10-6 K-1)
phous, and coarse grained polycrystalline
of nanocrystalline, amorphous, and
materials measured at 250 K
coarse grained materials
Coarse grained
Condition
Material Nanocrystalline Amorphous polycrystalline Temp.
range, Coarse
Cu 26 24
Pd 37
Material K Nanocrystalline Amorphous grained Ref.
27* 24
Ni-20 at-%Pt 25 24 22 Ni-P 300-400 21-6 14·2 13·7 182
Fe7SB,3Sig 300-500 14·1 7·4 6·9 138
* Extrapolated to pure Pd based on values for amorphous Pd72Si,sFe,o.
t Measured in temperature range 310-400 K.
Cu 110-293 31 16 9

International Materials Reviews 1995 Vol. 40 No.2

56 Suryanarayana Nanocrystalline materials
14 Discs of nanocrystalline Y203 showing that
optical transparency can be controlled by
changing pore size, see text (J. C. Parker,
personal communication, January 1994)
wavelength of visible light) do not scatter light and
so the samples are fairly transparent. On the other
hand, the sample on the left has a higher degree of
aggregation (i.e. larger pores), which causes enough
scattering of light to make the sample opaque.l'"
Similarly, by controlling the cluster size in CdSe (by
chemically capping them), Steigerwald and Brus18S
were able to synthesise clusters of very narrow size
distributions and show that they indicate varying
degrees of quantum confinement and different band
gaps. For example, clusters of 1·2-1·5 nm diameter
exhibit a band gap of 3·0 eV, those with a diameter
of 3·0-3·5 nm have a band gap of 2·3 eV, while the
bulk material has a band gap of 1·8 eV.
Recently, it has been shown that visually trans-
parent compacts should be produced by pressing
16 nm diameter Si3N4 amorphous powder particles
without outgassing and at liquid nitrogen temper-
ature. This transparency continued to be exhibited
even after subsequent pressureless sintering conducted
for 1 h at 1400°C (Ref. 186). However, samples com-
pacted at room temperature showed some degree of
translucency suggesting that cooling the powder with-
out outgassing to liquid nitrogen temperature pre-
vents the particles from developing strong bonds
prema turel y.
Magnetic properties
The ferromagnetic properties of materials are influ-
enced by changes in the interatomic distances. Thus,
the saturation magnetisation M; and ferromagnetic
transition temperature of nanocrystalline materials
are considerably reduced with respect to the bulk
materials. The M, of 6 nm Fe is 130 emu g-1
(Ref. 187), while that of normal polycrystalline o-Fe
is 220 emu g-\ and that in Fe-base metallic glasses
(extrapolated to pure Fe) is 215 emu g-1. Similarly, a
reduction of the Curie temperature Tc of Ni by about
40 K was reported if the crystal size was reduced to
about 70 nm (Ref. 188). These reductions were attri-
buted to the deviation of interatomic spacings in the
interfacial regions as compared with the crystalline
component; supported by Mossbauer spectroscopy
measurements.P? In the case of nanocrystalline Er,
at the lower end of the 10-70 nm grain size, the three
International Materials Reviews 1995 Vol. 40 No.2
normally observed magnetic transitions vanished and
a low temperature transition to superparamagnetic
behaviour was detected. On the other hand, at
larger grain sizes, these three magnetic transitions
reappeared, but at different temperatures, while the
low temperature superparamagnetic behaviour was
retained. 190
Recently, attractive magnetic properties have been
reported for nanocrystalline Fe-base alloys obtained
by crystallising an amorphous alloy ribbon produced
by the rapid solidification method." This triggered a
tremendous amount of activity in this area to optimise
the soft magnetic properties of nanocrystalline alloys
for potential applications. These materials are some-
times referred to as FINEMET since they have an
ultrafine grain structure of bee «-Fe solid solution in
an amorphous matrix.
Nanocrystalline alloys to obtain the best soft mag-
netic properties are produced by the addition of Cu
and at least one element selected from the group
consisting of Nb, W, Ta, Zr, Hf, Ti, and Mo to an
Fe-base alloy having an essential composition
Fe74os-xCuxNb3Si13osB9 (Ref. 46) .. In the as rapidly
solidified condition, the alloy has an amorphous
structure. After annealing these ribbons in the temper-
ature range 500-600°C for 1 h, they crystallised to
form crystallites with a grain size of 10-12 nm dis-
persed in an amorphous matrix. These crystals have
a bee «-Fe structure in which Si, B, etc., are dissolved.
The amorphous alloy exhibits a single crystallisation
peak in the absence of Cu. Two peaks are seen when
Cu is present (Cu also increases the nucleation rate)
and the temperature difference between these two
peaks increases with increasing Cu content up to
about 1 at.-%. This peak separation helps in con-
ducting the crystallisation studies between the two
peak temperatures to obtain the desired morphology
and microstructure. Presence of Nb increases the
thermal stability of the material and further, the
growth of «-Fe crystals is retarded.
The magnetic properties of nanocrystalline mater-
ials obtained by the above method depend on the
grain size. For example, Herzer191,192 and Herzer and
Warlimont':" produced grain sizes in the range
10- 300 nm by annealing the amorphous Fe-Cu-
Nb-Si-B alloy between 500 and 900°C and found
that the coercivities He and initial permeabilities J.li
varied over several orders of magnitude. It was noted
that with increasing grain size d, the coercivity steeply
increases following a d6 power law up to 50 nm,
reaches a maximum of He ~ 30 A em -1, and then
decreases for grain sizes above 150 nm according to
the well known d -1 law for polycrystalline magnets
(Fig. 15). The initial permeability was found to vary
in a similar manner, essentially being inversely pro-
portional to coercivity. However, mechanical alloying
seems to be unsuitable for the production of soft
magnetic low coercivity alloys, because of the signifi-
cant introduction of internal strain into the highly
magnetostrictive material, which is inevitable with
this proccss.l?" Strain removal by annealing leads to
undesirable grain growth. Thus, crystallisation of
amorphous alloy ribbons seems to be the only method
presently available to synthesise nanocrystalline
alloys with attractive soft magnetic properties.
 Suryanarayana Nanocrystalline materials 57

102..---------------------, coarse grained, and nanocrystalline materials are

• The announcement in 1984 of Nd-Fe-B permanent
10
'E
-c
(J
"U
d6
6 Cl
>-
t-
s sites in the unit cell.l"? This phase has been produced
(3 10-1
a:
W 0
0 blended elemental powders and subsequent heat treat-
o
10-2 amor-
phous
x- -
10-3
1nm
GRAIN SIZE (d)
15 Grain size and coercivity for various
magnetic materials (after Ref. 191)
The magnetic microstructure of nanocrystalline Fe
was found to differ from that in polycrystalline or
amorphous Fe and iron alloys. Whereas in both
polycrystalline coarse grained and amorphous allo!s
ferromagnetic domains are separated by domain
walls, no domain structure was observed in nanocrys-
talline Fe by Bitter technique, Kerr microscopy, and
Lorentz electron microscopy techniques." In fact,
every crystallite of a nanocrystalline Fe specimen
appeared to be a single ferromagnetic domain.
The magnetic properties of nanocrystalline mater-
ials produced by crystallisation of amorphous alloys
show a good combination. They have a low coercivity
(5-10 A cm-i), high permeability (100 000), almost
zero magneto stricti on (0 to 2 x 10-6), and low core
losses (f"'oJ 200 kW m - 3) due to the high electrical
resistivity (135 Jl!l em). Further, the shape of the
hysteresis loop can be altered by magnetic field
annealing. All the above characteristics, in combin-
ation with good thermal stability, suggest that nano-
crystalline Fe-based alloys are the most promising
candidates for soft magnetic applications. The core
losses of conventional coarse grained Fe-3·5Si,
amorphous Fe-9Si-13B (at.-%), and nanocrystalline
Fe-7Zr-6B-1Cu (at.-o/o) alloys are compared in
Fig. 16 (Ref. 195). It can be clearly seen that the core
losses are considerably lower for the nanocrystalline
material. The magnetic properties of amorphous,
compared in Table 6.
magnets having a high energy product'?" led to .a
number of investigations to optimise the magnetic
properties. It is now accepted that the intrinsic mag-
0 netic properties of these materials are attributed to
Fe-Si the tetragonal hard magnetic Nd2Fe14B phase; deter-
0
mined by the electronic structure of Fe and Nd atoms
0
and the crystallographic environment of their different
0
SONi-SOFe
Cl in nanometre dimensions by mechanical alloying of
ment at 700°C for 15-30 min (Ref. 198). However,
• since the grain structure by mechanical alloying and
•• heat treatment does not exhibit any crystallographic
Permalloy
• texture (and limits the energy product), maximum
energy products of 295 kJ m -3 were obtained by die
1Jlm 1mm upsetting the mechanically alloyed material.l"? T~e
high coercivities in these materials have been attn-
buted to the fine grain sizes and these values can be
soft further enhanced by partially substituting Dy for Nd
(Ref. 200).
Another useful magnetic property that nanocom-
posites offer is called the magneto caloric effect. When
a material containing extremely small magnetic par-
ticulates in a non-magnetic or weakly magnetic matrix
is placed in a magnetic field, the magnetic spins of
the particulates tend to align with the field. This
increase in magnetic order lowers the magnetic
entropy of the spin system. If this process is performed
adiabatically (i.e. no heat is exchanged with the
surroundings), the reduction in spin entropy is offset
by an increase in lattice entropy, and the specimen
temperature will rise. This temperature rise L\T is
reversible (the specimen cools down on removal of
the magnetic field) and is known as the magneto-
caloric effect. Shull and co_workers201-204 have exten-
sively investigated this phenomenon and predictedf'"
that the magnetocaloric effect may be enhanced at
low fields and high temperatures. Shull et a1.202 have
also shown that the magnetic nanocomposite
Gd3 Ga3-2SFe1-7s 012 exhibits the magneto caloric
effect between 6 and 30 K which at a magnetic field
of 1 Tesla exceeds that of Gd3Gas012' the best
paramagnetic refrigerant in this temperature range.
Catalytic properties
Since the majority of the methods for producing bulk
nanocrystalline materials involve consolidation of fine
particles (except, for example, in the crystallisation of
rapidly solidified amorphous alloy ribbons), the total

Table 6 Magnetic properties of amorphous and nanocrystalline alloys

Thickness, Induction Bs, Coercivity He' Permeability Jl Core loss, Magnetostriction Curie temp. Tc,
Alloy Jlm T Am-' (1 kHz) kWm-3 As K
Nanocrystalline
Fens co, Nb3 Si'3'S B9 18 1·24 0'53 100000 280 +2'1 x 10-6 843
Nanocrystalline
Fe73'SCu,Nb3Si,6·sB6 18 1·18 1'1 75000 280 ",0 833
Amorphous
CoFeSiBM 18 0'53 0'32 80000 300 ",0 453
Amorphous
FeSiBM 20 1'41 6'9 6000 460 +20 x 10-6 631

International Materials Reviews 1995 Vol. 40 No.2

58 Suryanarayana Nanocrystalline materials
f=50Hz
Fe-3.5Si
Ta = 993K
'0)
~
~ 10-1
en
en
s
w
a:
o
o
(a)
10-3 '----'----II...-_-'----L_.&--.a--
0.1 0.2 0.5
Bm,T
16 Comparison of core losses of conventional coarse grained Fe-3'5Si, amorphous Fe-9Si-13B (at.-%),
and nanocrystalline Fe-7Zr-6B-1Cu (at.-%) alloys as function of a maximum induction field 8m and
b frequency f; Ta is annealing temperature (after Ref. 195)
surface area available can be accurately tailored by
controlling the porosity in the samples. One can
obtain full theoretical density to achieve the best
mechanical properties, produce a highly porous
material to obtain very large surface areas, or have
an intermediate value of porosity.
Beck and Siegcl''?" have recently shown that the
chemical reactivity of nanocrystalline Ti02 which has
been only lightly consolidated (to maximise the
porosity and hence the surface area) is significantly
higher than that in other commercially available Ti02
samples. Figure 17 shows the catalytic activity for
S removal from H2 S via decomposition for several
forms of Ti02 having either the rutile or anatase
structure with different surface areas. It can be seen
that the nanocrystalline sample is far more reactive
than any of the other samples, both initially and even
after exposure for 7 h; the activity for nanocrystalline
Ti02 is about 5 times greater than for the next most
active materials. This greatly enhanced activity was
shown to result from a combination of unique and
controllable features of the nanocrystalline material
- its high surface area combined with its rutile struc-
ture and its oxygen deficient composition. Annealing
this material in an oxygen atmosphere decreased the
number of anion vacancies and lowered the activity.
Corrosion behaviour
The corrosion behaviour of nanocrystalline materials
has received very little attention until recently. Thorpe
et al.207 studied the corrosion behaviour of nanocrys-
talline Fe32Ni36Cr14P12B6alloy obtained by crystal-
lisation of the melt spun amorphous ribbon, while
International Materials Reviews 1995 Vol. 40
103.-------.-----,r----_.__----,
~
t:
-
-
(b)
.•.....•.
.-L-L-_-'----J r I
2 20 50 100 200 500
f, kHz
Rofagha et al.208,209 studied nanocrystalline Ni-P
alloys produced by the electrodeposition technique.
The average dissolution rate of nanocrystalline Ni
was found to be higher than that for coarse grained
material. However, while coarse grained Ni suffers
excessive intergranular corrosion in acidic media,
nanocrystalline Ni exhibited more uniform corrosion
morphology.i'" Superior localised corrosion .resist-
ance in HCI was observed for sputter deposited
nanocrystalline 304 stainless steel (Fe-18Cr-8Ni) in
comparison with conventional material. This is attri-
buted to the fine grain size and homogeneity of the
°
nanocrystalline material. 21 A similar behaviour was
noted in the Fe-Ni-Cr-P-B alloy and the improve-
ment was explained in terms of Cr enrichment of the
specimen surface as a result of having more rapid
grain boundary diffusion paths.i'"
Nanocrystalline Ni-P alloys were non-passivating
in O·lM H2S04, Their enhanced dissolution rates
over those of conventional polycrystalline Ni was
explained as due to the presence of P and the
high volume fraction of grain boundaries and triple
junctions. Further, anodic polarisation of the nano-
crystalline material resulted in the formation of
non-protective surface films.
Applications
N anocrystalline materials are relatively new and it is
only during the past five years that researchers have
started exploring the many potential benefits of these
materials. Although no component made of a nano-
crystalline material is in use in any industry now,
No.2
 Suryanarayana Nanocrystalline materials 59

0.5 ,..-----------------, 800-,-----------------......,

nanD
o Nanodyne nano 6 Co 0.3 urn
13Co 0.311m
C\I
T company A o
'E700
E • company B 15Co 0.3~m
~0.4 E nanD
z
(ij
mo w 600
o
z
C>
-c
en ~ 500 6Co1~m
U5
~ 0.3
~
t-=
w
a:
~ 400 15Co 1-2~m
.
6Co 0.8~m

z
w
•.... U5
z -c
20Co 1-2~m
00.2 • catalyst A T catalyst D
ffi<i 300 •
o 6Co1-2~m
w o catalyst 8 o catalyst E •
o .•. catalyst C
I o catalyst F 200-r--f"'-,.-r---r---r-~--,r__~___r____,___r-_r__~~
o,
.....J
1000 1200 1400 1600 1800 2000 2200 2400
~ 0.1 HARDNESS, kg mm-2

18 Abrasion resistance v. Vickers hardness of

conventional and nanocrystalline WC-Co
0~~~=6===6===::&:==~~~~
o 234 5 6 7
materials: 1 kg mm-2=9·8MNm-2
McCandlish, personal communication,
(L. E.
April
TIME OF EXPOSURE, h 1994)

17 Activity of nanocrystalline Ti02 for H2S

decomposition as function of exposure time at
500°C compared with that from several
commercial Ti02 materials and a reference -
A 76 m2 9 -1 nanocrystalline rutile; B 61 m2 g-1
anatase; C 2'4 m2 9-1 rutile; D 30 m2 g-1
anatase; E20 m2 g-1 rutile; Freference alumina
(after Ref. 206)
several potential applications are suggested, based on
their special attributes.
It has been known that the fracture toughness of
ceramics can be considerably enhanced by dispersing
a second phase on a microscopic scale. Since reducing
the grain size to nanometre dimensions can provide
increased strength and hardness, it is suggested that
fabrication of micro/nanohybrids will lead to a class
of supertough and superstrong ceramics. In these
hybrids, a nanocomposite matrix is reinforced with
submicrometre sized particles - whiskers, platelets, or
long fibres - and these hybrids show enhanced frac-
ture toughness and strength up to very high temper-
atures, whereas the properties of coarse grained
composites normally degrade. Further, nanoreinforce-
ments increase creep resistance by suppressing grain
boundary sliding. Consequently, nanoreinforcements
are now being used to boost the performance of a
growing number of composites. Nanoparticles of
SiC markedly improve the fracture toughness and
hardness of MgO-SiC composites developed by
Mitsubishi Mining and Cement Co., Ltd, Japan.
Nanocrystalline fibres also are used to reinforce com-
posites. Nextel 610, a polycrystalline Al203 fibre
developed by 3M (USA) has a grain size of 100 nm
and a strength of 2·4 GN m - 2. Microstructure of the
mullite based 3M fibre is a two phase nanocomposite
of 55% mullite and 450/0Al203 by weight, with 20%
200 nm mullite needles randomly dispersed in a
matrix of 100 nm Al203 particles. The fibre retains
85% of its tensile strength at 1200°C (Ref. 55). Such
superceramics may find use in severe engineering
applications such as high efficiency gas turbines, and
in aerospace and automotive components.
Nanocrystalline WC-Co composites produced by
Nanodyne, Inc. (USA) have been shown to have
higher hardness or toughness, four times better wear
resistance (Fig. 18), and more than double lifetime in
cutting tools than conventional coarse grained com-
posites.i!' Thus, the nanocrystalline powders can be
made into wear resistant coatings or pressed and
sintered to make rigid objects. Applications for such
powders include fine drill bits for drilling holes in
printed circuit boards and rotary cutting tools
(because of the fine grain size, sharp edges, and
smooth surface finish), turbine blade coatings, and
other high wear applications.
Since the optical transparency of nanocrystalline
ceramics can be controlled by controlling the grain
size and porosity in them, such ceramics may find
application in sensor and filtration technology.
The increased diffusion rates in nanocrystalline
metals and ceramics considerably reduce the temper-
atures at which sintering can occur in these materials.
The enhanced diffusivity can be used to make oxygen
sensors and fuel cells capable of operating at much
lower temperatures than systems currently in use
today. Nanocrystalline ceramics may also be a good
candidate material for joining ceramic parts. The
usual problems in joining conventional ceramics -
requirements of high pressures and temperatures for
diffusion bonding and non-retention of strength at
elevated temperatures for reactive braze metals and
molten glass - can be overcome with nanocrystalline
ceramics because of their high diffusivity and super-
plastic forming characteristics.
The electrical and magnetic properties of nanocrys-
talline materials will probably form the basis for their
wide spread and industrial applications. The phenom-
enon of giant magnetoresistance (GMR) has been
shown to be present even in equiaxed nanocrystalline
materials. The resistance drop is as much as 50-80%
(at liquid helium temperature) whereas it is only
International Materials Reviews 1995 Vol. 40 No.2
60 Suryanarayana Nanocrystalline materials
1-2% in a Ni-Fe (Permalloy) magnetoresistive sensor
in a weak magnetic field. Thus, materials exhibiting
this large G MR can be promising candidates for the
reading heads of the next generation of information
storage systems. However, it should be noted that the
large GMR can be observed only when the applied
magnetic field is about 1 T whereas in a Permalloy it
can be observed at a field of only 1 mT.
The excellent combination of soft magnetic prop-
erties can be useful in producing tape wound cores
for common mode chokes, saturable reactors, .high
frequency transformers, and magnetic heads. Another
useful property of nanocomposites is the magneto-
caloric effect. On cycling (applying and removing the
magnetic field), the magnetocaloric effect can be used
for transferring heat from one thermal reservoir to
another. Thus, the magneto caloric effect can be used
for magnetic refrigeration (solid magnetic materials
rather than compressed gases - and also avoiding the
harmful chlorofluorocarbons). Materials being used
for this purpose include Gd3 Ga3·2SFe1.7S 012' y-Fe203
stabilised in an ion exchange resin, etc.; and these can
be used at temperatures of 65-70 K in comparison
with < 15 K for the current magnetic refrigerator
substance Gd3Ga5012'
Concluding remarks
Nanocrystalline materials are novel materials which
are not only scientifically interesting but also hold
great potential for varied applications. Their prop-
erties are different from and often superior to those
of conventional coarse grained polycrystalline
materials and also amorphous alloys of the
same composition.
It has been shown that by decreasing the grain size
to nanometre levels, traditionally soft and ductile
metals can be made very hard and strong (and brittle?)
and conventional ceramics which are brittle can be
made to deform plastically like metals. The enhanced
diffusivity in these materials results in increased solid
solubilities, and synthesis of alloy phases from nor-
mally difficult to alloy metals and also allows the
sintering of powder compacts at temperatures much
lower than those required for coarse grained poly-
crystalline materials. The electrical, optical, chemical,
and magnetic properties have also been found to be
superior in the nanocrystalline state in comparison
with the coarse grained material.
Most of the early results were based on materials
produced by the gas condensation technique, and
porosity (very often an undetermined quantity in the
early studies) was an integral part of the material.
The properties of these materials were interpreted on
the basis of a two component mixture - crystalline
and interfacial components - whereas they should
have been interpreted by taking the porosity into
account as well. In fact, reduction in Young's modulus
values.P" increased diffusivities and, in general, vari-
ations in mechanical and physical properties have
now been ascribed to the presence of porosity in these
materials.
Widespread use and search for technological appli-
cations of nanocrystalline materials requires the
availability of large (tonnage) quantities of well
International Materials Reviews 1995 Vol. 40 No.2
characterised material with reproducible properties;
and this needs to be done economically. A solution
to these barriers can be identification of well defined
applications for these nanocrystalline materials and
this can be a driver for accelerated research. In this
context, development of novel techniques is an urgent
necessity. Developments in this field thus parallel
those of rapidly solidified (RS) metals.l? Even though
the RS materials exhibited a very interesting combin-
ation of properties, industrial exploitation of these
materials had to await innovations of new techniques
- the melt spinning and planar flow casting methods.
A similar revolution can be expected in the field of
nanocrystalline materials, especially with the launch-
ing of new companies to produce large quantities of
the powders and making them easily available for
characterisation and exploitation.
Consolidation of the fine powders and the thermal
stability of the nanometre sized grains is another
concern of materials scientists. It is gratifying to note
that optimisation of process parameters to consolidate
these materials to full density has been reported
recently. 53 Although the mechanisms are not clear,
the grain growth appears to be minimal and this
augurs well for the future of nanocrystalline materials.
The majority of investigations on nanocrystalline
materials to date have been concerned with materials
having a grain size of 10-100 nm. Conventional fine
grained polycrystalline materials have grain sizes of
about 10 000 nm or larger. Hence, materials with
grain sizes of about 100-1000 nm and also those in
the 1-2 nm range should be evaluated to determine
the full range of possible properties as a function of
grain size.
The optical, electrical, and magnetic properties of
nanocrystalline materials can now be tailored by
controlling the grain size and porosity heralding in
the principles of alloy design into this new class of
materials. For this line of investigations to grow
rapidly, it is essential that improved characterisation
techniques become available so that the crystalline
and interfacial components can be fully characterised.
Additionally, characterisation of the material with
respect to porosity is important since this has been
shown to affect the diffusivity, grain growth, and
zechanical properties. Work on modelling of these
materials also has just begun.212
Two exciting possibilities using the nanocrystalline
materials are being explored now. One of these is
nanoglasses wherein nanometre sized glassy particles
are produced and these are consolidated to a bulk
shape.213-215Since glassy materials have been shown
to have properties vastly improved over their crystal-
line counterparts, nanoglasses can be expected to
exhibit properties superior to those of even nanocrys-
talline materials. Another possibility is the synthesis
of nanocomposites - even more important in cer-
amics. Here, one can disperse nanometre sized
particles inside the grains, along the grain boundaries,
or both, of coarse grained or nanocrystalline ceramics
and such materials have been shown to have an
excellent combination of strength and ductility.
This review is concerned essentially with the struc-
ture and properties of three-dimensional nanocrys-
talline materials. Exciting developments are also
 Suryanarayana Nanocrystalline materials 61

occurring in one-dimensional layered nanostructures, 7. D. TURNBULL: Metall. Trans., 1981, A12, 695-708.
8.
e.g. enhanced wear behaviour.
It is only recently that clear comparisons have been
made of nanocrystalline, conventional coarse grained
polycrystalline, and amorphous alloys (of the same 9.
10.
chemical composition) as potential engineering mater- 11.
ials. This should slowly clear the way to establish 12.
unambiguously the characteristics of nanocrystalline
materials as superior to the other two categories.
Based on what is known so far, the future for 13.
14.
nanocrystalline materials seems to have been well 15.
established. The increasing number of investigations
on nanocrystalline materials is reflected in the obser-
vation that more than 50% of the references cited in 16.
this review are published during or after 1992. 17.
Sir Alan Cottrell216 recently pointed out that 'all 18.
materials consist of electrons and nuclei ... However, 19.
nature has the ability to magnify small variations into
20.
vast differences', and nanocrystalline materials are a 21.
perfect example of how the properties can be vastly
modified by decreasing the grain size. It also appears 22.
that we are now on the verge of making true 23.
Feynman's statement that 'I can hardly doubt that 24.
when we have some control of the arrangement of 25.
things on a small scale we will get an enormously
greater range of possible properties that substances 26.
can have.,217
27.
R. P. ANDRES, R. S. AVERBACK, W. L. BROWN, L. E. BRUS,
W. A. GODDARD, III, A. KALDOR, S. G. LOUIE, M. MUSCOVITS,
P. S. PEERCY, S. J. RILEY, R. W. SIEGEL, F. SPAEPEN, and Y. WANG:
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R. BlRRINGER: Mater. Sci. Eng., 1989, A117, 33-43.
F. H. FROES and c. SURYANARAYANA:JOM, 1989,41, (6),12-17.
H. GLEITER: Prog. Mater. Sci., 1989,33, 223-315.
C. SURYANARAYANAand F. H. FROES: in 'Physical chemistry of
powder metals production and processing', (ed. W. M. Small),
279-296; 1989, Warrendale, PA, TMS.
R. W. SIEGEL: MRS Bull., 1990, 15, (10), 60-67.
R. W. SIEGEL: Ann. Rev. Mater. Sci., 1991, 21, 559-578.
R. W. SIEGEL: in 'Processing of metals and alloys', 'Materials
science and technology', Vol. 15, (ed. R. W. Cahn), 583-614;
1991, Weinheim, Germany, VCH.
C. SURYANARAYANAand F. H. FROES: Metall. Trans., 1992, A23,
1071-1081.
R. DAGANI: Chem. Eng. News, 1992,70, (47),18-24.
H. GLEITER: Nanostruetured Mater., 1992, 1, 1-19.
v. G. GRYAZNOV, M. Yu. TANAKOV, and L. I. TRUSOV: J. Mater.
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R. D. SHULL: Nanostruetured Mater., 1993, 2, 213-216.
v. G. GRYAZNOV and L. I. TRUSOV: Prog. Mater. Sci., 1993,
37, 289-401.
R. A. ANDREIVSKI: J. Mater. Sci., 1994, 29, 614-631.
R. W. SIEGEL: Nanostruetured Mater., 1994, 4, 121-138.
R. W. SIEGEL: in 'Physics of new materials', (ed. F. E. Fujita),
65-105; 1994, Berlin, Heidelberg, Springer-Verlag.
T. MUTSCHELE and R. KIRCHHEIM: Sere Metall., 1987, 21,
1101-1104.
G. PALUMBO, S. J. THORPE, and K. T. AUST: Sere Metall. Mater.,
1990, 24, 1347-1350.
C. SURYANARAYANA,D. MUKHOPADHYAY, S. N. PATANKAR, and
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Acknowledgements 28. H. GLEITER: in 'Deformation of polycrystals: Mechanisms and

microstructures', (ed. N. Hansen et al.), 15-21; 1981, Roskilde,
The author has greatly benefited from many dis- Denmark, Rise National Laboratory.
cussions with several researchers in the field. I would 29. R. BIRRINGER, H. GLEITER, H. P. KLEIN, and P. MARQUART: Phys.
Lett., 1984, 102A, 365-369.
like especially to thank Professor H. Gleiter, 30. C. C. KOCH: Nanostruetured Mater., 1993, 2, 109-129.
Universitat des Saarlandes, Saarbrucken, Germany; 31. B. H. KEAR and L. E. McCANDLISH: Nanostruetured Mater., 1993,
Dr R. W. Siegel, Argonne National Laboratory, 3,19-30.
Argonne, IL, USA; Dr R. D. Shull, National Institute 32. H. CHANG, C. J. ALSTETTER, and R. S. AVERBACK: J. Mater. Res.,

of Standards and Technology, Gaithersburg, MD, 1992, 7, 2962-2970.

33. W. CHANG, G. SKANDAN, S. C. DANFORTH, and B. H. KEAR:
USA; Professor Carl C. Koch, North Carolina State Nanostruetured Mater., 1994, 4, 507-520.
University, Raleigh, NC, USA; Professor K. Lu, 34. D. S. LASHMORE and M. P. DARIEL: in 'Encyclopedia of materials
Institute of Metal Research, Academia Sinica, science and engineering', (ed. R. W. Cahn), Suppl. Vol. 1,
Shenyang, People's Republic of China, and Professor 136-140; 1988, Oxford, Pergamon.
35. J. J. RITTER, D. B. MINOR, R. D. McMICHAEL, and R. D. SHULL:
F. H. Froes, University of Idaho, Moscow, ID, USA. in 'Nanophases and nanocrystalline structures'. (ed.
I would also like to acknowledge useful information R. D. Shull and J. M. Sanchez), 33-40; 1993, Warrendale,
from Dr J. C. Parker of Nanophase Technologies, PA, TMS.
Darien, IL, USA, and Dr L. E. McCandlish of 36. M. J. MAYO: Mater. Design, 1993, 14, 323-329.
37. R. A. ROY and R. ROY: Mater. Res. Bull., 1984, 19, 169-177.
Nanodyne Inc., New Brunswick, NJ, USA. Finally, I 38. D. A. RIGNEY: Ann. Rev. Mater. Sci., 1988, 18, 141-163.
would like to thank Mrs Denise Davis, Ms Nicole 39. A. E. BERKOWITZ and J. L. WALTER: J. Mater. Res., 1987, 2,
Wilson, and Mrs JoAnn Long for their patience in· 277-288.
typing the manuscript. 40. C.-H. CHOU and J. PHILLIPS: J. Mater. Res., 1992, 7, 2107-2113.
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