Synthesis and consolidation of boron carbide: a review

Synthesis and consolidation of boron carbide:
a review
A. K. Suri, C. Subramanian*, J. K. Sonber and T. S. R. Ch. Murthy
Published by Maney Publishing (c) IOM Communications Ltd
Boron carbide is a strategic material, finding applications in nuclear industry, armour for
personnel and vehicle safety, rocket propellant, etc. Its high hardness makes it suitable for
grinding and cutting tools, ceramic bearing, wire drawing dies, etc. Boron carbide is
commercially produced either by carbothermic reduction of boric acid in electric furnaces or
by magnesiothermy in presence of carbon. Since many specialty applications of boron carbide
require dense bodies, its densification is of great importance. Hot pressing and hot isostatic
pressing are the main processes employed for densification. In the recent past, various
researchers have made attempts to improve the existing methods and also invent new processes
for synthesis and consolidation of boron carbide. All the techniques on synthesis and
consolidation of boron carbide are discussed in detail and critically reviewed.
Keywords: Synthesis, Densification, Boron carbide, Sintering, Hard material, Neutron absorber
Introduction
Boron carbide is a suitable material for many high
performance applications due to its attractive combination of properties such as high hardness (29?1 GPa),1
low density (2?52 gm cm23),1 high melting point
(2450uC),2 high elastic modulus (448 GPa),3 chemical
inertness,2,4 high neutron absorption cross-section (600
barns),4,5 excellent thermoelectric1,4 properties, etc. It
has found application in the form of powder, sintered
product as well as thin films. Boron carbide (also known
as black diamond) is the third hardest material after
diamond and cubic boron nitride. Its outstanding
hardness makes it a suitable abrasive powder for
lapping, polishing and water jet cutting of metals and
ceramic materials.4
Tools with boron carbide coating are used for cutting
of various alloys such as brass, stainless steel, titanium
alloys, aluminium alloys, cast iron, etc.1 In sintered
form, it is used as blasting nozzles,6 ceramic bearings
and wire drawing dies due to good wear resistance.1 The
combination of low specific weight, high hardness and
impact resistance makes it a suitable material as body
and vehicle armour. Modulus to density ratio of boron
carbide is 1?86107 m, which is higher than that of the
most of the high temperature materials and hence it
could be effectively used as a strengthening medium.7
Thin films of boron carbide find application as
protective coating in electronic industries.8,9
Boron carbide is extensively used as control
rod, shielding material and as neutron detector in
nuclear reactors due to its ability to absorb neutron
without forming long lived radionuclide.7,1017 Neutron
Materials Group, Bhabha Atomic Research Centre, Mumbai 400085, India
*Corresponding author, email csubra@barc.gov.in
absorption capacity of boron carbide can be increased

by enriching B10 isotope. Composite material containing
boron carbide with good thermal conductivity and
thermal shock resistance are found suitable as first wall
material of nuclear fusion reactors.1821 Boron carbide
based composites are potential inert matrix for actinide
burning.22 Boron carbide is also used for treatment of
cancer by neutron capture therapy.23
As it is a p-type semiconductor, boron carbide is
found to be a potential candidate material for electronic
devices that can be operated at high temperatures.24,25
Owing to its high Seebeck coefficient (300 mV K21),
boron carbide is an excellent thermoelectric material.26
Boron carbide is finding new applications as thermocouple, diode and transistor devices as well. Boron
carbide is an important component for the production
of refractory and other metal borides.2729 The low
density, high stiffness and low thermal expansion
characteristics of B4C make it attractive Be/Be alloy
replacement candidate for aerospace applications.30
Thevenot has compiled a comprehensive review on
boron carbide1 in 1990, in which synthesis, consolidation, analytical characterisation, phase diagrams, crystal
structure, properties and applications are discussed. This
paper critically examines various methods of synthesis
and consolidation of boron carbide and discusses their
merits and demerits along with structure, properties and
applications.
Structure of boron carbide

The bond between B-B atoms and B-C atoms play a key
role in deciding the crystal structure and properties of
boron carbide. Knowledge of these will help us in
understanding the complexities involved in processing
and achieving the desired properties. Boron carbide is a
compositionally disordered material that exists as
2010 Institute of Materials, Minerals and Mining and ASM International
International Materials Reviews
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Published by Maney for the Institute and ASM International

DOI 10.1179/095066009X12506721665211
Suri et al.
Synthesis and consolidation of boron carbide: a review
1 Phase homogeneity range in B-C phase diagram: reprinted with permission from Elsevier, J. Less Comm.
Met., 1979, 67, Fig. 2 in p. 329
rhombohedral phase in a wide range of composition,

which extends from B10?4C (8?8 at.-%C) to B4C
(20 at.-%C).3134 Among them, B4C is superior in
properties such as hardness, thermal conductivity etc.
Since B4C is in equilibrium with free carbon and is only
boundary between BnC and BnCzC (where 4,n,10),35
synthesis of B4C without free carbon is a great challenge.
Carbon content of boron carbide greatly influences the
structure and the properties of the compound and hence
the exact knowledge of B/C ratio of the phase is very
important. But the analytical study of B-C system is
difficult due to extreme hardness and chemical stability
of boron and boron carbide phases.33 Different limits of
homogeneity range are reported by researchers at the
carbon rich side of boron carbide, corresponding to
B4?3C (18?8%C),36 B4?0C (20%C),33,34 and B3?6C
(21?6%C).37 Difficulties associated with the estimation
of free and combined carbon could be accountable for
these inconsistent results.36 B-C phase diagram showing
homogeneity range from 8?8 to 20 at.-%C, as generated
by Bouchacourt et al.34 is presented in Fig. 1.
Crystal structure
The most widely accepted crystal structure of boron
carbide is rhombohedral, consisting of 12-atom icosahedra located at the corners of the unit cell. Schematic
diagram of the structure of boron carbide is presented in
Fig. 2.38 The longest diagonal of the rhombohedral unit
cell contains three atom linear chain (C-B-C). Each end
member of the chain is bonded covalently to an atom of
three different icosahedra.31 In general, icosahedra
consist of 11 boron atoms and one carbon atom. The
locations of carbon atoms within different icosahedra
are not ordered relative to one another. The icosohedral
configuration is the result of a tendency to form threecentre covalent bonds due to deficiency of valence
electrons of boron.39 Two crystallographically inequivalent sites exist in the icosahedron. Six atoms
reside in two polar triangles at the opposite ends of the
icosahedron and the remaining six atoms occupy
equatorial sites. The atoms at polar sites are directly
linked to neighbouring icosahedra via strong two-centre
bonds along the cell edges. The atoms in equatorial sites
either bond directly to other icosahedra through threecentre bonds or to chain structures.40,41 Most of the
icosahedra have a B11C structure with the C atom placed
in a polar site, and a few percent have a B12 structure or
a B10C2 structure with the two C atoms placed in two
antipodal polar sites.41
2 Schematic diagram of structure of boron carbide

Rhombohedral unit cell, consisting of 12-atom icosahedra located at the corners and C-B-C linear chain at
the diagonal of the unit cell is shown. Within the icosahedron, six atoms reside in two polar triangles at the
opposite ends of the icosahedron and the remaining
six atoms occupy equatorial sites: reprinted with permission from the American Physical Society, Phy. Rev.
Lett., 1999, 83, (16), Fig. 1 in p. 3230
Three types of three-atom chain are envisioned: C-BC, C-B-B and B-B-B. Variation in carbon concentration
changes the distribution of three-atom chains.31 B4C
(20%C) structure consists of B11C icosahedra and C-B-C
chains. As the composition becomes rich in boron,
carbon of the B11C icosahedra is retained, while one of
the carbon atoms on the C-B-C chains is replaced by
boron. Near the composition B13C2, the structure
consists of B11C icosahedra and C-B-B chains. On
further carbon reduction, some of the B11C icosahedra
are replaced by B12 icosahedra retaining the C-B-B
chain.40,42 Carbon-boron bonds present in the three
atom chains are much stronger than boron-boron bond
in icosahedra.40 The inter-icosahedra bonds are stiffer
than the intra-icosahedra bonds.43
Conflicting views still exist concerning the nature of
site occupancies. A model based on early X-ray diffraction data44,45 proposed that the B4C composition is
made up of B12 icosahedra and C-C-C chains. However
later studies38,4042,46,47 based on improved X-ray and
neutron diffraction, nuclear magnetic resonance studies,
theoretical calculations and vibrational spectra indicate
that the structure consist of B11C icosahedra and C-B-C
chains. Even among those who favour B11C icosahedra
and CBC chain model for 20 at.-% (B4C), there is
disagreement on the structural changes that occur in
boron carbides, as the carbon content is decreased
towards 13 at.-% (B13C2). Some workers46,48 propose
that carbon atoms are removed from the icosahedra to
form B12 icosahedra, while others40,42,49 propose that
carbon atom is replaced from three atom chains. Owing
to similarity of boron and carbon in electron density and
nuclear cross-section (B11 and C12), both X-ray and
neutron diffraction studies are not very successful in
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Suri et al.
First principle molecular dynamics simulations have

revealed that the depressurisation amorphisation results
from pressure induced irreversible bending of C-B-C
chains.53
Structure sensitive properties
3 Composition of structure elements (B12 and B11C icosahedra, C-B-C and C-B-B chains) in boron carbide unit
cell and chainless unit cells with variation of C content: reprinted with permission from Elsevier, Solid
State Commun., 1992, 83, Fig. 4 in p. 850
unambiguously assigning the exact site occupancies.48

The concentration of B12 and B11C icosahedra and C-BC and C-B-B chains vary and chainless unit cells also
occur.50,51 Variation of structure elements B12, B11C, CB-C and C-B-B in boron carbide unit cell with C content
is shown in Fig. 3.51 The carbon rich limit of homogeneity range which was assumed to contain B11C
icosahedra and C-B-C chains only, also contains 19% CB-B chains. The composition of B6?5C which was
attributed to be the most representative structure (B12,
C-B-C) and used for many model calculations has been
proved to be the least defined structure containing
60%B11C and 40%B12 icosahedra. These structural
changes could also explain the abrupt decrease in
thermal conductivity between B4C to B6?5C. Saal
et al.46 have recently applied ab initio calculations to
evolve the structure of boron carbide for the entire
composition range. The enthalpy of formation and
lattice parameters were calculated and compared with
the experimental data. For carbon rich composition
(20%C), B11C-CBC structure and for 13?33%C composition B12-CBC structure were found most stable. It
suggests that carbon atom is gradually replaced by
boron in icosahedra. This result is contradictory with
other researchers who suggest that carbon atom is
replaced from chain. At boron rich end, enthalpy and
lattice parameters of B12 BVaC (Va denotes vacancy)
structure is in good agreement with the experimental
values for boron carbide having 7?14 at.-%C. Since the
enthalpy of formation of B12 BVaC is positive it is
predicted that B12 BVaCs composition cannot be
reached by boron carbide and instead, pure boron will
precipitate out, which is in agreement with experimental
phase equilibrium. Radev et al.43 have found that metal
cations can replace a part of boron atoms in icosahedra
position and thus improves the stiffness, hardness and
wear resistance of boron carbide.
Recent observations by Raman spectroscopy suggest
structural phase transformation and the formation of
localised amorphous phase which is weaker than the
original crystalline phase under conditions of loading.52
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Thermal and electrical conductivity, heat capacity,

hardness, etc. strongly depend on structure of boron
carbide and the variations are brought out in the
following lines. Lattice parameter aR of rhombohedral
unit cell decreases with increase in carbon content but
the plot is discontinuous at the composition B13C2
(13?33 at.-%C). Density of boron carbide increases
linearly with carbon content within the homogeneity
range of the phase according to the relation d
(g cm23)52?422z0?0048[C] at.-% (r50?998) with
8?8 at.-%([C]>20?0 at.-%. The number of atoms per
unit cell is exactly 15 for B4C, but increases with the
boron content and approaches 15?3 for the boron rich
limit B10C.35 Hardness of boron carbide increases with
carbon within the homogeneity range as the structure
becomes stiffer.1 Shear modulus of boron carbide
increases with carbon from 185 GPa for B6?5C (13%C)
to 198 GPa for B4?3C (20%C).54 Fracture toughness and
Youngs modulus also increases with the carbon
content.1
Heat capacity of boron carbide increases with
decrease in carbon within the homogeneity range. This
increase is due to the change in lattice vibration mode
produced by reduction of the stiffness of the three-atom
chain accompanied with a change from C-B-C to C-BB.55 Thermal conductivity of B4C (20%C) falls with
temperature in the manner characteristic of crystalline
ceramics. However, thermal conductivity of boron
carbide with low carbon is relatively less and temperature independent, a behaviour more characteristic of
amorphous materials. These differences of thermal
transport can be explained if it is assumed that, the
thermal conductivity is dominated by the transfer of
vibrational energy through the inter-icosahedral chains
rather than within the softer icosahedra. As the C-B-C
chains are inhomogeneously replaced by C-B-B chains a
transition takes place from crystal-like transport to
glass-like transport. Moreover thermal conductivity falls
because B-B bonds are much softer than C-B
bonds.40,55,56 Gilchrist et al.57 have found that thermal
conductivity of B4C falls from 29 W m21 K21 at room
temperature to 12 W m21 K21 at 1000uC. Thermal
conductivity increases when 10B isotope replaces 11B in
boron carbide. This is attributed to the increase in the
bonding energy per unit mass and the phonon velocity
as a lighter isotope is substituted for a heavier isotope.58
Electrical conductivity in boron carbide was studied
by Wood et al.49 and Matusi et al.55 Charge carriers in
boron carbide are holes which form small polarons and
move by phonon assisted hoping between carbon atoms
located at geometrically non-equivalent sites.49 The nonequivalence arises from two sources. First, carbon atoms
can be distributed among non-equivalent sites within
B11C icosahedra. Second, only a fraction of the available
positions of inter-icosahedral chain is generally filled by
C-B-C chains. The carbon rich limit (B4C) resembles an
ideal crystal and therefore has the lowest electrical
conductivity.55 Electrical conductivity increases with
temperature, which is the sign of behaviour of a
semiconductor. Density of small polaron holes is
Suri et al.
independent of temperature but the mobility of holes

increases with temperature. Within the homogeneity
range, charge carrier density and electrical conductivity
decreases with increase in carbon content. The temperature dependence of electrical conductivity is essentially
independent of carbon concentration.49
Irradiation response
Neutron irradiation of boron carbide results in extensive
intergranular cracking due to the formation of helium
bubble as per the following equation5961
7
10
1
4
:
5 B z0 n ?3 Li z2 He z2 6
MeV
(1)
Formation of these cracks, which prevent heat conduction and the atomic disorder resulting in high phonon
dispersion, decrease the thermal conductivity during
irradiation.59 The anisotropic precipitation of helium
not only changes the microstructure but degrades the
mechanical and physical properties as well. When grain
boundary cracking occurs, a large amount of trapped
helium is released simultaneously with the occurrence of
bulk swelling.62,63 Considerable amount of tritium is
produced in B4C by fast neutron irradiation, which is
retained up to 700uC even on annealing and is released
only at temperature higher than 900uC.62,64 Copeland
et al.65,66 have reported that irradiation of boron carbide
with neutron causes lattice strains due to the formation
of lithium and helium as reaction product as well as
some atomic displacements. Inui et al.67 have reported
that a complete crystalline to amorphous transition
takes place by electron irradiation with energy .2 MeV
and at temperature ,163 K. They also found that the
amorphous boron carbide remains in amorphous state
on annealing at 1273 K. They suggested a possibility,
that, in boron carbide, the individual B12 icosahedra
themselves are not destroyed by electron irradiation but
their regular spatial arrangement in the B12C3 lattice is
perturbed and is gradually put in disorder with
increasing electron dosage, resulting in an amorphous
state.67 Froment et al.59 have noticed that boron rich
B8C is more resistant to radiation damage compared to
B4C and hence becomes a possible candidate for new
absorbing materials. 11B4C is found to be very stable
after fast neutron irradiation in reactors. Dimensional
changes and thermal conductivity of 11B4C are substantially smaller than that of 10B4C.68
Synthesis of boron carbide

Boron carbide was discovered in nineteenth century as a
byproduct of reaction involving metal borides. The
purity of boron carbide produced by early researchers
was less than 75% and in 1933, Ridgway69 claimed to
have produced crystalline B4C of 90% purity by
carbothermic process. Lipp4 has presented a review of
boron carbide production, properties and applications
in 1965. Spohn70 has also mentioned the synthesis routes
for boron carbide production and its uses in his article.
In this section, different routes for B4C synthesis will be
discussed. The methods of boron carbide synthesis are
classified as:
(i) carbothermic reduction
(ii) magnesiothermic reduction
(iii) synthesis from elements
(iv) vapour phase reactions
(v) synthesis from polymer precursors
(vi) liquid phase reactions

(vii) ion beam synthesis
(viii) VLS growth.
Carbothermic reduction of boric acid

Carbon reduction of boric acid and boron trioxide is the
commercial method for the production of boron
carbide. The overall carbothermic reduction reaction
can be presented as follows
4H3 BO3 z7C?B4 Cz6COz6H2 O
(2)
This reaction proceeds in the following three steps70

4H3 BO3 ?2B2 O3 z6H2 O
(3)
B2 O3 z3CO?2Bz3CO2
(4)
4BzC?B4 C
(5)
Boric acid on heating converts to B2O3 by releasing

water. The reduction of B2O3 with carbon monoxide
becomes thermodynamically feasible above 1400uC. The
furnace temperature is usually maintained at .2000uC
to enhance the rate of overall reaction. The process is
highly endothermic, needing 16 800 kJ mol21 B4C.71
Three types of electric heating furnaces, namely
tubular, electric arc and Acheson type (graphite rod as
resistance element) are used for the production of boron
carbide. Tubular electric furnaces using graphite tubes
as heating element are in use for carrying out reactions
for scientific study only. These furnaces are limited in
size, dependent on the size of the availability of graphite
tubes. Hence large scale production is not feasible using
tubular furnaces.
Arc furnace process
Electric arc furnace process for making boron carbide

has been patented by Schroll et al.72 in the year 1939,
wherein the mixture of boric acid and petroleum coke is
melted in an arc furnace followed by crushing the
resultant product and mixing it with substantially the
same quantity of boric acid and remelting the mixture a
second time. The design and operation of the electric arc
furnace for the large scale production of boron carbide
has been explained by Scott.73 In the arc furnace
process, the temperatures are generally very high due
to localised electric arcs, which are responsible for heavy
loss of boron by evaporation of its oxides. Moreover the
product obtained is chunks of melted boron carbide,
which needs subsequent laborious crushing and grinding
operations.
Acheson type furnace
Acheson type furnaces, where a graphite rod is used as

heating element, surrounding which the reactants are
charged is also used for production of boron carbide.
Early patents by Ridgway69,74 give the details of the
furnace and the process. Operational details of the
Acheson furnace are explained below. Partially reacted
charge from the previous run is assembled around the
new graphite heating rod. Above this, the new charge
mixture consisting of boric acid and carbon is added. On
heating, the reaction initiates near the graphite rod and
carbon dioxide escapes to the atmosphere through the
charge above. As the reaction proceeds, the charge gets
heated by conduction as well as by the heat of the
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4 Thermogravimetric analysis plot of carbothermic reduction of boric acid80
escaping CO. Boric acid initially loses its water and

converts to B2O3. On further heating, B2O3 melts and
forms a glassy film preventing the escape of CO from the
reduction zone. The product gases form bubbles and
grow in size near or just above the reaction site and as
the pressure increases, the bubbles burst pushing the
charge above. During these bursts some of the partially
reacted charge is thrown out of the furnace and boron
also escapes to the atmosphere in the form of boron
oxide vapours. These bubble bursts and evaporation
losses affect the efficiency of the process considerably.
After completion of the run, the top is broken open
and the boron carbide surrounding the graphite rod is
manually collected. Operator experience plays a major
role in identifying the completely reacted product so that
less amount of oxides enter the boron carbide portion.
The reacted product is crushed in jaw crushers and
further ground to finer size. Ground powder is washed
in water and leached in acid to remove the contamination due to grinding media and also the accompanying
unreduced or partially reduced oxides of boron from the
reduced product. In each run, only a small portion of the
charge gets converted to carbide and the balance
material is recirculated in further runs. Some quantity
of boron oxides escapes to the atmosphere along with
carbon monoxide. Hence in this process, conversion in
each run is low and boron loss is high. As the raw
materials used are cheap and the process is simple, this
process has been adopted for commercial production.
Though the method of raw material charging and
collection of reacted product could be different in arc
furnace and Acheson processes, the reaction sequence is
very similar.
As temperature is an important process parameter in
carbothermic reduction process and the heat transfer
plays an important role in the formation of boron
carbide Rao et al.75,76 have devised a method of core
temperature measurement in boron carbide manufacturing process. They have analysed the heat transfer
process inside the reactor and the effect of it on the
formation of boron carbide based on the recorded data.
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Process kinetics
Kinetics of the reaction and also the product quality is

strongly influenced by porosity of the charge, type of
carbon used for reduction, rate of heating and the final
core temperature. Process kinetics, influence of process
parameters and the means of improving the product
quality and conversion efficiency have been investigated
by many researchers. Petroleum coke is found to be a
better reducing agent than graphite, charcoal and
activated charcoal.77 Boric acid to coke ratio of 3?3
3?5 is found optimum and at higher ratios, though boron
carbide free of carbon could be obtained, recovery is
poor. Alizadeh et al.78 have optimised the boron oxide/
carbon (petroleum coke) ratio to yield boron carbide
with low (0?65%) carbon. Addition of small amount of
sodium chloride (1?5%) is found to be effective in
increasing the yield.71,79 Start of formation of B4C has
been noticed by Subramanian et al.80 at 1200uC by
thermogravimetric studies on the reduction of boric acid
by petroleum coke in vacuum. Figure 480 shows the
weight change of the charge with temperature up to
1400uC. Formation of boron carbide by carbothermic
reduction is highly dependent on the phase changes of
reactant boron oxide from solid to liquid to gaseous
boron sub oxides and the effect of reaction environment
(heating rate and ultimate temperature).81 Slow heating
(,100 K s21) of the charge results in the formation of
boron carbide by a nucleation and growth mechanism as
the reaction proceeds through a liquid boron oxide path.
Intermediate heating rates (103 to 105 K s21) result in
the formation of both large and small crystallites,
indicating the reaction of carbon with both liquid boron
oxide and gaseous boron suboxides. Rapid heating rates
(.105 K s21) result in smaller crystallite size, indicating
the occurrence of reaction through gaseous boron
suboxides.
Dacic et al.82 have studied the thermodynamics of gas
phase carbothermic reduction of boron anhydride. B2O2
and BO are formed by carbothermic reduction of B2O3
according to reactions (6) and (7) and then reduced to B
or B4C.
Suri et al.
5 Effect of feed composition and temperature on calculated product composition in carbothermic reduction of
1 mol B2O3 (l) as per Dacic et al.:82 reprinted with permission from Elsevier, J. Alloys Compd, 2006, 413,
Fig. 2 in p. 200
B2 O3 zC?B2 O2 zCO
(6)
B2 O3 zC?2BOzCO
(7)
The effect of the feed composition and temperature on

the product composition in carbothermic reduction is
shown in Fig. 5.82 A decrease in the partial pressure of
CO facilitates synthesis of B4C by boosting the
generation of B2O2 and BO.
Production of boron carbide by carbothermy has been
essentially a batch process. Tumanov83 has reported the
development of a continuous process for the production
of boron carbide, by direct inductive heating of a charge
made of boron oxide and carbon black. An alternate
reduction method patented by Rafaniello84 explains the
process for producing submicrometre size boron carbide
powders. The type of carbon used, method of preparation of the charge mixture and the fast heating rates (70
10 000uC min21) are responsible in obtaining fine
powders. Weimer et al.85,86 have designed a vertical
apparatus comprising of cooled reactant transport
member, reaction chamber, heating element and cooling
chamber for the continuous production of submicrometre B4C powder. Modelling of carbothermic reduction process for the production of boron carbide has not
been attempted by anybody so far.
Preparation of dense articles need fine boron carbide
powders in micrometre size. The product of conventional process has to undergo series of size reduction
processes to obtain such powders. Such grinding operations contaminate the product necessitating additional
purification steps. Availability of nanosized powders will
not only avoid the grinding operations but also reduce
the temperature of densification substantially.
Nanocrystalline boron carbide
Preparation of nanosized particles of boron carbide is of

recent interest. B4C particles in the nanosize range
(260 nm) can be prepared by reduction of B2O3 vapour
by carbon black at 1350uC.87 Above this temperature,
yield is low due to loss of B2O3 from reaction mixture.
Addition of cobalt as catalyst is found to be helpful in
yield of nanorods.88 Ma et al.89 have prepared high

purity boron carbide nanowires from mixed powder
precursor containing boron, boron oxide and carbon
black. The mixture is heated quickly to 1650uC and held
at that temperature for 2 h under flowing argon.
Vapours of B2O3, B2O2 and CO react to form B4C solid
nanowires with a mean diameter of y50 nm and lengths
of several hundreds of micrometres (Fig. 6).89 Large
scale boron carbide nanowires of size 80100 nm
diameter and 510 mm in length have been synthesised
using B/B2O3/C powder precursor under argon flow at
1100uC.90 Xu et al.91 have synthesised nanostructures of
boron carbide by heating B2O3 powder to 1950uC in a
graphite crucible covered with a boron nitride disc.
Majority of the crystallites deposited on boron nitride
disc show a belt-like morphology with average width
and length of about 510 and 50100 mm, while the
thickness was in the nanoscale range (20100 nm). A
number of perfect icosahedral quasicrystal particles
(Fig. 7a)91 and multiply twinned particles normally in
rod shape were also present (Fig. 7b).91 These particles
have very large sizes (y20 mm). Thus it was found that
when the reaction takes place in gas phase or the
product could be nanocrystalline B4C. Presence of some
catalyst also promotes the formation of nanopowders.
Although carbothermic reduction results in lower
yield due to loss of boron in the form of its oxides, this
route is adopted as commercial method mainly because
of the simple equipments and cheap raw materials which
make this route the most economical. This route is not
only useful for commercial powder production but also
for the production of nanocrystalline B4C. Details of
experimental studies on carbothermic reduction, giving
charge composition, processing conditions and product
quality of boron carbide obtained by various researchers
are summarised in Table 1.69,72,7779,8385,92
Magnesiothermic reduction of B2O3

An alternate method for the production of boron
carbide is by magnesiothermic reduction of boron
anhydride in presence of carbon as given below
2B2 O3 z6MgzC?B4 Cz6MgO
(8)
This reaction takes place in two steps:

step 1
2B2 O3 z6Mg?4Bz6MgO
(9)
step 2
4BzC?B4 C
(10)
The reaction is exothermic (DH51812 kJ mol21) in

nature. As the vapour pressure of magnesium is high
at the reaction temperature of .1000uC, a cover gas
such as argon or hydrogen is used and also the system
pressure maintained high. The products of the reaction
are processed by aqueous methods to remove magnesium oxide from boron carbide. The carbide is still
contaminated with magnesium borides formed as stable
compounds. This reduction technique yields very fine
amorphous powder, which is well suited for use in the
fabrication of sintered products. One method of
controlling the temperature and the particle size of the
product is by choosing the right size of the reactants.
Post reductive sintering at temperatures 200300uC
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a,b long straight segments; c,d curly tufts

6 Image (SEM) of high purity single crystalline boron carbide nanowires formed by thermal evaporation of B/B2O3/C powder precursor at 1650uC under argon atmosphere:89 reprinted with permission from Elsevier, Chem. Phy. Lett., 2002,
364, Fig. 1 in p. 315
higher than the reaction temperature increases the

particle size of the product. Seeding of the charge with
a small quantity (12%) of boron carbide has been found
to increase the growth of B4C particles and the yield
significantly.93
An early patent by Gray94 explains the process for the
production of boron carbide powders by magnesiothermic
reduction of B2O3 or alkali Na2B4O7 in presence of carbon
7 a perfect icosahedral B4C particle and b rod shaped

twinned particles by carbothermic reduction of B2O3
(scale bars: 10 mm):91 reprinted with permission from
American Chemical Society, J. Phys. Chem. B, 2004,
108B, Fig. 4 in p. 7653
10
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at 16501700uC. Addition of metallic sulphates as catalyst

has been found to reduce the reaction temperature to
700uC.95 The heat of magnesiothermic reaction is sufficient
enough for self high temperature synthesis route.
Formation of ultra fine B4C powder from the stoichiometric mixture of H3BO3, Mg and C by self-propagating
high temperature synthesis (SHS) has been studied by
Zhang et al.96 and Khanra et al.95,97 The ignition
temperature of this mixture was found to be 670uC by
thermal analysis method. Mechanical alloying has also
been utilised as a means of synthesising submicrometre
B4C particles by magnesiothermic reduction.98
Wang et al.99 have studied the synthesis of B4C fibre
MgO composites by combustion of B2O3zMgzCfibre
samples in an argon filled chamber. The degree of
conversion was influenced by pressure of the ambient
argon gas which influences the evaporation of magnesium and thereby the combustion temperature and
conversion. Calcium can also be used as reductant in
place of Mg. Berchman et al.100 have recently reported
synthesis of boron carbide powder by calciothermic
reduction of borax (Na2B4O7) or B2O3 in presence of
carbon at 1000uC in argon.
Though boron carbide has been produced by magnesiothermic reduction and used for applications defined
by its high calorific value, the high cost of magnesium
will soon make this process obsolete for regular
production. Table 29399 presents a summary of studies
on synthesis of boron carbide by magnesiothermic
reduction.
Synthesis from elements

Synthesis of boron carbide from its elements is
considered uneconomical due to the high cost of
Suri et al.
Table 1 Charge composition, processing conditions and product quality on synthesis of boron carbide by carbothermic
reduction*
Serial
no.
Reactants
Process parameters
Product quality
Ref. (year)
2400uC
Crystalline B4C 90% pure
69 (1933)
Boron carbide with 15%C
72 (1939)
Crystalline B4C 2530 mm
79 (2004)
Crystalline B4C 2530 mm
78 (2006)
B2O3zPC
H3BO3zcharcoal
Batch (resistance
furnace)
Batch (arc furnace)
H3BO3zPC
Batch
B2O3zPC/carbon active
Batch
B2O3 and carbon
Batch
Melting temperature
of charge
1470uC; HR:
100uC min21, 5 h, Ar
1470uC; HR: 100u min21,
15 h, Ar
1800uC, 20300 min, Ar
H3BO3zPC
Batch (Acheson)
.2000uC
Continuous (induction 2227uC

B2O3zcarbon black/
graphite/activated charcoal heating)
Continuous
1820uC; HR: 900uC s21,
H3BO3zVulcan XC-72
carbon black
3 min, Ar
2000uC; HR: 1000
H3BO3zacetylene carbon
black
2000uC s21, 3 min, Ar
1580uC; HR: 755uC s21,
H3BO3zactivated carbon
3 min, Ar
Continuous
1950uC, Ar
H3BO3zcorn starch
Process type
Boric oxide and carbon
Crystalline B4C without free 92 (2004)

carbon
Partially sintered and dense 77 (1986)
product B4C conversion:
6973%
Crystalline B4C
83 (1979)
Equiaxed crystals of 0.5 mm 84 (1989)
Submicrometre particles
0.10.2 mm
Submicrometre and uniform
sized crystals
0.1 mm
0.020.1 mm
1850uC, Ar
85 (1992)
*PC: petroleum coke, HR: heating rate.
elemental boron and hence employed for specialised

applications101,102 only, such as B10 enriched or very
pure boron carbide. For synthesis of enriched boron
carbide, carbothermic reduction is not suitable due to
loss of boron as well as boron hold-up in the furnace
and hence this process is the only suitable economical
method. Although formation of boron carbide from its
elements is thermodynamically possible at room temperature, the heat of reaction (239 kJ mol21) is not
sufficient to carry out in a self-sustaining fashion.103
Formation of boron carbide layer slows down further
reaction, due to slow diffusion of reacting species
through this layer, thus necessitating high temperature
and longer duration for complete conversion of the
elements into the compound. For synthesis from
elements, boron and carbon are thoroughly mixed to
form uniform powder mixture, which is then pelletised
and reacted at high temperatures of .1500uC in vacuum
or inert atmosphere. The partially sintered pellet of
boron carbide is then crushed and ground to get fine
B4C powder. To achieve a high purity product of B4C,
high purity elemental boron powder produced by fused
salt electrolytic process104,105 is often used.
Mechanical alloying of BC mixtures followed by

heat treatment is one of the methods being investigated
for the synthesis of boron carbide. Room temperature
milling is carried out in planetary mills for prolonged
duration to activate the powders and the alloyed mixture
is then annealed to obtain boron carbide. Spark plasma
synthesis is a new technique, in which a pulsed high dc
current is passed through the charge mixture contained
in a cavity along with the application of uniaxial
pressure. In this process, the start and completion of
formation has been noted at 1000 and 1200uC respectively. Combination of mechanical alloying followed by
spark plasma sintering has been studied by Hian et al.106
to obtain 95% pure boron carbide.
Shock wave technique has also been attempted for
boron carbide synthesis from amorphous boron and
graphite powder107 using trimethyl enetrinitramine as
detonator. The resultant product exhibited several
different morphologies, such as filaments, distorted
ellipsoid, plates and polyhedron particles of nanosize.
In this technique reactants are kept inside a steel
container which is placed in plastic tube. A detonator
is placed between container and the plastic tube.
Table 2 Charge composition, processing

magnesiothermic reduction*
product
conditions
and
quality
on
synthesis
of
boron
carbide
by
Serial
no.
Reactants
Process type
Process parameters
Quality of B4C
Ref. (year)
1
2
3
4
B2O3zMgzC
B2O3zMgzC
B2O3zMgzC
B2O3zMgzC
Tubular furnace
SHS
Batch
Mechanical alloying
Fine powder
Fine powder 98% pure
Boron: 74.6% Carbon: 25.2%
93
96
95
88
5
6
7
B2O3zMgzCFibre
H3BO3zMgzC
Na2B4O7zMgzC
Combustion synthesis
SHS
Continuous
9501200uC, H2
700uC, Ar, 1 h catalyst: K2SO4

Rotation speed: 200 rev min21
Ball to load ratio: 5 : 1 72 h
Ar
670uC, Ar
16501700uC, H2
B4C fibrezMgO composites

824 mm size, 8% free carbon
Powder boron: 77.5% Carbon:
21.3%
99 (1994)
97 (2005)
94 (1958)
(2002)
(2003)
(1967)
(2006)
*SHS: self-propagating high temperature synthesis.
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Initiation of explosive detonation was carried out by an

electric detonator. After the shock treatments, samples
were recovered by shaving off the container with a lathe.
In this technique very high heating and cooling rates are
achieved along with high pressure. The chemical
reaction is completed in micro to milliseconds. Hence
this is suitable for the preparation of crystals of various
morphology and non-equilibrium phases which are hard
to be produced in thermal equilibrium conditions.
A few attempts have been noticed on the preparation
of nanostructure boron carbide from its elements. Wei
et al.108 have prepared boron carbide nanorods by
reacting carbon nanotubes (CNT) with boron powder at
1150uC under argon atmosphere. Chen et al.109 have
synthesised boron carbide nanoparticles by reacting
multiwall CNT with magnesium diboride at 1150uC for
3 h in vacuum. At this temperature, magnesium diboride
decomposes and gives elemental boron. Recently Chang
et al.110 has attempted the preparation of boron carbide
nanoparticles (200 nm) by direct reaction between
amorphous boron and amorphous carbon at 1550uC.
The crystals obtained had a high density twin structures
with variation of B/C ratio from particle to particle.
Table 3106108,110113 gives a comparative summary of
studies reported on the synthesis of B4C from its
elements. Synthesis of boron carbide from its elements
is suitable for the production of pure B4C. Though the
cost of production is high due to the high cost of
elemental boron, for specialised applications such as in
nuclear industry this method is preferred.
Vapour phase reaction

Synthesis of boron carbide by carrying out reaction
between boron and carbon containing gaseous species
has been extensively studied. This method is gainfully
adopted for the formation of boron carbide coatings and
synthesis of powders and whiskers in submicrometre
sizes. Boron halides such as BCl3, BBr3 and BI3 are
suitable boron source but BCl3 is the most preferred due
to its ready availability and low cost. Apart from
halides, borane (B6H6) and oxide (B2O3) are also useful
boron sources. Hydrocarbon gases such as CH4, C2H4,
C2H6, C2H2 and carbon tetra chloride (CCl4) are
employed as carbon source. Synthesis of boron carbide
takes place in the reaction chamber, which is kept at a
desired temperature, pressure and atmosphere.

Generally hydrogen is present in the atmosphere, which
reacts with the halogen forming hydrogen chloride as
per the following reactions
4BCl3 zCCl4 z8H2 ?B4 Cz16HCl
(11)
4BCl3 zCz6H2 ?B4 Cz12HCl
(12)
4BCl3 zCH4 z4H2 ?B4 Cz12HCl
(13)
The flow of reactants and other process parameters

decide the composition and structure of the product
formed.
One such set-up for vapour phase reaction is
described by Bourdeau in his patent.114 The process of
producing boron carbide by reacting a halide of boron
in vapour phase with hydrocarbon in the temperature
range 15002500uC has been explained. Clifton et al.115
described a process for producing boron carbide
whiskers in the size range of 0?05 to 0?25 mm by the
reaction of B2O3 vapours with the hydrocarbon gas
between 700 and 1600uC. James et al.116 have patented a
process for the production of boron carbide whiskers
and the use of catalytic elements to enhance the yield
of the gas phase reaction process. Dieter et al.117 have
described a process for the production of boron carbide
powder of fine size with a surface area >100 m2 g21.
MacKinnon et al.118 have reported that when boron
trichloride is reacted with CH4H2 mixture in a radio
frequency argon plasma, boron carbides of variable B/C
ratios are obtained as submicrometre powders, the
product stoichiometry depending on the reactant
composition.
Chemical vapour deposition (CVD)
Deposition of different types of boron carbide films

(B13C2, B4C, metastable phases, highly strained structures, etc.) by CVD techniques has been reported in
literature. The actual deposition is controlled by mass
transfer and surface kinetics, which affects the stoichiometry and properties of the boron carbide phases grown.
Graphite, single crystal silicon, carbon fibre and boron
are the substrate materials used for thin film synthesis.
Generally the process is carried out in vacuum in the
Table 3 Charge composition, processing conditions and product quality on synthesis of boron carbide from elements*
Serial
no.
Reactants
Process type
Process parameters
Product quality
Ref. (year)
Solid state thermal

reaction
Hot pressing
1550uC, 4 h, Ar
BzC
MAzannealing
BzC
MAzspark plasma
sintering
Amor. boronzcarbon
black
Spark plasma synthesis
.1200uC, 10 min
Amor. boronzgraphite
Shock wave technique
Amor. boronzCNT
Solid state reaction
Detonator: trimethyl
enetrinitramine Detonation
velocity: 6.4 km s21
1150uC, Ar
Nanoparticles
15350 nm
Articles of near
theoretical density
B4C with some
unknown peaks
95% dense pellet
of high purity boron
carbide
Sintered B4C,
disordered fine
crystalline
Nanosized particles
of crystalline B4C
110 (2007)
Amor. boronzAmor.
carbon
BzC
18002200uC, 34 h
MA for 90 h Annealing
at 1200uC
1650uC, 16 min
*Amor.: amorphous; MA: mechanical alloying; CNT: carbon nanotube.
12
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Straight nanorods
111 (1975)
112 (2006)
106 (2004)
113 (2005)
107 (1996)
108 (2002)
Suri et al.
temperature range of 450 to 1450uC. Substrate temperature has strong influence on the process and product
quality. High substrate temperature results in poor
adhesion whereas deposition rate is low at low
temperature. Amorphous boron carbide coating can be
obtained at a low temperature of y500uC whereas
crystalline film is obtained at higher temperatures
.1100uC. Amorphous boron carbide coatings on SiC
have been obtained by CVD from CH4BCl3H2Ar
mixtures at low temperature (9001050uC) and reduced
pressure (10 kPa).119
Preparation of boron carbide fibres by the reaction of
boron halides with woven cloth of carbonisable material
in hydrogen atmosphere has been patented by Wainer
et al.120,121 Jaziehpour et al.122 have prepared boron
carbide nanorods on graphite substrate at 1400uC by
CVD using charge mixture of boron oxide, activated
carbon and sodium chloride. Shu-Fang et al.123 have
grown novel boron carbide nanoropes by CVD using ocarborane (C2H12B10) as precursor and ferrocene
(C10H10Fe) as catalyst. Karaman et al.124 have studied
the kinetics of CVD of B4C on tungsten substrate using
BCl3CH4H2 gas mixture. They proposed that two
major reactions take place during the process
1
BCl3 gz CH4 gzH2 g?
4
1
B4 C sz3HCl g
4
BCl3 gzH2 g?BHCl2 gzHCl g
(14)
(15)
Reaction rate of boron carbide formation is lower than

that of dichloroborane formation over the entire range
of temperatures (1000 to 1400uC) studied. Schouler
et al.125 obtained BCx (x>3) phase having whisker-like
morphology by reacting BCl3 and B6H6 at 1000uC on
quartz substrate in presence of hydrogen and nickel.
Sezer and Brand126 have written a comprehensive review
on CVD of boron carbide. The mechanical, thermal and
electrical properties of CVD boron carbides are comparable to other important refractory materials and promise
a wide range of application areas, particularly in the
nuclear industry. They have also discussed the thermodynamic modelling used by many researchers and have
concluded that the process takes place far from
equilibrium and that, thermodynamic modelling is not
sufficient to represent experimental deposition conditions. Table 4114118,127147 presents a summary of
studies reported on vapour phase reaction synthesis of
boron carbide.
Many modifications such as laser CVD (LCVD),
plasma enhanced CVD (PECVD), hot filament CVD
(HFCVD), etc. have been tested for the formation of
boron carbide films.
Laser CVD
In this technique the energy of a laser beam is used to
heat the surface of a substrate to the temperature
required for chemical deposition. It allows superb
spatial resolution (y5 mm) because the chemical reactions are restricted to the heated zone created by the
focused laser spot, in contrast to the traditional CVD
furnace which heats the entire surface of the substrate.148 Laser CVD results in deposits with high purity,
high degree of crystallinity, low porosity, excellent
mechanical properties and thermal stability. These

attributes are the result of deposition occurring one
atom at a time. Deposition rates in LCVD techniques
are orders of magnitude higher than that in traditional
CVD. The deposition rate and surface microstructure
strongly depend on laser power and hydrogen content in
the gas phase.127 Control of laser power density allows
for codeposition of r-(B4C) and disordered graphite,
which can be beneficial for tailoring the thermal and
electronic properties of boron carbide.128 The reactive
atmosphere composition is the most important parameter in laser CVD. When the relative amount of
carbon to boron in the gas phase is high, a disordered
graphitic phase is deposited along with boron carbide
and when the carbon is low, tetragonal and metastable
boron rich phase, B25C is codeposited with boron
carbide.129 Patterned deposits can be obtained by direct
writing process, in which a pattern of thin lines
deposited on the substrate by moving the substrate
perpendicular to the axis of the laser beam. Fibre
depositions are also possible by moving away the
substrate parallel to the laser beam axis at a rate equal
to the deposition rate of the fibre. Direct writing and
fibre growth methods can be combined to produce threedimensional structures.148
Plasma enhanced CVD
In PECVD chemical reaction takes place after the
creation of plasma of reacting gases. The plasma is
generally created by radio frequency (ac) or dc discharge
between two electrodes, the space between which is filled
with the reacting gases. The necessary energy for the
chemical reaction is not introduced by heating the whole
reaction chamber but just by heated gas or plasma. The
deposition takes place at lower temperature as compared
to traditional CVD. Since the formation of the reactive
and energetic species in the gas phase occurs by collision
in the gas phase, the substrate can be maintained at a
low temperature. Hence, film formation can occur on
substrates at a lower temperature than is possible in the
conventional CVD process, which is a major advantage
of PECVD.149
Plasma enhanced CVD has been used by many
researchers for the fabrication of boron carbide (B-C)
diodes which could accurately detect single neutrons,
giving very high efficiencies. These diodes have been
used to fabricate the first real time, solid state neutron
detectors which are more efficient and reliable than any
other neutron detecting semiconductor reported to
date.150 Lee et al.25,151 have fabricated photoactive p-n
hetrojunction diode by PECVD of boron carbide thin
films from nido-pentaborane (B5H9) and methane(CH4)
on Si (111). A B5C/Si(111) hetrojunction diode by a
synchrotron radiation induced decomposition of orthocarborane fabricated by Byun et al.152 has been found to
be comparable with PECVD diodes. Hwang et al.153
have successfully fabricated and tested a boron carbide/
boron diode on aluminium substrates and a boron
carbide/boron
junction
field
affect
transistor.
Robertson et al.154 have fabricated real time solid
state neutron detector by PECVD using closo-1,2dicarbadodecaborane. Adenwalla et al.155 have reported
the fabrication and characterisation of boron carbide/
silicon carbide hetrojunction diodes by PECVD. The
literature is abundant on various possible combinations
2010
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of source, method of fabrication, uses, etc. and only a

few examples are given above.
Hot filament CVD
Hot filament CVD is an attractive technique due to its
simple design and its amenability to fundamental
chemical kinetic modelling in understanding the process

chemistry. Hot filament CVD systems are based on
thermal catalytic cracking of the precursors on the
surface of a high temperature filament usually ranging
from 1000 to 2500uC. The substrate materials are usually
heated by radiation from the hot filament and the
Table 4 Charge composition, processing conditions and product quality on vapour phase synthesis of boron carbide*
Serial
no.
1
2
Reactants
Process parameters
Product quality
Ref. (year)
Vapour phase
reaction
Vapour phase
reaction
BCl3zCH4
1900uC; vacuum:
5 mm of Hg
Exothermic reaction
and needs to be
ignited only by spark
plug
1075uC, 18 h
Boron carbide crystals
114 (1967)
Amor. porous boron

carbide powder of
submicrometre size
117 (1977)
Whiskers length:
0.54 inch; diameter:
0.050.25 mm
Whiskers length: 50 mm;
diameter: 10 mm
Submicrometre size powder
115 (1970)
118 (1975)
Crystalline B4C coating
130 (1996)
Metastable phases, highly

strained microstructure
131,132 (1989)
Pure long crystalline B4C;

hardness: 412.7 GPa
Amor. coating
133 (1965)
134 (1981)
B4C coating
135 (1968)
B4C coating (B: 74 to 76%)

specific gravity of 2.32 gm cm23
Amor. boron carbide
Crystalline B4C
136 (1974)
137 (2006)
124 (2006)
Crystalline B4C
128 (1999)
Crystalline B4C
138 (1996)
Ultra fine and crystalline B4C
139 (1990)
Adherent, crystalline B4C,

1522%C
Crystalline B4C and B25C
127 (2002)
B2H6zC2H2
Vapour phase
reaction
B2O3zCH4
BCl3zCH4zH2
BCl3zCH4zH2
Vapour phase
reaction
RF plasma
assisted synthesis
CVD
CVD
BCl3zCH4zH2
CVD
BCl3zCCl4zH2
CVD
BCl3zC3H8zH2
10
CVD
BCl3zCH4zH2
11
CVD
BCl3zCH4zH2
12
13
CVD
CVD
BCl3zCH4zH2
BCl3zCH4zH2
14
Laser CVD
BCl3zCH4zH2
15
Laser CVD
BCl3zCH4zH2
16
Laser CVD
17
Laser CVD
BCl3zCH4/
C2H4zH2
BCl3zC2H4
18
Laser CVD
BCl3zCH4zH2
19
Pulsed laser
induced CVD
Plasma enhanced
CVD
Microwave plasma
assisted CVD
C6H6zBCl3
Process
20
21
22
BCl3zCH4zH2
1650uC, 5 h; vacuum
catalyst: VCl4
Ar plasma
1350uC; Sub.: carbon
fibre
11271227uC; Sub.:
boron coated Mo,
vacuum
1550uC, 45 h, Sub.:
graphite
8501000uC, 36 h;
Sub.: graphite cloth;
vacuum: 1525 torr
1300uC,6 h; Sub.:
graphite; vacuum:
10 mm of Hg
1300uC, 3 h; Sub.:
tungsten, graphite
8001050uC, vacuum
10001400uC; Sub.:
tungsten
Laser: CO2; Sub.:
fused silica; Ar pressure:
atmospheric
Laser: CO2; Sub.:
fused silica
Laser: CO2
Laser: CO2; Sub.: fused
silica, Ar
Laser: CO2; Sub.: fused
silica,
Nd:YAG laser
C2B10H12
(orthocarborane)
BBr3zCH4zH2
11001200uC; Sub.:
Si (100)
500600uC; Sub.:
graphite
BCl3zCH4
500600uC; Sub.: Si
(100), ArzH2
1600uC, 36 h BCl3:
615 mL min21; CH4:
25 mL min21; H2:
500 mL min21
1000 to 1400uC; Sub.:
graphite, vacuum
2100uC (filament)
450uC (substrate);
Sub.: Si (100), vacuum
Room temperature;
Sub.: Si (100)
23
Supersonic plasma
jet CVD
Thermal CVD
BCl3zCH4zH2
24
Hot wall CVD
BCl3zCH4zH2
25
Hot filament activated

CVD
BCl3zCH4zH2
26
Electron beam
evaporation
BzC
2010
VOL
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129 (1997)
14 to 33 nm B4C crystals
encapsulated in graphite
B4C nanowires diameter:
18150 nm; length: 13 mm
Amor. boron carbide large
composition range (0 to
40 at.-%C
Microcrystalline film hardness:
2232 GPa
Various composition between
B4C and B13C2
140 (1999)
Crystalline B13C2, long columnar

grains
Amor. boron carbide, high purity
and good adhesion
145 (1998)
Thin films of crystalline boron

carbide
*CVD: chemical vapour deposition; Sub.: substrate; Amor.: amorphous; RF: radio frequency.
14
116 (1969)
141 (1999)
142 (1990)
143 (1998)
144 (1992)
146 (1994)
147 (2008)
Suri et al.
substrate surface temperature is usually ,500uC.146 The

deposition is carried out under high vacuum conditions
to avoid oxygen contamination of the boron carbide
phase. Deshpande et al.146 have obtained adhesive
coating of boron carbide on silicon substrate and the
wear resistance of the coated surface was found to be
extremely high when tested using a WC/Co ball as the
pin.
Vapour phase synthesis methods are suitable for thin
film coating of boron carbide and preparation of fine
powder, fibres, whiskers, etc. However the powders
produced by this process are generally nonstoichiometric and not suitable for fabrication of dense
products. These methods are best suited for laboratory
studies.
Synthesis from polymer precursors

As an alternative to high temperature reaction techniques, there is great interest in development of polymer
precursors to produce ceramic materials at lower temperatures. Some of the boron loaded organic compounds such as carborane (C2BnHnz2), triphenylborane,
polyvinyl pentaborane and borazines on pyrolysis yield
B4C. Generally this process is carried out in the temperature range 10001500uC in vacuum or inert atmosphere. A US patent156 describes a process for making a
free flowing boron carbide powder from boric acid and
sugar. The mixture dissolved in ethylene glycol is dried
in air at 180uC and then heated in hydrogen at 700uC.
This reaction product is ground and fired at 1700uC for
7 h to yield fine boron carbide powder. Mondal et al.157
describe a low temperature synthetic route in which a
polymeric precursor is synthesised by the reaction of
boric acid and polyvinyl alcohol, which on pyrolysis at
400/800uC gives crystalline boron carbide. Sinha et al.158
have presented a process in which, a stable gel is formed
from aqueous solution of boric acid and citric acid. This
gel is further processed to yield a precursor which on
heating under vacuum to 1450uC produces B4C.
Economy et al.159 have prepared boron carbide fibre
by heating amine treated B2O3 fibre in inert atmosphere at 20002350uC. Cihangir et al.160 have developed a method based on sulphuric acid dehydration of
sugar to synthesise a precursor material which on
heating to temperature between 1400 and 1600uC
yields crystallised B4C and B4C/SiC composites.
Table 5156159,161167 gives the comparative summary of
studies reported on the synthesis of B4C using polymer
precursors.
Liquid phase reaction

Synthesis of ultra fine boron carbide powder using liquid
precursors has been attempted by a few. This method is
also known as solvothermal process or coreduction
method. Unlike conventional methods, this can be
operated at much lower temperatures to yield boron
carbide of desired properties. Shi et al.168 have studied
the formation of ultra fine boron carbide powders by
coreduction of boron tri bromide and carbon tetrachloride using sodium as reducing agent as per the
following reaction
4BBr3 zCCl4 z16Na?B4 Cz4NaClz12NaBr
(16)
The reaction was carried out in an autoclave at 450uC.

B4C crystals obtained were composed of uniform
spherical (80 nm dia) and rod-like (200 nm diameter
and 2?5 mm long) particles (Fig. 8).168 Gu et al.169 have
observed the formation of nanocrystalline B4C by
solvothermal reduction of CCl4 using lithium in
presence of amorphous boron powder in an autoclave
at 600uC.
4BzCCl4 z4Li?B4 Cz4LiCl
(17)
Hexagonal B4C crystals with a particle size of approximately 1540 nm diameters were obtained.
Ion beam synthesis

Boron carbide thin films can be grown by direct
deposition of Bz and Cz ions. In this process,
parameters such as ion energy, ion flux ratio of different
Table 5 Charge composition, processing conditions and product quality on synthesis of boron carbide using polymer
precursor
Serial
no.
Polymer precursors
Temperature,
uC
Atmosphere
Holding
time, h Product quality
Ref. (year)
1
2
1300
1500
Argon
Vacuum
5
2.5
161 (2009)
162 (2006)
400800
Air
1450
Vacuum
1400
1500
Ar
Crystalline
Crystalline, micrometre
sized, free carbon: 2.38%
Crystalline (orthorhombic),
boric acid as impurity
Crystalline, free carbon
11.1 wt-%
B/C composite containing
crystalline B4C
Crystalline
1000
Ar
165 (1988)
1450
1400
Ar
Ar
48
2
Amorphous, black and

shiny
crystalline
Crystalline
1215
Vacuum
,1
1700
H2
20002350
Inert atmosphere
3
4
5
6
7
8
9
10
11
Polyvinyl borate
Reaction product of H3BO3
and citric acid
and polyvinyl alcohol
and citric acid
Solution product of H3BO3
and glucose
Condensation product of H3BO3
and 2-hydroxy benzyl alcohol (HBA)
Polyvinyl pentaborane
Condensation product of H3BO3

and 1,2,3 propanetriol
Ethyl Decaborane (C2H5B10H13)
Solution product of H3BO3, sugar

and ethylene glycol
Amine treated B2O3 fibre
157 (2005)
158 (2002)
163 (2002)
164 (1999)
165 (1988)
166 (1985)
Crystalline B4C coating

(0.005 inch) on tungsten
wire
Crystalline B4C powder
156 (1975)
Boron carbide fibre
159 (1974)
2010
167 (1969)
VOL
55
NO
15
Suri et al.
8 Image (TEM) of B4C rod-like particles (200 nm diameter

and 2?5 mm long) prepared at 450uC by sodium reduction of BBr3 and CCl4:168 reprinted with permission
from Elsevier, Solid State Commun., 2003, 128,
Fig. 3(c) in p. 7
ion species and the substrate temperature, which can be

independently controlled, could be advantageously used
for obtaining the preferred composition and nature of
the boron carbide film. Ronning et al.170 have grown
thin film of boron carbide (BxC) by direct ion beam
deposition on silicon using an ion energy of 100 eV at
room temperature. Todorovic et al.171 have observed the
formation of amorphous boron carbide (BxC) by
bombardment of Bz and B3z ions on fullerene. Beam
energies were in the range of 15 keV for Bz to 45 keV
for B3z and fluences were between 261014 and
261016 cm22.
Vapour liquid solid (VLS) growth

Boron carbide whiskers can be grown by carbothermal
VLS growth mechanism. This mechanism involves the
transport of boron and carbon as gas phase species to a
liquid catalyst metal (Fe, Ni or Co) in which whisker
constituents get dissolved. When the catalyst becomes
supersaturated with boron and carbon, boron carbide
whiskers precipitate out of the metal droplets. Carlsson
et al.172 have prepared B4C whiskers and platelets using
this technique. B2O3 and carbon black were used as
source of boron and carbon respectively. NaCl and Co
were added to facilitate the growth of whiskers. B2O3
reacts with NaCl to form BCl, which along with carbon
dissolve in liquid cobalt and then precipitate as boron
carbide whiskers. Rao et al.173 have studied the
formation of boron carbide whiskers using K2CO3 and
NiCl2 as a low melting liquid and catalyst to enhance the
formation of B4C whiskers and platelets. An et al.174
have used gallium oxide and sodium chloride to prepare
boron carbide nanobelts having a length of around 1 to
10 mm and thickness of around 80 to 150 nm, which is
shown in Fig. 9.174 Ma et al.175 have investigated the
growth of boron carbide nanowires by the addition of
iron to the precursor mixture containing carbon, boron
and boron trioxide. This resulted in reduction of
diameter of nanowires from 50200 nm to 1030 nm.
Scanning electron micrograph of the nanowires is shown
in Fig. 10.175 A comparative study of various methods
of boron carbide synthesis is presented in Table 6.
Some of the attempts to produce boron carbide
cannot fall into any of the classifications discussed
16
2010
VOL
55
NO
9 Boron carbide nanobelts prepared by VLS growth from

charge of boron oxide, activated carbon, gallium oxide
and sodium chloride at 1400uC:174 reprinted with permission from Trans. Tech. Publications, Key Eng.
Mater., 2007, 336338, (III), Fig. 1 in p. 2167
above. Thakkar et al.176 have synthesised high purity

ultra fine boron carbide powders by reacting B2O3 with
methane in a non transferred arc dc thermal plasma
reactor. A recent article177 explains the process of
making boron carbidecarbon eutectic containing
39 wt-%C by melting B2CN in graphite crucible at
2600uC.
Boron carbide powder is either utilised directly or
consolidated to dense bodies. Various methods of
densification, the mechanisms involved and the product
quality are discussed in the following pages. Densification techniques can be broadly classified as pressureless sintering and pressurised sintering. Atmospheric/
reaction/microwave and thermal plasma sintering are
termed as pressureless sintering techniques. The nuances
of densification of powder compacts, complexity and the
reasons for incomplete densification by pressureless
sintering are discussed in detail by Lange.178
Pressurised sintering can be classified as solid and gas
compaction methods. Solid compaction methods are hot
10 Boron carbide nanowires prepared by VLS growth

with help of iron addition:175 reprinted with permission
from American Chemical Society, Chem. Mater., 2002,
14, Fig. 5(b) in p. 4405
Suri et al.
pressing, spark plasma sintering and super high pressure

sintering. Gas compaction methods are hot isostatic
pressing and high pressure gas reaction sintering.
Densification of boron carbide

In spite of its high temperature strength, application of
B4C is rather limited, in real life, due to difficulties in
densification, low fracture toughness and low oxidation
resistance beyond 1000uC. Consolidation of B4C is
complicated due to its high melting point, low selfdiffusion coefficient and high vapour pressure. Very high
sintering temperatures are required for densification due
to the presence of predominantly covalent bonds in B4C.
Boron carbide particles generally have a thin coating of
surface oxide layer which hinders the densifications
process. At temperatures ,2000uC, surface diffusion
and evaporation condensation mechanism occur, which
results in mass transfer without densification. Densification is achieved only at temperatures .2000uC, by
grain boundary and volume diffusion mechanisms. At
higher temperature exaggerated grain growth also takes
place resulting in poor mechanical properties. One more
observation at temperatures .2150uC is volatilisation of
non-stoichiometric boron carbide, leaving minute carbon behind at the grain boundaries.
Dole et al.179 have observed the microstructure of B4C
compacts fired above 2000uC to be highly porous
interconnected structure with clusters of grains connected by small neck like regions and separated by large,
channelled porosity. Grabchuk et al.180182 have found
that shrinkage starts at 1500uC, recrystallisation above
1800uC and rapid grain growth above 2200uC. At
temperatures above 2250uC, the sintered body contains
,5% residual porosity. Lee et al.183,184 have observed
the start of densification at 1800uC, rapid increase in
densification 18702010uC and a slow down in densification rate 20102140uC. The surge in densification
18702010uC is attributed to the presence of oxide layer
which helps in precipitation of B4C through liquid B2O3
or due to evaporation and condensation of rapidly
evolving oxide gases (BO and CO). Slower densification
at temperatures above 2010uC is attributed to evaporation and condensation of B4C. Figure 11183 shows the
changes in weight, dimension and grain size while
sintering of boron carbide.
Densification of boron carbide without deterioration
of mechanical properties can be achieved either by using
a suitable sintering aid and/or applying the external
pressure (e.g. hot pressing, hot isostatic pressing).
Selection of the additive and the method of consolidation are generally dictated by the end use of the product
and the properties that are required. The additive by
itself or due to in situ reaction with boron carbide would
form a non volatile second phase aiding in densification
and property enhancement. Hence, selection of the
additive should be directed towards the formation of a
suitable structure providing the correct properties for
use. Recent or advanced techniques such as microwave/
spark plasma sintering, explosive compaction, etc. help
to obtain dense products without microstructural
coarsening. These techniques are presently limited to
laboratory scale only. Detailed literature survey on
pressureless sintering with or without sintering aids, hot
pressing, hot isostatic pressing, spark plasma and
microwave sintering of boron carbide are presented in
the following sessions.
Pressureless sintering
Pressureless sintering is a simple and economic process
to produce dense compacts. This operation is carried out
in two steps. In the first step green compacts with
Table 6 Comparison of boron carbide synthesis methods*

Method
Boron source
Carbon source
Advantage
Disadvantage
Carbothermic reduction
H3BO3 or B2O3
PC, graphite,
activated carbon
Cheap raw material,

suitable for commercial
production
Magnesiothermic reduction B2O3 or Na2B4O7
PC, graphite,
activated carbon
Synthesis from elements
Boron
PC, graphite,
activated carbon
Vapour phase synthesis
BCl3, BBr3, BI3,

B6H6, B2O3
CH4, C2H4, C2H6,

C2H2, CCl4
Fine powder, exothermic

reaction, suitable for SHS
process
No loss of boron, good
control over purity and
carbon content of product
Suitable for thin films, fine
powder, fibers, whiskers
High boron losses,

obtained in lump form,
need grinding for powder
production
Product contaminated
with Mg, MgB2
Synthesis from polymer

precursors
Liquid phase reaction
Ion beam synthesis

Vapour liquid solid growth
High cost of elemental

boron
Difficult to produce B4C

powder suitable for
densification, not amenable
for large scale production
Polyvinyl alcohol,
Low temperature process High free carbon content,
Boric acid, B2O3,
polyvinyl pentaborane, citric acid, hydroxyl
still in laboratory stage
polyvinyl borate, ethyl benzyl alcohol,
decaborane
sugar, ethylene
glycol
CCl4
Low temperature process, Need of reactive metal
BBr3, boron
suitable for nanoparticles such as Na or Li, new
method of synthesis
Only for thin films, of
Boron
Carbon
Suitable for BxC
academic interest only
Carbon black
Suitable for whisker
Need of molten metal
B2O3
catalyst, of academic
interest only
*PC: petroleum coke; SHS: self-propagating high temperature synthesis.
2010
VOL
55
NO
17
Suri et al.
11 Sintering of boron carbide compact: change in weight, dimension, grain size and coefcient of thermal expansion up
to 2300uC:183 reprinted with permission from Wiley-Blackwell, J. Am. Ceram. Soc., 2003, 86, (9), Fig. 8 in p. 1472
sufficient handling strength are prepared by uniaxial die

compaction. These green pellets are then fired at chosen
high temperatures in controlled atmosphere. A recently
developed new technique, combustion driven compact
process, yields much higher green density and strength
than the normal die compaction.185 In this process, high
pressure generated by ignition of a combustion gas
mixture which raises the pressure in the chamber
dramatically in a very short period of time and pushes
down the top ram on the powder at an extremely high
speed realising the compaction.
Sintering of B4C powder compacts is commonly
performed in an inert gas medium. But the application
of vacuum helps in evaporation of the surface oxide
layer and also prevents further oxidation, there by
promoting the sintering mechanisms. Removal of the
oxide layer by heating in a reducing atmosphere before
sintering also has a similar effect. Literature data on
pressureless sintering of boron carbide and the product
evaluation are presented in Table 7.179,183,186204
Increase in particle surface area (9 to 17 m2 g21) and
sintering temperature (2100 to 2190uC) give higher
densities (56 to 71% TD).187 Densities of .90% TD
are achieved by sintering at a temperature of .2200uC
with particles close to or ,1 mm size. Grain coarsening
is the common feature in compacts with high densities
obtained by pressureless sintering.191,193 Microstructures
of samples with 87 and 93% TD, obtained by pressureless sintering of 0?8 mm median diameter powders at
2300 and 2375uC are presented in Fig. 12.193 Grain sizes
are in the range 40100 mm indicating large grain
growth. Surface to surface mass transport which is
active at temperatures below which densification can
proceed is responsible for the coarsening process. At
higher temperatures, vapour phase diffusion of boron
carbide is the important transport mechanism for
coarsening. Rapid heating is helpful in achieving higher
densities with fine microstructure, as the compacts can
be heated to a temperature where densification can take
place before the microstructure becomes highly coarsened.179,183,188,205 Appearance of twins in the grains is
characteristic of boron carbide. These twins slowly
18
2010
VOL
55
NO
vanish during high temperature annealing. Vickers

hardness and flexural strength of the pressureless
sintered boron carbide samples are in the range 18
24 GPa and 120200 MPa respectively, which are lower
than theoretical values. One can conclude that, with
pure B4C, a densification .90% TD is possible only at
very high sintering temperatures of y2300uC. Such
compacts have a coarse grained microstructure of
12 Microstructure of pressureless sintered boron carbide

(0?8 mm) at a 2300uC and b 2375uC showing grains in
range 40100 mm indicating large grain growth:193 reprinted with permission from Elsevier, Ceram. Int.,
2006, 32, Fig. 2(b) and (g) in p. 230231
B4C
B4Cz3 wt-%C (phenolic resin)
B4C
B4C
B4Cz3 wt-%C
B4Cz5 wt-%C
B4Cz7.5 wt-%C
B4Cz9 wt-%C
B4C
B4Cz4%C
B4Cz4%B
10
B4Cz4%SiC
B4Cz4%TiB2
B4C
B4Cz1 wt-%C
B4Cz3 wt-%C
B4Cz5 wt-%ZrO2
B4Cz5 wt-%TiB2
B4C
B4Cz5 wt-%TiB2
B4Cz10 wt-%TiB2
B4Cz15 wt-%TiB2
B4Cz20 wt-%TiB2
B4Cz25 wt-%TiB2
B4Cz30 wt-%TiB2
B4C
B4C
B4Cz6 wt-%C
B4C
B4Cz3 wt-%C (phenolic resin)
B4C
B4Cz(polycarbosilanez
phenolic resin510%)
D5051.33
SS: 6.64
B/C53.8 to 3.9
D5050.5 to 2
(Acheson)
B: 78%; C: 19.05%; O: 0.5%
D50<3
SS: 18.8; O: 1.23%; N: 0.4%
Carbon black: D50520 nm;
SS: 120
SiC (SS): 11.59
TiB2: D90<4
SS: 2.53
B/C: 4.32
D50(0.84
SS: 18.8
B/C53.76
2250uC,
2250uC,
2375uC,
2325uC,
2325uC,
2275uC,
2375uC,
2150uC,
2200uC,
2250uC,
2250uC,
2250uC,
2250uC,
2250uC,
2250uC,
2250uC,
2250uC,
2250uC
2250uC
h
h
h
h
h
h
h,Ar
h, Ar
h,Ar
2 h, Ar
2 h, Ar
1 h, vacuum
1 h, vacuum
1 h, vacuum
1 h, vacuum
1 h, vacuum
vacuum
1
1
1
1
1
1
2
2
2
2175uC, 15 min, Ar
Starck make B/C53.7 to 3.8;

D5050.8; SS: 1520
B4C
2170 to 2230uC, 15 min,

Ar
2190uC, 1 h, Ar (up to
2000uC in vacuum)
2250uC
2300uC
2300uC
2150uC, 15 min, Ar
FC: 24.9; D5052.0 to 10.5
B4C
D5051
SS: 12
D50(1
SS: 22
D50,5
SS: 10.5
Processing conditions
Starting powder details
Material composition, wt-%
Serial
no.
90.8
95.4
93
91
90
93
82
86
90
93
96
96
98
98.5
78.6
82.5
92
93
89
86
95.5
97.7
87.0
91.392.7
98.498.6
65%
7072%
.95%
78
96
95
9495
94.095.6
Sintered
density
rth, %
B4C:
B4C:
B4C:
B4C:
B4C:
B4C:
B4C:
B4C:
B4C:
2010
10
14
17
50120
y20
y10
y5
y15
30
B4C: 28
B4C: 50
B4C: 13
SiC: ,3
B4C: 2.58 3.11
B4C: 2.262.4
Coarse
Coarse
Fine
B4C: 6
B4C: 4
B4C: 105
B4C: 28
Microstructure,
mm
Table 7 Powder details, sintering parameters and characteristics of sintered boron carbide by pressureless sintering*
22
26
29
31
29
26
23
32
1923
2125
2425
1921
1921
1820
12.025.5
Vickers
hardness,
GPa
2.2
2.6
2.8
2.85
2.9
3.05
3.4
3.2
2.913.19
KIC,
MPa m1/2
220
260
290
360
320
280
270
174
350
353
160180
Flexural
strength,
MPa
213 (2008)
193 (2006)
192 (2005)
191 (2003)
183 (2003)
190 (1987)
189 (1981)
179 (1989)
188 (2004)
186 (1988)
Ref. (year)
Suri et al.
VOL
55
NO
19
20
2010
VOL
55
NO
15
14
13
12
11
Serial
no.
B4Cz10
B4Cz20
B4Cz30
B4Cz40
wt-%TiO2
wt-%TiO2
wt-%TiO2
wt-%TiO2
B4Cz5 wt-%TiO2
B4Cz10 wt-%TiO2
B4Cz15 wt-%TiO2
B4Cz20 wt-%TiO2
B4C
B4C
B4C
B4Cz5 wt-%ZrO2
B4Cz10 wt-%ZrO2
B4Cz15 wt-%ZrO2
B4Cz20 wt-%ZrO2
B4Cz25 wt-%ZrO2
B4Cz30 wt-%ZrO2
B4C
B4Cz5 wt-%Ti
B4Cz10 wt-%Ti
B4Cz15 wt-%Ti
B4Cz20 wt-%Ti
B4Cz20 wt-% talc

B4Cz25 wt-% talc
B4Cz30 wt-% talc
B4C
B4Cz2.5 wt-%ZrO2
B4Cz5 wt-%ZrO2
B4Cz10 wt-%ZrO2
B4Cz15 wt-%ZrO2
B4Cz20 wt-%ZrO2
B4Cz25 wt-%ZrO2
B4Cz30 wt-%ZrO2
B4C
B4C
B4Cz5 wt-% talc
B4Cz10 wt-% talc
B4Cz15 wt-% talc
Table 7 Continued
D5055 to 7
SS: 17
TiO2: D100(2
D50 ,1
SS: 917
TiO2: D50,2 (up to
1500uC: vacuum)
D5051
SS: 14
ZrO2z3 wt-%Y2O3
D5050.8
SS: 16
B4C: D50<1
B/C54.09
ZrO2 reactor grade
D5051.33
SS: 6.64
B/C53.8 to 3.9
Talc: 26.62%Al2O3,
47.78%SiO2, 25.6%MgO
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
h,
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
inert
inert
inert
vacuum
inert
inert
inert
inert
inert
2160uC, 1 h, Ar
2160uC, 1 h, Ar
2160uC, 1 h, Ar
2160uC, 1 h, Ar
2190uC, 1 h, Ar (up
to 1500uC: vacuum)
2050uC,
2150uC,
2150uC,
2150uC,
2150uC,
2150uC,
2150uC,
2150uC,
2190uC,
2190uC,
2190uC,
2190uC,
2190uC,
2150uC,
2150uC,
2150uC,
2275uC,
2050uC,
2150uC,
2150uC,
2150uC,
2150uC,
73
75
80
93
72
77
88
95
71
72
75
79
86
97
97
97
98
62
67
73
78
86
92
95
98
86.63
89.56
93.86
95.3
95.5
93.08
95.82
92.34
74
78
82
85
90
Sintered
density
rth, %
ZrB2
ZrB2
ZrB2
ZrB2
ZrB2
ZrB2
ZrB2
ZrB2
B4C: 10
TiB2: 5
B4C: 10
TiB2: 57
B4C
B4C,
B4C,
B4C,
B4C,
B4C,
B4C,
B4C,
B4C,
Microstructure,
mm
19
22
25
27
28
29
27
26
26
27
23
26.85
31.68
31.18
30.19
30.95
31.71
31.07
18
21
22
23
25
Vickers
hardness,
GPa
2.0
2.1
2.2
2.6
2.9
3.0
3.0
3.1
2.4
2.6
2.7
1.9
2.0
2.1
2.2
2.3
KIC,
MPa m1/2
200
300
330
400
200
300
350
420
120
190
200
205
210
220
235
260
340
50
Flexural
strength,
MPa
187 (2000)
197 (1999)
196 (2006)
221 (2008)
195 (2006)
Ref. (year)
Suri et al.
D100: submicrometre
SS: 15.0
O2: 0.98%; N2: 0.32%
FC: 0.64%
TiC: D5051.5
O: 0.53%; N: 0.10%
D5050.08
SS: 16.1
B/C: 3.57
BeC: submicrometre
B4C: D5059; SiC: D5052.5
D5050.43
SS: 15.3
O2: 2% max.
Fe: 140 ppm
Al: 50 ppm
CrB2: D5053.5
B4C
B4Cz22 vol.-%ZrO2
B4Cz28 vol.-%TiO2
B4Cz8 vol.-%Y2O3
B4C
B4Cz1 wt-%Al2O3
B4Cz2 wt-%Al2O3
B4Cz3 wt-%Al2O3
B4Cz4 wt-%Al2O3
B4Cz5 wt-%Al2O3
B4Cz1.5%TiC
B4Cz1.5%TiC
B4Cz3.0%TiC
B4Cz4.5%TiC
B4Cz6.0%TiC
B4C
B4Cz1.0 wt-%BeC
B4Cz1.0 wt-%BeC
B4Cz1.0 wt-%BeC
B4Cz10 wt-%SiCz3 wt-%Al
B4Cz25 wt-%CrB2
B4Cz27.9 wt-%CrB2
B4Cz25 wt-%CrB2
B4Cz27.9 wt-%CrB2
17
18
20
2010
D50<0.9 (B/C53.9)
(1 wt-%O2 and 0.4% N2)
Al2O3: 99.99% pure
h,
h,
h,
h,
h,
Ar
Ar
Ar
Ar
Ar
15 min,
15 min,
15 min,
15 min,
10 min,
1 h, Ar
2
2
2
2
2
2030uC, 1 h, Ar
2030uC, 1 h, Ar
2015uC, 1 h, Ar
2260uC,
2130uC,
2230uC,
2280uC,
2150uC,
2015uC,
2175uC,
2200uC,
2200uC,
2200uC,
2200uC,
ArN2
ArN2
ArN2
ArN2
Ar
2150uC, 15 min, Ar
*FC: free carbon in B4C; D50: mean particle diameter, mm; SS: specific surface area, m2 g21.
21
22
19
B4Cz0 to 30 wt-%TiO2z1
to 6 wt-%C
16
2180uC, 2 h, Ar
19002050uC, 1 h, Ar
B4C: D5050.639
SS: 19.8
Purity: 99.89%
TiO2 and C: submicrometre
D5051.6 (B/C53.9)
O2: 1.7%
ZrO2: submicrometre
TiO2: submicrometre
Y2O3: submicrometre
Serial
no.
Table 7 Continued
98.1
96.3
93.3
B4C: 2050
B4C: 20
CrB2: 20
B4C: 100150
8.92
12, TiB2
18, TiB2
11, TiB2, C
8, TiB2, C
5, TiB2, C
B4C: 7.07
71.9
80.1
85.5
94.0
94
90.2
3.63
5.35
B4C:
B4C:
B4C:
B4C:
B4C:
B4C:
B4C:
B4C:
TiB2: 610
B4C: 222
Microstructure,
mm
85
92
93
96
88
86
96.3
94.9
96.6
98.1
98.4
83
98
98
97.5
Up to 99%
Sintered
density
rth, %
31
29
28
28
2731
2833
2730
Vickers
hardness,
GPa
3.7
5.8
2.7
2.6
4.0
3.7
3.23.71
KIC,
MPa m1/2
525
108
400
404
286
266
350
375
180
350513
Flexural
strength,
MPa
202 (1982)
203, 204 (2002,
2002)
201 (1977)
200 (1998)
199 (1992)
198 (2007)
216 (1996)
Ref. (year)
Suri et al.
VOL
55
NO
21
Suri et al.
13 a TEM image of pressureless sintered boron carbide with 7?9 wt-% phenolic resin at 2250uC showing graphite crystal
at triple points and b high resolution TEM image of grain boundary of same sample:209 reprinted with permission
from the Ceramic Society of Japan, J. Ceram. Soc. Jpn, 2004, 112, (5), Figs. 2 and 3 in p. S400
y50 mm, high amount of intragranular porosity and

poor flexural strength (y200 MPa).
Carbon as sinter additive
Various sinter additives have been tested to increase the

rate of densification, control grain growth and improve
mechanical properties of boron carbide. Carbon has
been found to be very effective, primarily in reducing the
oxide layer of the boron carbide powders, there by
promoting sintering and hindering grain growth.
Carbon, well distributed between the particles reacts
with B2O3 coating according to the reaction
2B2 O3 z6C?B4 Cz6CO
(18)
Removal of oxide layer allows direct contact between

B4C particles, permitting sintering to initiate at significantly lower temperature (y1350uC). In addition,
carbon at the grain boundaries enhances diffusion,
facilitating accelerated solid state sintering. Various
types of carbon such as petroleum coke, carbon black,
graphite, glucose and phenolic resin (e.g. phenol
formaldehyde) can be used as sintering aid. If carbon
in solid form such as coke, graphite or carbon black is
chosen, it is mandatory that very fine size is used and the
mixing carried out thoroughly, in mixtures such as
planetary mill/attritor to form an intimate contact such
as a fine coating on boron carbide particles. An additive
such as phenol formaldehyde resin plays two roles;
namely as binder while cold pressing and as carbon
precursor which is uniformly distributed on the surface
of the grains. Any carbon which is not consumed by the
reduction reaction is left in the compact as excess
carbon. High densities of 98?65% TD with a fine grain
size of 2?34 mm have been achieved by the addition of
3%C in the form of phenolic resin.183 Compacts
exhibiting a finer, less faceted grain structure with
smaller and more uniformly distributed pores were
prepared by the addition of 6 wt-%C (in the form of a
thermoset resin).179 Carbon addition inhibits the coarsening process, thereby preventing the formation of
large unsinterable pores. As a result, carbon doped B4C
22
2010
VOL
55
NO
undergoes normal sintering and nearly full density can

be achieved. Much of the carbon remains in the B4C
microstructure as graphite particle. Phenolic resin as
carbon addition is found better than carbon black and
glucose.191 With 3 and 5 wt-%C the density obtained
was 92 and 93% TD respectively. With higher amounts
of carbon (>7?5%C), a reversal in densification was
observed. Yin et al.206 have studied the sintering kinetics
of pure and carbon doped boron carbide with 0?42 mm
sized B4C powders in the temperature range 1900
2200uC and a period of 545 min. They have deduced,
the main sintering mechanisms to be volume and grain
boundary diffusion for pure boron carbide and grain
boundary diffusion for carbon doped boron carbide
showing activated sintering. Schwetz et al.189,207 have
obtained compacts of 9798% TD with the addition of
13% phenolic type of carbon using a powder of large
surface area (22 m2 g21). A fine grained (78 mm)
compact with superior mechanical properties (flexural
strength: 351353 MPa and fracture toughness:
3?3 MPa m1/2) was obtained.
Very fine powders in the range of nanosizes would
increase the rate of sintering due to very large surface
area and particle to particle contact. Zorzi et al.192 have
used carbon black of 20 nm size (specific surface area:
120 m2 g21) with boron carbide powder of surface
area18?8 m2 g21 to obtain 97?7% TD compacts having
Knoop hardness in the range 1921 GPa by sintering at
2250uC for 2 h. While studying the densification
behaviour of nanosized boron carbide, it has been
found that solid state sintering (1500 to 1850uC) starts
only after the evaporation of B2O3. The formation of
eutectic (B4C-C) liquid droplets appears on the surface
of graphite coated B4C particles above 1920uC, which
form the weaker regions in the sintered product.208
Sample sintered at 2300uC, showed the grain boundary
to be free from carbon and the excess carbon present as
fine graphite crystals at the triple point resulting in
excellent mechanical properties (Fig. 13a).209 High
resolution TEM image of the sample shows no
boundary or amorphous layer (Fig. 13b).209 Large,
Suri et al.
complex boron carbide shapes of density .94% are

fabricated by slip casting method using a binder and
sintering at 2280uC for 2 h.210
Thermosetting phenolic types of resins are most
suitable as carbon precursors as they give a complete
uniform coating of carbon on the surface of carbide
particles. Carbon can be replaced by boron to react with
surface oxide layer of B4C to achieve similar effects. In
addition boron will also react with free carbon of B4C to
form carbide.192
Addition of a small amount (35 wt-%) of carbon to
B4C plays an important role in eliminating the surface
oxide layer, thereby achieving higher densities (y97%
TD) with fine grains and improved mechanical properties (hardness: 1925 GPa; flexural strength: 160
350 MPa). The quantity and the method of carbon
addition have to be carefully chosen to avoid free carbon
in the sintered body.
Role of carbide/boride additives
In addition to carbon, other grain refinement agents for

B4C are Si and Al. Although the strength can be significantly improved by grain size reduction, the toughness
remains low. Addition of carbides and borides have been
found to increase the flexural strength and fracture
toughness of B4C by grain refinement and crack propagation influencing mechanisms such as crack deflection, micro crack interaction and crack impediment.211
Carbides/borides can either be directly added or formed
by in situ reaction with B4C while sintering. Faber
and Evans212 have predicted that fracture toughness
increases due to crack deflection around second phase
particles in two-phase ceramic materials. The ideal
second phase, in addition to maintaining chemical
compatibility, should be present in amounts of 10 to
20 vol.-%. Greater amounts may diminish the toughness
increase due to overlapping particles. Particles with high
aspect ratios are most suitable for maximum toughening
especially particles with rod shaped morphologies.
Zorzi et al.192 have reported that addition of
4 wt-%TiB2 to B4C lead to good results in final density,
hardness and wear resistance. Baharvandi and
Hadian213 have reported the addition of TiB2 on
sinterability and mechanical properties of B4C. Density
and fracture toughness values were found to increase
with TiB2 fraction in the entire range of 0 to 30%,
whereas bending strength and hardness improve to
certain amount (15%TiB2) and then start decreasing.
With 30%TiB2 the highest density and fracture toughness of 98?5% TD and 3?4 MPa m1/2 were achieved
respectively. At 15%TiB2 the highest hardness of 31 GPa
and flexural strength of 360 MPa were obtained. TiB2
also acted as a grain growth inhibitor. TiB2 is formed by
reaction sintering of boron carbide with titanium oxide
at y1500uC as per the following reaction
B4 Cz2TiO2 z3C?2TiB2 z4CO:
197
(19)
Levin et al.
have found that TiO2 is reduced by
carbon originated from the carbide phase. This leads to
the formation of substoichiometric boron carbide, which
is responsible for increased rate of sintering. Addition of
40 wt-%TiO2 to B4C powder (17 m2 g21 specific area)
gives a compact of 95% TD after sintering for 1 h at
2160uC.187,197 Presence of TiB2 results in lowering of
activation energy for sintering and hence very high
densities of 99% could be achieved without pressure at

temperatures of 20502100uC.214,215 Metallographic
examination revealed a two phase microstructure with
B4C grains of 10 and TiB2 of 57 mm size. Grain size
of B4C was found inversely proportional to the quantity
of carbon in the sample. Increase in volume fraction of
TiB2 led to an increase in flexural strength and fracture
toughness to a maximum of 513 MPa and 3?7 MPa m1/2
respectively at 15 vol.-%.216,217 The observed increase in
strength and fracture toughness are due to the interaction between the propagating crack front and local
thermal mismatch stress associated with TiB2 particles.
Titanium carbide also reacts with boron carbide to
form TiB2 as per the reaction
B4 Cz2TiC?3Cz2TiB2
(20)
The amount of second phase TiB2 and excess carbon

play a distinct role in sintering. Densities higher than
95% TD were obtained by sintering at temperatures
above 2150uC.200 As the carbon content increased from
1?5 to 6?0%, the grain size of B4C decreased from 10 to
3 mm, flexural strength increased from 292 to 502 MPa,
and toughness decreased from 4?2 to 2?9 MPa m1/2.
Addition of various transition metal (Ti, Zr, Hf, V,
Nb and Ta) carbides/borides for preparing dense boron
carbide pellets have been patented.218,219 Boron carbide
is reacted at approximately 1500uC with the transition
metal oxide/carbide to form a mixture of boron
carbidezmetallic carbide/boride, which is sintered at
temperatures .2000uC to obtain densities .95%.
Goldstein et al.198 have studied the reaction between
B4C and MeO mixtures (MeOTiO2, ZrO2, V2O5,
Cr2O3, Y2O3 and La2O3) fired up to 2180uC for 2 h in
argon. The main solid reaction products are found to be
borides. Such composites exhibited a sintering aptitude
higher than that of monolithic B4C, increasing with the
amount of metal oxide in the initial mixture. The
hardness and strength of composite were comparable to
that of hot pressed B4C. Khazai et al.220 have patented a
process for the preparation of boron carbide/titanium
diboride composite with uniform distribution of both.
Baharvandi et al.196 have studied the effect of addition
of Yttria doped zirconia on sintering behaviour
(between 2050 and 2150uC in argon for 1 h) and
mechanical properties of B4C. Densities of 97% TD
were obtained in samples with >15%ZrO2 addition.
Boron carbide reacts with ZrO2 during sintering to form
ZrB2 as per the following reaction
B4 Cz2ZrO2 ?2ZrB2 zB2 O3 zCO:
(21)
Fracture toughness and flexural strength of the compacts increased from 2?1 to 3?1 MPa m1/2 and 200 to
340 MPa respectively with the increase of ZrO2 content
from 0 to 30%. Processing in vacuum and higher
temperature (2275uC) increased the hardness to
.30 GPa.221 Figure 14 presents the variation in hardness of pressureless sintered B4C with ZrO2 addition.
Hardness in the entire range of composite is y30 GPa
compared to 27 GPa for pure B4C. Backscattered image
of this sample shows a white phase containing up to
1?2%Zr distributed in B4C matrix (Fig. 15).
Fractography (Fig. 16)221 shows the mode of fracture
to be a combination of transgranular and intergranular.
The in situ reactions for the formation of carbide/
boride consume some of the carbon from boron carbide,
2010
VOL
55
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23
Suri et al.
14 Variation in hardness of pressureless sintered B4C

with ZrO2 addition (hardness in entire range of composite is y30 GPa compared to 27 GPa for pure
B4C):221 reprinted with permission from Elsevier,
Ceram. Int., 2008, 34, Fig. 3 in p. 1545
thereby generating substoichiometric boron carbide.

This defective structure enhances diffusion kinetics
thereby improving the rate of sintering. The improved
mechanical properties are attributed to the presence of
fine distribution of secondary phase particles in the
matrix. If the second phase is not as hard as boron
carbide and then presence of large volume is likely to
deteriorate the mechanical properties and hence one has
to optimise the level of second phase addition to obtain
the best properties.
Liquid phase sintering
Liquid phase sintering is carried out either by the

addition of a substance with low melting point or by the
formation of a low melting substance by in situ reaction
of the additive with boron carbide. Wettability, capillary
action, dissolution and reprecipitation are the important
parameters, which decide the ability to sinter and the
mechanical properties. Wetting of polycrystalline B4C
by molten aluminium between 900 and 1200uC have
been studies by Lin et al.222 They found the Wettability
of B4C to be strongly depend on temperature and the
formation of different reaction products such as
Al2?1B51C8, Al3BC, AlB2, Al3B48C2 at the interface.
15 Backscattered image of sintered boron carbide with

ZrO2: white regions analysed to contain 1?2%Zr
24
2010
VOL
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16 Image (SEM) of fractured surface of sintered boron

carbide with ZrO2 addition: mode of fracture seen as
combination of trans- and intergranular:221 reprinted
with permission from Elsevier, Ceram. Int., 2008, 34,
Fig. 6 in p. 1547
Danny et al.223 have studied the problems of B4CAl

particulate composite fabrication and explained that
chemical reactions between B4C and aluminium occur
between 800 and 1400uC much faster than capillary
induced liquid rearrangement, inhibiting the densification process. It is suggested that the application of
external pressure during sintering to accelerate densification faster than the kinetics of phase formation.
Attempts have been recently made to prepare B4C
CeB6/Al composite with improved strength and toughness by pressureless infiltration technology.224
Silicon with a melting point of 1410uC, when added to
boron carbide acts as a liquid sinter additive and in
addition reacts with carbon of boron carbide to form
silicon carbide, thus helping the sintering process and
also strengthening the matrix. Silicon carbide has
attractive properties, similar to that of boron carbide
such as high hardness (28 GPa), low specific gravity
(3?1 g cm23) and good wear resistance and hence
considered an attractive sinter addition to boron
carbide. Taylor et al.225 describe a process where silicon
is infiltrated into a porous body of boron carbide and
then sintered in the temperature range 15002200uC to
obtain dense (2?57 g cm23) non-porous boron carbide
body which is extremely hard (modulus of rupture
235 MPa, modulus of elasticity 353 GPa). X-ray diffraction pattern obtained correspond to normal B4C,
second boron carbide type having an expanded lattice,
alpha and beta silicon carbides and silicon. The chemical
analysis showed 16?5%C, 32?6% total silicon, 50?9%
total boron, 0?16% free carbon and 12?6% free Si. The
presence of unreacted, free silicon lowers mechanical
properties of reaction bonded B4C. The fraction of free
Si can be reduced by increasing the green density of the
initial boron carbide preforms.226 Mallick et al.227 have
demonstrated the possibility of net shape production via
infiltration of Si melt into porous preform containing
B4C and carbon. Chen et al.228 have studied the
formation and sintering mechanisms of reaction bonded
silicon carbide boron carbide composites. In the product
sintered at 1450uC, a non-stoichiometric boron carbide
Suri et al.
phase B12(C,Si,B)3 and a minor phase rich in B10C or

B49C1?82 were seen. Microcracks were also observed in
boron carbide grains. B4C cermets, for application as
neutron absorber have been prepared by sintering with a
eutectic alloy of AlSi at a low temperature of 550uC.229
The role of iron in the sinterability of B4C has been
studied by contact angle measurement and dilatometric
densification. The interaction zone consisted of a fine
mixture of FeB and graphite. The sintering kinetics
confirmed the liquid phase sintering leading to improved
mass transfer.230 Mizrahi et al.231 have also attributed
the formation of liquid phase promoting the mass
transfer mechanism in B4CFe mixtures. Iron additions
also provide the desired porosity for successful infiltration of preforms.
Addition of carbon to react with infiltrated silicon for
forming silicon carbide rather than with boron carbide is
beneficial as silicon carbide has a lower hardness and
higher specific gravity compared to boron carbide.232
Hayun et al.233 have found that presence of a large
fraction of plate-like SiC in samples formed due to initial
higher porosity, are responsible for increased flexural
strength and fracture toughness on account of strengthening effect of the high aspect ratio of the second phase
particles. The dynamic strength and the dynamic
fracture toughness K1d are significantly higher than the
corresponding static properties and are insensitive to the
residual silicon fraction and to the strain rate (up to
5103 s21). Properties of the B4C material prepared by
this method are given as: density, 2?57 g cm23; youngs
modulus, 382 GPa; flexural strength, 278 MPa and
fracture toughness, 5?0 MPa m1/2. Organosilicon polymers such as polycarbosilane,190 polysiloxanes, polysilazanes,
polysilanes,
metallopolysiloxanes
and
metallopolysilanes,234 which upon pyrolysis yield SiC
and free carbon have been found to be very effective in
pressureless sintering of boron carbide. Weaver202 has
patented a process where in a mixture of boron carbide
and silicon carbide are mixed in an aluminium mill to a
composition of 87B4C10SiC3Al which is sintered at
18002300uC to densities up to 94% TD.
Chromium boride forms a eutectic liquid phase with
B4C at a temperature of 2150uC. The fractured surface
of the B4C specimen with 20 mol.-%CrB2 prepared at
2000uC showed the CrB2 particles to be partially
melted and wetted with the adjacent B4C particles
(Fig. 17).203,204,235 There was no significant growth of
B4C grains and the densification was mainly attributed
to B4C particles rearrangement caused by the CrB2B4C
eutectic liquid formation. However at temperatures
above 2200uC, abnormal grain growth of B4C occurred.
Specimen with 98?1% TD (20 mol.-%CrB2, sintered at
2030uC) showed a high flexural strength of 525 MPa and
a moderate fracture toughness of 3?7 MPa m1/2. The
improvement in fracture toughness is due to the
formation of microcracks and the deflection of propagating cracks due to the thermal mismatch of CrB2 and
B4C.
Addition of alumina improves the densification of
boron carbide with the formation of liquid phase
AlB12C2 by the reaction between B4C and Al2O3.
Maximum density of 96% TD was achieved by the
addition of 3 wt-% alumina doped B4C sintered at
2150uC for 15 min.199 Exaggerated grain growth was
observed in the specimen containing .4% alumina.
17 Fracture surface of B4CCrB2 specimen indicating

partially melted CrB2:204 reprinted with permission
from Springer, J. Mater. Sci. Lett., 2002, 21, Fig. 4 in
p. 1446
Baharvandi et al.195 have studied the effect of high

alumina talc (26?62Al2O347?78SiO225?6MgO) powder
as a sintering aid. The sample sintered at 2050uC for 1 h
showed the formation of MgB2, SiC and Al2O3. The
mechanism of sintering is due to the formation of liquid
phase anstatite at 2000uC and its reaction with B4C to
form SiC, MgB2 and Al2O3. Though the density (78
98%) and fracture toughness (22?8 MPa m1/2) of the
compact increased with the quantity of talc in the charge
up to 30%, microhardness attained a peak value of
26 GPa at 25% and then fell down.
A US patent236 explains a process wherein boron
carbide powder is mixed with aqueous sodium silicate
(to give SiO2 equivalent of 0?751?5 wt-%B4C) and
alumina (13 wt-%), compacted and sintered at 2100uC
to give compacts exceeding 90% TD. As per another US
patent by Prochazka201 addition of 0?53 wt-%BeC to
boron carbide helps in achieving a density of 8594%
TD by sintering at 22002280uC. Weaver in his patent202
has mentioned a process to obtain refractory bodies
composed of 6098 wt-% boron carbide, 240 wt-%
silicon carbide and 010 wt-% aluminium with densities
exceeding 94% TD by cold pressing followed by a
pressureless heat treatment.
Low melting metals/alloys such as Al and AlSi have
been used to bind boron carbide particles to different
shapes for neutron absorber applications. Liquid phase
sintering of boron carbide is carried out by in situ
reaction with alumina, silica, BeC, CrB2, etc. This
reduces the sintering temperature by a few hundred
degrees and the sintered product has a fine microstructure and moderate mechanical properties. Silicon is
found to be an excellent additive which is introduced
into a sintered porous body of B4C by infiltration
technique. This helps in two ways: by liquid phase
sintering and by SiC formation which greatly improves
the mechanical properties. Owing to fine grain structure
and high fracture toughness of the end product, this is
the method chosen for the manufacture of B4C based
armour shields.
Hot pressing
In conventional sintering, the rate of densification is
very slow. Though higher densification can be achieved
at higher temperatures, it is difficult to prevent grain
2010
VOL
55
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25
Suri et al.
19 Boron carbide pellets of various sizes compacted by

hot pressing
18 Vacuum hot press with front door open showing graphite heaters and insulation
growth. Addition of second phase can only retard but

not completely prevent the grain growth. Pressure
assisted consolidation/sintering generally involves heating a powder compact, with the simultaneous application of pressure. The powder compacts are typically
heated externally using graphite heating elements and
the pressure is applied hydraulically. A photograph of a
vacuum hot press with front door open showing the
graphite die and heaters is presented in Fig. 18. Hot
pressing is the most common method for fabricating
dense articles of pure B4C. Without sinter additives B4C
can be fully densified by hot pressing .2100uC with an
applied load of >30 MPa. Photographs of boron
carbide pellets of various sizes compacted by hot
pressing are presented in Fig. 19. Densification by
sintering during hot pressing results from three successive mechanisms:
(i) particle rearrangement, where the total and open
porosities decrease and the closed porosity remains
constant (temperature range: 18001950uC)
(ii) plastic flow, leading to the closing of open
porosity without significantly affecting the closed
pores (19502100uC)
(iii) volume diffusion and pore elimination at the end
of the hot pressing (21002200uC).1,186,237239
The density, porosity and microstructure of hot pressed
B4C depend on the hot pressing parameters, such as
temperature, pressure, time, heating/cooling rate, etc.
Though very fine particles are not a precondition, the
size of boron carbide used for hot pressing generally falls
in the range 110 mm. Table 8179,194,234,239258 presents
the literature data on hot pressing of boron carbide with/
without additives.
The density of the compacts obtained under identical
hot pressing conditions (2150uC for 10 min) were 91?6
26
2010
VOL
55
NO
and 99?7% TD with starting powders of 3?85 and

0?35 mm respectively.259 Though at lower temperatures,
heating rate influences the rate of densification, at
temperatures .2000uC it has no important influence on
densification.240 A temperature of >2100uC and a
pressure of 34?4 MPa are necessary to obtain density
close to 100% TD. Slow cooling after densification has
been found to be responsible for reduction in the final
density due to the formation of pores while cooling. As
boron carbide reacts with the die material, inner lining
of the graphite die is essential to prevent this reaction.
BN lining has been found to be most suitable. The
microstructure of hot pressed specimens show no grain
growth (1?52?0 mm) up to 1950uC, a steady even growth
up to 2050uC (the final grain size 5 mm) and an uneven
sized growth and the presence of large number of twins
at 21502200uC.239 Fast heating rates and application of
high pressure (40 MPa) have been helpful in obtaining
full densification at a lower temperature of 1900uC.179
Samples obtained under these conditions show a
microstructure, free of grain boundary phases, with an
average grain size of 2 mm and faceted submicrometre
pores accounting for ,1 vol.-% porosity. Jianxin250 has
prepared boron carbide nozzles by hot pressing at
2150uC in an inert atmosphere with a pressure of
36 MPa using starting powders of ,3 mm size with a
density, hardness, fracture toughness and flexural
strength of 95?5% TD, 32?5 GPa, 2?53?0 MPa m1/2
and 300400 MPa respectively. He has also studied the
erosion wear of this by abrasive air jets using SiO2, SiC
and Al2O3 powders. While studying the densification by
hot pressing, Ostapenko et al.239 have found that the
densification of boron carbide is controlled by a process
leading to non-linear creep, whose rate is a function of
the square of stress. Experimenting on the activated
sintering kinetics by the addition of iron, Kovalchenko
et al.238 have noted that, dislocation climb is the main
mechanism leading to creep; whose rate is a quadratic
function of stress. Properties of dense B4C compacts
prepared by hot pressing generally have the best
properties with the following values:260 hardness, 29
35 GPa; fracture toughness, 2?82?9 MPa m1/2; elastic
modulus, 450470 GPa; thermal conductivity, 30
42 W m21 K21; coefficient of thermal expansion,
B4C
B4C
bBzC
Amorphous BzC
aBzC
B4C
3
4
5
11
10
2010
B4Cz5.3%Mo
B4Cz5%TiCz5%Mo
B4Cz10%TiCz4.7%Mo
B4Cz15%TiCz4.5%Mo
B4Cz20%TiCz4%Mo
B4C: D5053 to 5; TiC: D5051

to 2; Mo: D5051 to 3
1950uC,
1950uC,
1950uC,
1950uC,
1950uC,
35
35
35
35
35
MPa,
MPa,
MPa,
MPa,
MPa,
50
50
50
50
50
65
50
40
30
65
min,
min,
min,
min,
min,
min,
min,
min,
min,
min,
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar
Ar, 1 h, HR:
2000uC, 20 MPa,
1525uC min21
2150uC, 35 MPa,
1850uC, 35 MPa,
1850uC, 35 MPa,
1850uC, 35 MPa,
2150uC, 35 MPa,
B4Cz23.4%TiO2z5.28%
carbon black
B4C
B4Cz10%(W,Ti)C
B4Cz30%(W,Ti)C
B4Cz50%(W,Ti)C
B4C
B4C: D5050.63; SS: 19.8;

TiO2 99.9% pure, submicrometre
B4C: D5053 to 5
(W,Ti)C: D5051 to 2
2100uC, 35 MPa, 8 min
2000uC, 50 MPa, 1 h, Ar
B4CzTiO2zC
B4C: D5050.50; SS: 21.5

B4C: D5050.44; SS: 15.5
B4C: D550.41; SS: 22.5
B: D50520
D5051.5 synthesis from the

elements
D5051; SS: 12
D50,3
D5052.0; SS: 1.27
D5050.2; SS: 12.76
D5052.74; SS: 0.89
B4C: D50510; O: 0.11.0 wt-%
2100uC, 40 MPa, 30 min, Ar
2150uC, 36 MPa, 60 min
1950uC, 30 MPa
1800uC, 30 MPa
1800uC, 30 MPa
2200uC, 34.5 MPa, 1 h, HR:
0.5 K s21, CR: 1.7 K s21
34.4 MPa, 2.7 ks, heating rate: 1775

330 K ks21; cooling rate:
1665 K ks21
1975
2175
2325
2375
2475
2200uC, 22 MPa, 10 min
FC: 1.4%
D5052.9
SS: 0.246.2
Hot pressing conditions
B4Cz5%B
B4Cz15%B
B4CzTiO2zC
TiO2: D50, nanosize
B4C
B4C
Serial Material composition,

no.
wt-%
K
K
K
K
K
96.5
99.1
99.2
99.0
98.5
95.0
98.5
99.2
99.5
95.0
2.49 g cc21
2.42 g cc21
100
100
100
.95
.95
95.5
87
99
91
2.5 g cc21
72.4
80.2
98.5
98.4
99.6
98
K 65.1
12
12
12
12
12
1040
B4C: 3.8, TiB2
B4C: 3.4, TiB2
B4C: 3.9, TiB2
0%TiB2
5% TiB2
10%TiB2
20%TiB2
30%TiB2
40%TiB2
15 vol.-%TiB2; rest:
B4C
B4C: 610
12, TiB2, W2B5
0.51.5
,1
58
1050
22
25
24.5
23.5
29
28
26
23
21
27
30
32
34
30
28
3.40
4.25
3.75
3.60
2.5
2.8
3.9
4.5
2.60
3.1
2.8
3.2
3.1
4.0
5.0
5.1
4.6
4.3
6.1
2.53.0
239 (1979)
240 (1983)
550
695
625
550
245
400
550
690
540
190
200
870
720
815
200
350
500
630
530
400
621
240
247 (2009)
246 (2002)
244 (2000)
257 (1990)
243 (2005)
242 (1979)
179 (1989)
300400 250 (2005)
241 (2000)
Vickers
Indentation Flexural
hardness, toughness, strength,
GPa
MPa m1/2 MPa
Reference (year)
7.0
12.1
13.5
15.2
16.4
.5, a large number
of twins
23
48
32.5
6.0
Microstructure,
Sintered
density rth, % mm
Table 8 Powder details, sintering parameters and characteristics of sintered boron carbide by hot pressing*
Suri et al.
VOL
55
NO
27
28
2010
VOL
55
NO
20
19
18
17
16
15
14
13
12
B4C
B4Cz10 wt-% BN
B4Cz20 wt-% BN
B4Cz30 wt-% BN
B4Cz40 wt-% BN
B4Cz60%Al2O3
B4Cz70%Al2O3
B4Cz80%Al2O3
B4Cz90%Al2O3
B4CzAl2O3
B4CzAl2O3z5%TiC
B4CzAl2O3z10%TiC
B4CzAl2O3z15%TiC
B4CzAl2O3z20%TiC
66 MPa, 3 min, heating rate:

40 K min21; cooling rate:
100 K min21
1900uC, 30 MPa, 30 min, Ar; HR:

15150uC min21
B/C54.1; B: D5051.5; O: ,4%
MPa,
MPa,
MPa,
MPa,
MPa,
65
60
60
60
60
min,
min,
min,
min,
min,
2150uC,
1950uC,
1950uC,
1950uC,
1950uC,
(B4C/Al2O3518 : 1)
B4C: D5053 to 5, .95%
Al2O3: D5051 to 2, .99%
TiC: D5051 to 2, .99%
35
35
35
35
35
1700uC, 35 MPa, 1 h, Ar
B4C: D5051.0
Al2O3: D5050.2
B4C: D5053.5; BN: D50, nanosized 1850uC, 30 MPa, 1 h, N2
Ar
Ar
Ar
Ar
Ar
1750uC, 24 MPa, 10 min to 4 h
2275uC, 28 MPa, 1 h, Ar
1900uC, 50 MPa, 1 h, Ar
1620uC
1670uC
1720uC
1820uC
1920uC
2120uC
B4C: D5050.43
CrB2: D5053.5
B4C: D5050.43; SS: 15.3; O2:

2050uC, 5 MPa, 1 h, Ar
2 wt-%; Fe: 140 ppm, Al: 50 ppm
CrB2: D5053.5
SizBzC
C, SS: 80; Si: D10055
B4Cz8 to 13% siloxane/
phenolic
B4C: D5050.1 to 1
B4Czsodium silicatez
magnesium nitratezFe3O4
B4C
B4Cz5%CrB2
B4Cz10%CrB2
B4Cz15%CrB2
B4Cz20%CrB2
B4Cz25%CrB2
B4Cz50%SiC
B4Cz10%CrB2
B4Cz15%CrB2
B4Cz20%CrB2
B4Cz22.5%CrB2
B4Cz25%CrB2
B4C
D50,1
B4C: 29.557%; B: 18.3
35.5%; Si: 3.87.5%; WCz
TiC: 045.3%; Co: 02.8%

no.
wt-%
Table 8 Continued
4598.4
99.5
99.2
99.0
98.5
98.1
3.53
3.65
3.77
3.86
95.5
98.7
98.9
98.7
98.5
4568
21
2.74 g cc
9799.7
86
94
95
96
98
95
99.0
99.6
99.7
99.0
99.0
98.6
2.50 g cc21
3.5 g cc21
3.6 g cc21
3.59 g cc21
3.5 g cc21
3.45 g cc21
3.2 g cc21
79.3
3.0
3.2
3.4
B4C:
B4C,
B4C:
B4C,
B4C,
25
TiB2
0.51.5, TiB2
TiB2
TiB2
B4C, nano-h-BN
B4C, SiC
B4C, SiC/C
B4C, SiC
Eutectic liquid of
CrB2zB4C
B4CTiB2W2B5
Microstructure,
Sintered
density rth, % mm
21
15
11
8
7
28
27
23
21
22.41.2
24.11.1
24.71.0
24.31.0
23.21.0
25
12
26
30
28
25
26
2.2
2.5
2.8
3.2
3.2
3.2
2.5
2.6
2.7
2.8
3.5
3.4
5.4
6.0
5.2
5.0
4.3
4.20.7
4.20.4
4.30.5
3.50.5
3.20.5
4.10.5
4.70.4
4.50.4
4.20.4
249 (1974)
234 (1996)
273 (1993)
248 (2003)
256 (2003)
245 (1986)
410
254 (2008)
420
410
360
310
53030 258 (2005)
56030
60070
55045
30034 271 (2008)
43031
44530
38629
32332
350
500
550
620
684
660
675
551
580
630
630
580
1.9
550
620
710
830
710
580
180
Vickers
GPa
MPa m1/2 MPa
Reference (year)
Suri et al.
*FC: free carbon in B4C; HR: heating rate; CR: cooling rate; D50: mean particle diameter, mm; SS: specific surface area, m2 g21; RE: rare earth.
81.9
73.6
B4C/Cu578 : 22
B4C/Cu592 : 8
24
23
22
253 (1999)
194 (1978)
1.75 g cc21
B4C: 260 mesh

600, 16.3 MPa, 40 min
Al: 2325 mesh
B4C: D5055 to 40; Cu: D5051 to 8 1050uC, 39 MPa, 1 h
99.6100
18252000uC, 10.3 MPa, Ar
B/C5 3.8 to 4.5; D5050.7 to 3.0
700800 252 (2007)

3.03.9
2527
251 (2008)
156.76
97 HRA
B4C, Al8B4C7,
LaAlO3,
B4C: 12
92.5
1850uC, 20 MPa, 1 h, vacuum
21
B4Cz6%La2O3z
12%Al2O3z12%C
90 to 99%B4Cz0 to
1% BN/AlNzrest RE
oxide-Al2O3
B4Cz30%Al

no.
wt-%
Table 8 Continued
Microstructure,
Sintered
density rth, % mm
Vickers
GPa
MPa m1/2 MPa
Reference (year)
Suri et al.
20 Microstructure of hot pressed boron carbide showing

transgranular fracture:193 reprinted with permission
from Elsevier, Ceram. Int., 2006, 32, Fig. 4(a) in p. 232
561026 K21; flexural strength, 350 MPa; compressive

strength, 14003400 MPa.
Fractography of fully dense boron carbide compact is
shown in Fig. 20.193 The mode of fracture appears to be
transgranular.
Fabrication of boron carbide shapes by hot pressing
the mixture of particulate boron and carbon is also
practised.111 Kalandadze et al.241 compacted boron and
carbon powders in ampoules up to 30% TD, by shock
compression, as a result of an explosive detonation.
These pellets were densified by hot pressing at temperatures 19002100uC and pressures 2040 MPa in boron
nitride lined graphite moulds. A comparison between arhombohedral, b-rhombohedral, and amorphous boron
indicated that sintering into the b-rhombohedral phase
at the final stage can give higher densities as follows:
BbRBaRBamorphous, which is attributed to the phase
transformation occurrence from amorphous boron to brhombohedral boron through a-rhombohedral boron
modification.
Compacts with densities higher than that achievable
by pressureless sintering process are produced by hot
pressing of boron carbide powders. The added advantages of hot pressed compacts are fine grained structure,
very low porosity and improved mechanical properties.
Larger size powders in the range 310 mm can be
sintered to near theoretical densities by hot pressing at
y2000uC and 3040 MPa pressure. For application
such as in nuclear industry, where pure boron carbide is
essential and impurities/additives cannot be tolerated,
hot pressing is the preferred method to produce dense,
pure compacts.
Role of sinter additives
Earlier we have seen that carbon additive greatly

enhances the sintering kinetics in pressureless sintering.
Such an effect is not expected in the case of hot pressing
as the sintering mechanisms are different. In the
literature also one does not find any report on hot
pressing of B4C with carbon addition. However addition
of boron would consume the free carbon available in the
boron carbide. It is seen that small additions of B (1 to
5%) improves the strength of boron carbide specimens at
2010
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Suri et al.
lower hot pressing temperatures.242 Similar to preparation of boron carbide based cermets for nuclear
applications boron carbide rings with adequate strength
have been prepared by hot pressing technique with
y30 wt-% aluminium as binder for possible use as
neutron absorber.194 A high density B4C/Cu cermet with
70 vol.-%B4C exhibiting high thermal conductivity has
been prepared by hot pressing of Cu coated B4C
powders for the application of absorber materials in
liquid metal cooled fast breeder reactor.253 Though
boron carbide in various forms is used in nuclear
industry, literature data on the production methods is
scarce. An US patent261 explains a process for producing
B4C armour plates with improved ballistic properties by
the addition of Cr, B, or mixtures thereof.
Role of TiB2
Reaction sintering of boron carbide with the addition of

titanium oxide and carbon as per reaction (19) produces
extremely fine high surface area particles of TiB2 which
promote densification and limit the grain growth of the
boron carbide matrix. This microstructure with TiB2
particles uniformly distributed in a fine grained B4C
matrix is responsible for the increase in fracture
toughness and strength. B4C15 vol.-%TiB2 composite
with a flexural strength of 621 MPa and fracture
toughness of 6?1 MPa m1/2 have been prepared by hot
pressing at 2000uC and a pressure of 20 MPa in argon
atmosphere for 1 h by Skorokhod et al.244 They have
observed that factors for the increased strength are due
to the healing of the cracks during sintering and the
presence of TiB2 particle which force the crack to
propagate in a non-planar fashion thus enhancing the
energy dissipation at the crack tip. An US patent243
explains a process to prepare boron carbide composites
containing 5 to 30 mol.-% titanium diboride with very
high flexural strength (870 MPa) and fracture toughness
(3?4 MPa m1/2). Addition of Fe in small amounts (0?5%)
has been found to be effective in increasing the final
densities of B4CTiB2 composite due to the formation of
FeTi rich liquid phase at the grain junctions.262
Role of mixed borides
As seen in the previous lines addition of TiO2 has

brought down the hot pressing temperature of B4C by
>100uC. Further attempts to reduce the sintering temperature without compromising the strength are given
below. Reaction sintering of B4C with 30 wt-%(W,Ti)C
at 1850uC for 30 min showed increase in fracture
toughness and flexural strength up to 50 wt-%(W,Ti)C
content. Fine grains of (0?52 mm) TiB2 and W2B5 were
seen in the microstructure. The sintering temperature of
this composite is 300uC lower than that of monolithic
B4C. Flexural strength and fracture toughness for
composite with 40 to 50% additive were 700 MPa and
4?5 MPa m1/2. The increase in fracture toughness is
attributed to the residual stresses generated by differences in the thermal expansion coefficient between B4C,
TiB2 and W2B5. The effect of TiB2/W2B5 on the path of
crack and deflection in the composite is shown in
Fig. 21.246 Further reduction in sintering temperature
was achieved by the addition of B, Si and Co to the
above referred mixture. Reaction sintering of B4C with
WC, TiC, B, Si and Co by attrition milling followed by
hot pressing at 1720uC for 2 h gave a compact with three
distinct phases of B4C, W2B5, and TiB2, hardness in the
30
2010
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21 Crack path produced by Vickers indentation on

polished surface of hot pressed B4C30 wt-%(W,Ti)C
composite:246 reprinted with permission from Elsevier,
Ceram. Int., 2002, 28, Fig. 10 in p. 429
range 2833 GPa and flexural strength of 830 MPa

max.245 US patent by Petzow et al.263 describes a process
for the preparation of boron carbide/transition metal
boride moulded articles comprising of B4C, Si, WC and/
or TiC and Co by hot pressing between 1550 and
1850uC. Effect of variation of TiC addition on hot
pressing of B4C/TiB2/Mo composite has been studied by
Jianxin et al.247 and the maximum values of fracture
toughness, flexural strength and hardness reported are
4?3 MPa m1/2, 695 MPa and 25?0 GPa respectively.
During ball milling/mixing of B4C with additives, the
powders get contaminated and the microstructure of the
composite appears very complicated after hot pressing
due to the diffusion of W, Co, Ni, Cr, etc. either into the
TiB2 grains to form (Ti,M)B2 or (Ti,M)B2 coated grains,
and Ti, Fe, Co, Ni, and Cr into W2B5 to form boron rich
boride or the interfacial layer.264
Role of carbides/nitrides
Li et al.265 have prepared a composite containing B4C,

SiC, TiB2 and BN by reactive hot pressing of B4C,
Si3N4, a-SiC and TiC powders and the hardness,
bending strength, fracture toughness and relative density
of the composite were 88?6 HRA, 554 MPa,
5?6 MPa m1/2 and 95?6% respectively. Microstructure
analysis showed the presence of laminated structure and
a clubbed frame dispersion phase and bunchy dispersion
phase among the matrix. Fractography and crack
propagation suggested that crack deflection and bridging are the possible toughening mechanisms.
Han et al.266 have synthesised a high strength (400
570 MPa, 69?5 MPa m1/2) B4CTiB2SiCgraphite
composite by reactive hot pressing using B4C, TiC and
SiC powders. The crack deflection at the phase
boundary between B4C matrix and dispersions consisting of SiC and TiB2, which occur by residual stresses due
to the differences in thermal expansion coefficients of
B4C, TiB2 and SiC while cooling from the fabrication
temperature is responsible for the enhanced fracture
toughness values. Similar very high strength material
(four point bend strength: 850 MPa; fracture toughness:
6?1 MPa m1/2) has been prepared by the addition of
530 vol.-%Mo to B4C/(W,Mo)B2 by hot pressing at
1900uC.267 Fractography of this sample showing the
crack propagation path is depicted in Fig. 22.267 When
Suri et al.
22 Crack propagation path with considerable deection

in hot pressed B4C/30W20Mo composite:267 reprinted
with permission from Japan Society of Powder and
Powder Metallurgy, J. Jpn Soc. Powder Powder
Metall., 1999, 47, (1), Fig. 8 in p. 28
boron is added to the above mixture, hardness of the

compact increases due to the inhibition of B4C decomposition but the bending strength and the fracture
toughness reduce.268 A composite B4CVB2C obtained
by reaction synthesis with hot pressing has been found
to exhibit high hardness and bending strength suitable
for application as wear and shock resistance components.269 Cr and V carbides are also found to be effective
in obtaining high densities and fine grained structure.270
A process in which a preceramic organosilicon polymer
which on pyrolysis yields SiC and free carbon has been
patented for preparation of dense bodies of boron
carbide (.97% TD) by hot pressing in inert atmosphere
at a temperature of 2275uC and a pressure of 28 MPa.234
Reaction sintering of boron carbide with the addition
of oxides/carbides/nitrides has been successfully
employed to obtain a microstructure of fine particles
of reaction product (borides/carbides/nitrides) in B4C
matrix. These additions lower the sintering temperature
than that of monolithic B4C. Flexural strength and
fracture toughness of these composites are very high due
to the residual stresses generated by differences in the
thermal expansion coefficient between B4C and reaction
products, crack bridging and deflection mechanisms at
the interface, etc. Small quantities of B, Si, Ti, Fe, Co,
Ni, Cr, W, etc. either intentionally added or accidentally
acquired during the grinding/mixing operations are also
found to be effective in marginally reducing the sintering
temperature and improving the flexural strength/fracture
toughness due to the formation of complex boride
phases and multi interfaces.
Liquid phase sintering
Addition of CrB2 aids in lowering the hot pressing

temperature due to the formation of CrB2B4C eutectic
at 2150uC. B4C20 mol.-%CrB2 composite fabricated
by hot pressing at 1900uC shows a high strength of
630 MPa and a modest fracture toughness of
3?5 MPa m1/2. The very fine grained microstructure is
responsible for high flexural strength and residual
stresses caused by thermal expansion mismatch of
CrB2 and B4C for increasing toughness.243,248,256
Similarly addition of Al2O3 enhances the sintering
kinetics of boron carbide due to a liquid phase
formation at 1950uC.249 Jianxin and Junlong271 have
studied the effect of TiC content on the microstructure, mechanical properties and sand erosion rate
of B4C/Al2O3/TiC composites. Addition of TiC

increased the hardness of the composite and the
hardness had direct influence on the erosion rate of the
nozzles. The addition of rare earth (RE) oxides such as
Y2O3, La2O3 reduces the sintering temperature due to
the formation of a liquid phase near the yttrium
aluminate composition (60 wt-%Y2O340 wt-%Al2O3,
melting point 1870uC).251 Pore free sintered boron
carbide materials with high strength (700800 MPa)
and fracture toughness (3?63?9 MPa m1/2) have been
prepared by low pressure hot pressing with the addition
of BN/AlN and oxide binder (RE oxideAl2O3).252
Additives such as CrB2, Al2O3, Y2O3, La2O3 etc. bring
down the sintering temperature of B4C due to liquid
phase formation. The reaction products formed are
boride of the respective oxide, which enhances the
mechanical properties. Addition of TiC with other
oxides increases the hardness and erosion resistance of
B4C composite.
A number of new processing methods are envisaged to
produce materials with designed structure and properties. A machinable B4C/BN nanocompoisite has been
fabricated by hot pressing microsized B4C particles
coated with amorphous nanosized BN particles.254 The
hardness of composite decreased with increase content
of BN while the machinability improved significantly. A
composite with .20 wt-%BN content exhibited excellent machinability.272 The surface hardness and wear
resistance of this composite has been improved by
silicon infiltration process.255 Combination of SHS technique with hot pressing (called combustion hot pressing)
has been used to prepare a composite, containing B4C
and SiC formed by reaction among Si, B and C, in the
form of interlocked matrices with very low porosity and
uniform microstructure.273 Graded porosity B4C materials can be produced by a layering approach using
different size distributions of B4C powders in the green
state, and then densifying the layered assembly by hot
pressing at 1900uC.274 Cobalt as sinter additive has also
been attempted for hot pressing of boron carbide
powders with 5 wt-%TiC at temperatures ,1500uC
and a high pressure of 56 GPa.275
Hot isostatic pressing (HIP)

The HIP process, originally known as gas pressure
bonding, uses the combination of elevated temperature
and high pressure to form/densify raw materials or
preformed components. The application of the pressure
is carried out inside a pressure vessel, typically using an
inert gas as the pressure transmitting medium with or
without glass encapsulation of the part. A resistance
heated furnace inside the vessel is the temperature
source. Parts are loaded into the vessel and pressurisation occurs usually simultaneously with the heating. The
high pressure provides a driving force for material
transport during sintering which allows the densification
to proceed at considerably lower temperature in
comparison to that of traditional sintering. In addition,
particularly during the initial stages of the process, the
high pressure induces particle rearrangement and high
stresses at the particle contact points. A virtually pore
free product can be produced at a relatively low
temperature. The pressure level used in the HIP process
typically is 100300 MPa, as compared to 3050 MPa in
uniaxial hot pressing, and the isostatic mode of
application of pressure is generally more efficient than
2010
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Suri et al.
23 B4C specimen pressureless sintered and hipped at

2150uC and 310 MPa to 99?1% relative density:279 reprinted with permission from Materials Research
Society, J. Mater. Res., 2005, 20, (8), Fig. 6 in p. 2115
the uniaxial one.276,277 Larsson et al.278 have studied the

effect of addition of boron, silicon and silicon carbide
while hot Isostatic pressing boron carbide at 1850uC for
1 h under a pressure of 160 MPa. Addition of boron was
found effective in reducing the pores and graphite
inclusions and improved particle erosion resistance.
Boron carbide (100% TD) could be obtained by a
combination of pressureless sintering and post-HIP at
2150uC for 125 min under 310 MPa of argon pressure.279,280 The combination of pressureless sintering
and post-HIP is gaining importance for fabrication of
dense bodies with higher densities, lower graphite
contents and significantly higher Vickers hardness than
commercially hot pressed B4C.279281 Elimination of
residual porosity and significant improvements in
flexural strength, elastic constants and wear resistance
were observed with the addition of 1 and 3 wt-%C in the
above process.282 Fully dense and very fine grained
boron carbide has been prepared by the fabrication
route, injection moulding/pressureless sintering (2175uC)/
post-HIP (200 MPa, Ar) from B4C doped with 4 wt-%
carbon black.283 Near net shape with full density can be
achieved by HIP.284286 Figure 23279 shows the microstructure of post hipped boron carbide to full theoretical
density. Equiaxed uniform size grains and thin grain
boundary are the special features of this material with
very high hardness.279281 A patented process explains
the preparation of boron carbide shapes containing
metallic diborides (of Ti, Zr, Hf, V, Nb and Ta), sintered
in the temperature 2100 to 2200uC to give a density of
2?47 g cc21, which on further hot isostatic pressing at
2100uC under an argon pressure of 200 MPa to achieve
a theoretical density of 2?56 g cc21.219
Porosity severely degrades the ballistic properties of
ceramic armour as it acts as a crack initiator. Sintering
aids generally degrade hardness and ballistic properties.
Therefore, boron carbide protective inserts for personal
armour is hot pressed to minimise porosity (y98%
relative density), yielding acceptable performance. Posthipping of pressureless sintered boron carbide is gaining
importance for this purpose. This will not only yield
lighter weight armour but also enable forming of
complex shapes.
Major equipments needed for pressureless sintering
are cold compaction press and sintering furnace. For hot
pressing, a graphite die is assembled between the rams of
32
2010
VOL
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NO
the press and heated by the furnace surrounding it.

Multi cavity dies are used for increasing the rate of
production. In HIP the whole equipment has to be
designed for high temperature and high pressure
operation. This puts a limitation on the size of the
equipment and the number of compacts that can be
fabricated at a time. Compacts produced by pressureless
sintering generally needs a finishing process of surface
grinding and end finishing to obtain desired shape and
size. Hot pressed objects also undergo surface finishing
operations at times to remove any contamination from
the die material. Hipped compacts do not need any
further processing and can be directly used.
Manufacturing costs and throughput of pressureless
sintering with post-HIP are attractive compared to hot
pressing.281
Spark plasma sintering

Conventional pressure assisted consolidation techniques, such as hot pressing, hot isostatic pressing, etc.,
require long processing time and high temperature in
order to produce high density parts. In order to
minimise expensive machining, the powder densification
process must be capable of near net shaping. One such
process and the apparatus for rapid bonding of ceramic
materials have been patented by Yoo et al.287 The
materials to be consolidated are placed in a graphite die
and punch assembly. The driving force for densification
is provided by passing current directly through the
particle material, with simultaneously applying high
shear and high pressure in separate steps. High shear
force in combination with pulsed electric power is
initially applied to the particle material to generate
electrical discharge that activates the particle surface by
evaporation of oxide film, impurities and moisture.
Subsequently bonding is accomplished by resistance
heating at the contact points between the activated
particles in the presence of high pressure. The time and
temperature required for consolidation is lowered as
high current density is applied in addition to high shear
and high pressure (up to 2000 MPa) which leads to
localised heating and plastic deformation at interparticle
contact areas. The rapid sintering which preferably lasts
for less than a few minutes prevents grain growth and
allows the particles to retain their microstructure. Spark
plasma sintering (SPS), plasma activated sintering,
plasma pressure consolidation/P2C and instrumented
pulse electrodischarge consolidation are the different
names given for the same process.
Ghosh et al.52 have consolidated submicrometre sized
commercial boron carbide to near theoretical densities
using plasma pressure compaction technique. The
densities obtained at 1750uC by the application of
88 MPa pressure in 2 and 5 min were 96 and 99?2% TD
respectively. The average grain size of these compacts
was 1?6 and 2 mm. Optical micrograph (Fig. 24)52
reveals nearly equiaxed fine grained microstructure.
The hardness and fracture toughness values were in
the range of 25?41 to 27?45 GPa and 3?22 to
3?61 MPa m1/2 under static testing conditions.
Addition of graphite and TiB2 do not aid in consolidation of B4C by this method. Addition of small amounts
of Al2O3 and Fe has been found to be effective in
achieving higher densities by SPS of B4C due to
formation a liquid phase.288290
Suri et al.
24 Microstructure of boron carbide densied by SPS at

1750uC for 5 min, showing nearly equiaxed ne
grained microstructure:52 reprinted with permission
from Wiley-Blackwell, J. Am. Ceram. Soc., 2007, 90,
(6), Fig. 4 in p. 1853
In situ synthesis and densification
Influence of temperature on synthesis and consolidation

has been studied by Tamburini et al.113 Formation of
B4C commences at y1000uC and is complete by 1200uC,
with a hold time of 10 min. Significant densification
occurs above 1600uC, but the material shows evidence of
extensive crystallographic disorder due to twins which
however decrease at higher temperatures. Kodera
et al.291 while heating B-C powders by SPS have
observed that, formation of B4C starts at 1300uC,
consolidation with twins initiates at 1600uC and 98%
density obtained at 1900uC. Heian et al.106 have also
noted similar structural defects in the material prepared
by mechanical activation followed by field assisted
combustion. Wang et al.292 have noticed that B and C
begin to react from 1300uC and the product was B rich
boron carbide (B4zxC) and free C. With increasing
temperature C atoms diffused into B4zxC lattice,
resulting in the reduction of free carbon content and
decrease in lattice parameters of B4zxC. Densification of
the synthesised boron carbide occurred from 1700 to
1900uC. Simultaneous synthesis and densification of
B3?5C, B4C and B4?5C by spark plasma sintering has
shown that carbon free boron rich compounds are
formed in the temperature range 13001600uC and
consolidation occurs above 1700uC.293
Fabrication of functionally graded B4C cermets
Continuous functionally graded boron carbide aluminium cermets have been prepared by spark plasma
sintering of B4C from boron and carbon followed by
infiltration of aluminium.294 This processing route
results in a material with very promising properties
and interesting microstructural features. Hardness profile of functionally graded material before and after Al
melt infiltration is shown in Fig. 25.294 A B4C/Cu graded
composite as plasma facing component for fusion
reactors with performance better than nuclear grade
graphite has been prepared by rapid self-resistance
sintering under ultra high pressure.295
Microwave processing
Microwave sintering has the advantages of uniform and
rapid heating since the energy is directly coupled into the
specimen rather than being conducted into the specimen
25 Hardness versus position prole of functionally

graded boron carbide with and without Al inltration:294 reprinted with permission from Elsevier, Mater.
Sci. Eng. A, 2008, A488, Fig. 8 in p. 337
from an external heat source. Enhanced densification

and finer microstructures, not feasible in the conventional furnaces are possible through the use of microwave systems. The sample size and shape, the
distribution of the microwave energy inside the cavity,
and the magnetic field of the electromagnetic radiation
are all important in heating and sintering.296 Literature
on microwave sintering of boron carbide is scarce. One
of the recent articles describes the behaviour of B4C/SiC/
Al mixtures during microwave heating in air. A dense
composite with B4C skeleton and the voids filled with
the reaction products of Al and B4C were obtained. SiC
was not attacked by oxygen and was able to contribute
to matrix toughness. This material with low specific
gravity and high hardness is attractive for use in
lightweight armour.297 One can expect more research
using microwave heating as and when bigger size units
with higher power ratings become available in the
market.
A novel floating zone method has been adopted for
preparing directionally reinforced B4CTiB2 composite.298 Temperature dependence of the bending strength
of this composite was evaluated in the temperature
range 251600uC. With increasing temperature, its value
decreases to 120 MPa at 800uC and then increased to
230 MPa at 10001400uC. Even at 1600uC, the bending
strength was as high as 200 MPa.298 The development of
non-aqueous gel casting process for preparation of B4C
Al composites has been reported by Zhang et al.299
Conclusions
The understanding of the crystal structure of boron
carbide has been evolving over the years and even today
cannot be said to be fully elucidated. Carbothermic
reduction of boric acid has been the commercial method
for the production of boron carbide in spite of the
shortcomings. Need of the hour in carbothermic reduction is process modelling, which will greatly help in
tuning the process to achieve improved productivity and
uniform quality. Though a continuous method has been
established for the production of SiC,300 a similar
method has to be adopted for B4C also. Solgel method
appears to be a promising technique for production of
suitable fine boron carbide powders for direct consolidation. Vapour phase synthesis, still in laboratory scale,
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is an attractive process for the preparation of submicrometre sized powders, whiskers, etc. Though thermodynamic models based on Gibbs free energy
minimisation have been used to predict experimental
conditions, models based on mass transfer and kinetics
in addition are needed to understand the deposition
mechanism and the growth process. Boron carbide
based coatings by CVD methods for various semiconducting applications such as diode, transistor, thermoelectric converter, thermocouple, neutron sensors, etc.
are gaining importance and the use of boron carbide in
this field will increase manifold in the coming years. In
addition to the established uses, the future of boron
carbide will depend on the possible production of
micrometre/nanosized powders, whiskers and advanced
coating techniques to meet the varying demands.
On consolidation, the research so far has been focused
on reducing the sintering temperature, inhibit grain
growth and improve the mechanical properties. Carbon
has been the chief architect of these improvements. Additives based on carbides/borides/nitrides are also found to
be effective in obtaining a fine grained structure with
higher fracture toughness/flexural strength. Hot pressing
and HIP have remained the main densification methods
for production of pore free pure boron carbide due to their
ability to achieve near theoretical density without grain
coarsening. The process of silicon impregnation into a
sintered porous boron carbide body produces a very high
dense compact with improved mechanical properties due
to the presence of fine SiC particles. Post-hipped pressureless sintering is gaining importance for manufacture
of complex shapes with fine grains especially for armour
material. Production of nanosized particles followed by
SPS for consolidation will revolutionise the method of
B4C component manufacture. The mechanism, microstructure and properties of compacts by SPS technique are
yet to be fully understood. Various available methods of
powder production and consolidation techniques have
been exploited for fabrication of boron carbide components with tailor made properties.
B4C to be considered as high temperature structure
material should have good thermal and oxidation
resistive properties. Detailed investigations on oxidation
characteristics of B4C at high temperatures have been
carried out by Steinbruck et al.301,302 and others.303,304
Higher oxidation stability of B4C with the addition of
Zr, Cr and W borides have also been reported by Radev
et al.305 Serious efforts on oxidation prevention of boron
carbide at high temperatures and improvement of
thermal properties have not been attempted. It may be
worthwhile to investigate composites with silicides and
RE borides. With excellent dielectric properties, thermal
and chemical stability, and erosion resistance in high
intensity laser beams, BNB4C composite materials
could find a unique place for high temperature applications.306 From the point of view of application, boron
carbide has established as the material for abrasive
applications, neutron absorber and armour material. Its
use in electronic industry and high temperature applications will see a higher growth in the coming years.
A recent study regarding road map for advanced
ceramics provides guide lines for future investments.307
1. Development of innovative process technologies to
transfer new knowledge on functional and structural
properties into ceramic materials and devices.
34
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2. In the long run, usage of tailor made powders

(complex composition, compositional gradient in particle, well defined particle shape) and reliable usage of
nanoscale powders will become more important.
3. Techniques for near net shape forming should be
considered a field for fruitful further activity.
All these points are truly applicable to boron carbide
also.
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Synthesis and consolidation of boron carbide: a review

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absorption capacity of boron carbide can be increased

Structure of boron carbide

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