Indian Journal of Engineering & Materials Sciences

Vol. 13, April 2006, pp. 129-134

Sintering of boron carbide under high pressures and temperatures

S K Singhal & B P Singh*
Division of Engineering Materials, National Physical Laboratory
Dr K S Krishnan Road, New Delhi 110 012, India
Received 10 January 2005; accepted 25 January 2006
Sintered compacts of boron carbide were prepared by subjecting fine powder of boron carbide to high pressures and
temperatures (5-6 GPa, 1000-1500C) in the presence of a suitable binding material, namely TiC (5wt.%) or Co (5wt.%).
The composites prepared by this method showed a microhardness of about 2800 kg/mm2, which is very close to the
microhardness of pure boron carbide. The compacts were characterized using scanning electron microscopy, and X-ray
diffraction techniques. SEM study showed that the grains of boron carbide were uniformly distributed throughout the
binding material and no grain growth was observed in the composites. Although composites of diameter 6.0 mm and 2-3
mm thickness are synthesized in this method, the process can be up-scaled for producing large size (12 mm diameter)
composites required in various cutting tools and other applications.
IPC Code: C04B 35/563

Boron carbide (B4C) is a superhard abrasive material

with a microhardness of about 3000 kg/mm2 which is
next only to diamond (9000 kg/mm2) and cubic boron
nitride (4400 kg/mm2). Its hot hardness is even better
than diamond and cubic boron nitride. Because of
high hardness it is extensively used as a lapping agent
in place of diamond. It is also used for polishing high
speed steel and carbide tip tools although its reaction
with many metals under high-temperature conditions
prohibits its use as a die material for wire drawing. It
is reported that the development of hard metal cutting
tools and high speed steels could not have been
possible without the availability of boron carbide as a
grinding medium. Boron carbide is brittle and not
especially impact resistant. It is, therefore, often used
after shrink finishing parts into metal sleeves to
maintain forces on the parts. Apart from machining
operations sintered B4C finds wide applications as
sand blasting nozzles and hard ceramic bearings. In
aerospace industry boron carbide due to its capability
to generate tremendous amount of heat (12400
kcal/kg) in combination with oxygen is finding use as
a rocket propellant. In nuclear industry it is well
accepted as a control and shielding material for
neutrons due to its favourable absorption
characteristics. The presence of strong directed
covalent bonds in the compound lattice determines its
physico-mechanical properties and extraordinary
__________________
*For correspondence (E-mail: [email protected])

chemical stability. Commercially, it is produced by

reacting and fusing boric oxide and carbon in an
electric arc furnace. However, not much information
is available for producing the dense polycrystalline
sintered boron carbide because of the proprietary
nature of this material. One method of making the
dense polycrystalline boron carbide is by hot pressing
(including hot isostatic pressing)1. In some cases
densification is conducted by hot pressing (19002200C at 0.02-0.04 GPa for 15-45 min) in graphite
dies under vacuum or argon atmosphere. To prevent
reaction with the mold, which can result in damaged
parts and dies, a BN coating is used on the inner mold
surfaces. However, this process is expensive and
limited to providing simple shapes. B4C can also be
sintered to about 93% of theoretical density by
combining fine powder of boron carbide with the
addition of small amount of carbon. In this case
powders of extremely small particle size are required
to obtain high density. Sintering can be done in
induction or resistance heating furnaces in an inert
atmosphere. Sintering aids, e.g., SiC have been found
to enhance sintered densities. However, hot pressing
limits the size and complexity of shapes, which can be
produced, and to shape these diamonds grinding is
used. In this method the pressure-less sintering is
normally achieved by sintering the material at about
2000-2500C either directly or with the aid of some
suitable binders selected from the carbides of group
IV-VI (Ti, V, W, Cr)2-17, but in most of cases the

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INDIAN J ENG. MATER. SCI., APRIL 2006

relative densities of the as-sintered materials do not

exceed 93% of theoretical density (2.51 g/cm3). It is
well known that the use of high-pressure powders of
hard materials (diamond, cubic boron nitride and
silicon nitride) can be effectively and efficiently
sintered into a large size hard and tough mass at
relatively lower temperatures either directly or with
the use of suitable binders. The binding materials
generally used in case of diamond or cBN are the
carbides, nitride and silicides of Ti, V, W and Cr. All
these binding materials have a high hardness, melting
temperature, and thermal conductivity and impart
almost the desired properties in the sintered compacts
as required in cutting tools and other applications.
Usually, a small amount of some metals such as Al,
Co and Ni is added to these binders in order to impart
sufficient toughness in the composites. Therefore, we
have undertaken this work of producing the sintered
composites of B4C under high pressure and
temperature with the aid of titanium carbide and
cobalt as the binding materials.
Experimental Procedure
The high pressure sintering of boron carbide
samples was carried out in a 200-ton cubic press of
H.Tracy Halls design. This press is capable of
generating pressures up to about 6 GPa in a
pyrophyllite cubic capsule of 16 mm edge. A
schematic diagram of the cube in a 200-ton cubic
press is shown in Fig. 1. A through-hole of 8 mm was
drilled in the pyrophyllite cube to contain the
experimental materials. The sample was heated
indirectly by passing a heavy current drawn from a
low-voltage a.c. source through a graphite sleeve
surrounding the sample. A high-current step-down
transformer provided the low-voltage a.c. source. The
pressure calibration was carried out using standard
fixed points of phase transitions of Bi (I-II) at 2.54

Fig. 1Schematic diagram of the cube in a 200 ton cubic press.

GPa, Yb (fcc-bcc) at 3.9 GPa and Ba (I-II) at 5.5 GPa.

The temperature was calibrated in terms of electric
power input in watts using a Pt-Pt/Rh10 %
thermocouple placed at the center of the reaction cell.
Commercially available B4C powder (5-10 m, NRD
corporation, Japan) was homogeneously mixed with
either 5 wt.% of TiC powder (2-5 m, NRD
corporation, Japan) or 5 wt.% of Co powder (< 2 m,
Aldrich Chemical Company, USA). The mixture was
facilitated by the addition of a small quantity of
methanol, which was later removed by heating the
powder to 200C. The powder mixture was pressed
into a disc of 6 mm in a carver press using a steel die
and punch at a pressure of about 0.3 GPa and packed
in a reaction cell as shown in Fig. 2.
It has been found that generally a thin layer of
boric oxide is formed on the surface of boron carbide
fine powder, which limits its densification. Therefore,
it is necessary to suppress the detrimental role of boric
oxide, which could be done7 either by heating it at
temperatures higher than 1300C in presence of
amorphous carbon so that any small amount of boric
oxide can be eliminated as indicated in the following
reaction:
2B2O3 + 7 C B4C + 6 CO
There are a number of ways of introducing carbon
into boron carbide powders. One method uses the
pyrolysis of phenol formaldehyde resin at
temperatures higher than 600C which on
decomposition gives amorphous carbon and removes
B2O3 as indicated in the abovementioned reaction. In
the other method MC type carbides was added to the
reaction charge (M denotes a transition metal of
groups IV-VI).
B4C + 2MC 3 C + 2 MB2

Fig.2Reaction cell assembly used to sinter boron carbide.

SINGHAL & SINGH : SINTERING OF BORON CARBIDE

From the experimental results as observed by XRD

analysis it appears that this is a temperature dependent
reaction and the minimum temperature required is
about 1000C or higher. This was confirmed by the
very low peak intensity of carbon as observed in the
B4C compacts sintered at 5.5 GPa and 1000C. The
peak intensity of carbon was relatively high as
observed in the B4C composites sintered at 5.5 GPa
and 1300C. The X-ray diffraction pattern of the
starting boron carbide powder used in the present
study is shown in Fig. 3. It can be seen from this XRD
pattern that most of the peaks corresponding to B4C
are present. Two series of experiments on high
pressure sintering of boron carbide were carried out.
In the first series titanium carbide was used as the
main binding material and in the second series of
experiments cobalt powder was used as the binder.
B4C composites synthesized with the use of TiC are
labelled as Type A and those sintered using cobalt
binder are labelled as Type B. Different weight ratios
of the binders (5-10 wt.%) was used in the
compaction of B4C. In both cases it was found that
optimum value of hardness is obtained if B4C and
TiC/Co was used in a ratio of 95 : 5 wt.%. In the
following the results of characterization of these
compacts using X-ray diffraction technique, scanning
electron microscopy, microhardness measurement are
described.

131

be seen that the observed XRD patterns demonstrate

the presence of B4C and TiC crystalline phases.
However, a closer look at the XRD pattern suggests
that in the B4C compacts synthesized at higher
temperatures (1300C, Fig. 4b) a minor phase of TiB2
is also formed as a result of solid state reaction during
high pressure - high temperature sintering. This minor
phase (TiB2) is not present in B4C compacts
synthesized at lower temperatures (1000C, Fig. 4a).
In the case of composite synthesized at 1300C
presence of some peaks of Cg (002) and (101) were
observed with d values of 3.362 and 2.039
respectively presumably due to the reaction of the
sample and graphite heater used to heat the specimen
at higher temperatures. The formation of TiB2 at
higher temperatures could be understood on the basis
of following chemical reaction:
B4C + 2TiC 3 C + 2 TiB2
Formation of TiB2 in B4C composites is not
deleterious in its mechanical properties. Its presence
is expected to improve the mechanical properties as it
is also used as the binding material in the compaction
of hard ceramics.

Results and Discussion

X-ray characterization

Figs 4a and 4b show typical X-ray diffraction

patterns of the sample of Type A synthesized at 5.5
GPa and temperatures of 1000C and 1300C
respectively using TiC as the binding material. It can

Fig. 3X-ray diffraction pattern of pure boron carbide powder.

Fig. 4XRD pattern of a B4C composite sintered at 5.5 GPa

using TiC as the binding material (a) 1000C and (b) 1300C

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INDIAN J ENG. MATER. SCI., APRIL 2006

Fig. 5 depicts typical X-ray diffractogram of B4C

composite of Type B synthesized at: (a) 5.5 GPa,
1000C; (b) 5.5 GPa, 1200C using cobalt as the
binding material. In this case also the major
crystalline phases present correspond to that of the
starting mixture namely B4C and cobalt carbides such
as Co3C and Co2C which were formed during the high
pressure-high
temperature
sintering
reaction.
Formation of carbides of cobalt also improves the
toughness of synthesized B4C composites.
Microstructure evaluation

Fig. 6a shows a typical SEM micrograph of B4C

compact of Type A recorded in secondary electron
emission mode with 0 tilt using 5% TiC as the
binding material and sintered at 5.5 GPa, 1300C. The
black contrast represents B4C grains and the white
contrast represents the binder (TiC). It can be seen
that the binder grains are uniformly distributed within
the B4C matrix lying within the interspaces of B4C
grains, which facilitate the binding of B4C grains. No
appreciable grain growth was observed in these
compacts as revealed from the recorded SEM

Fig. 5XRD pattern of a B4C composite sintered at 5.5 GPa

using Co as the binding material (a) 1000C and (b) 1200C

micrographs. No major cracks or micro-pores were

observed in the investigated composites. However,
some micro cracks were observed occasionally in few
specimens. Similar features were also observed for
Type B B4C compacts which were synthesized using
cobalt as the binder as can be seen in the SEM
micrograph shown in Fig. 6b and sintered at 5.5 GPa,
1200C.
Microhardness measurements and sintering mechanism

The Knoop microhardness of the sintered B4C

compacts was measured under a load of 500 g on a
Zwick 3212 microhardness tester. Prior to such
hardness measurements the B4C samples were lapped
and polished by fine diamond paste to obtain a mirrorlike finish on the surface so that the indentation could
be measured accurately.
Microhardness measurements on B4C compacts of
Type A and B showed a point to point variation of

Fig. 6SEM micrograph of a B4C compact sintered at 5.5 GPa

(a) using TiC, 1300C and (b) using Co, 1200C

SINGHAL & SINGH : SINTERING OF BORON CARBIDE

Knoop hardness on the specimens surface, although

the variation was not large. The samples synthesized
at lower temperatures (1000C) were found to be
relatively soft in their hardness values (1100-1400
kg/mm2) as compared to those sintered at higher
temperatures (1200-1300C). The best B4C compacts
of both the types showed a Knoop hardness value of
around 2800 kg/mm2 which is quite close to the
hardness of pure boron carbide (3000 kg/mm2). In
order to further assess the extent of sintering achieved
in B4C composites synthesized by using TiC and Co
as the binders under high P-T conditions density
measurements were carried out on these specimens.
Table 1 shows the results of these measurements. This
table includes the density of same specimens whose
microhardness values are reported here. It is observed
that in case of Type A specimens synthesized with 5%
TiC binder at 5.5 GPa and 1300C about 99 %
densification (density = 2.57 g/cc) was achieved with
a microhardness value of about 2800 kg/mm2. As
expected there exists a good co-relationship between
the degree of compaction and microhardness. In case
of specimens synthesized at lower temperatures the
measured density values were found to be lower (2.49
g/cc) resulting in samples with less densification of
B4C powders. This result is corroborated with the
observation of lower values of microhardness (about
1400 kg/mm2). Similar observations were observed in
case of B4C composites of Type B with 5% Co as the
binding material with a maximum microhardness
value of about 2500 kg/mm2 at 5.5 GPa and 1200C.
A co-relationship between the microstructure and
the hardness values was observed in synthesized B4C
composites. Lower values of microhardness were
related to the segregation of binders leading to
localized clustering. The small variation of
microhardness on the specimen surface of wellsynthesized compacts is apparently related to
microstructural fluctuations.
The sintering mechanism of B4C composites is
more or less similar to that observed for other super
Table 1The values of density of specimens
B4C Composite
Theoritical Practical % Degree of
density density Diff. compaction
Type A (using 5 % TiC)
P = 5.5 GPa, T = 1000C
2.59
2.49 3.8
96.2
P= 5.5 GPa, T = 1300C
2.59
2.57 0.77
99.2
Type B (using 5 % Co)
P = 5.5 GPa, T = 1000C
2.82
2.77
5
95
P = 5.5 GPa, T = 1200C
2.82
2.79 1.06
98.9

133

hard materials namely diamond or cubic boron

nitride. By sintering one means bonding together a
mass of small particles into a large, coherent piece.
During this process the contact patches between
particles grow and the total volume of the mass
shrinks leading to a sufficiently dense and strong
mass even though some voids may remain. Sintering
of pure B4C is extremely difficult. Due to the high
fraction of covalent bonding (>90 %) pore eliminating
mass transport mechanisms such as grain boundary
and volume diffusion become effective at
temperatures of the order of 2000C. Generally for
pure materials the sintering temperature is about 6070 % that of the melting temperature. As the melting
temperature of B4C is about 2450C, a suitable
sintering temperature will be about 1600C or higher.
Therefore, in case of pressure-less sintering a
temperature of the the order of about 2000-2300C is
required and in case of hot pressing a sintering
temperature of about 1900-2000C is required at a
pressure of about 0.02 - 0.04 GPa under vacuum or Ar
atmosphere. Vacuum or inert atmosphere is necessary
as above 500-600C it starts converting from diamond
structure into the graphite structure. Application of
high pressure and temperature help in densification
and composite formation by particle rearrangement
followed by considerable plastic deformation.
However, as in case of diamond or cubic boron nitride
the sintering of pure B4C is very difficult because of
its high microhardness (3000 kg/mm2). If the sintering
is performed directly without using any binding
material, then the pressure gradient inside the vessel is
expected to be very high. The pressure at the points
where B4C grains are in direct contact with each other
is believed be very high and in other places (most
places) the local pressure is that of the voids. Thus,
because of the presence of these voids the
microhardness of the resultant B4C is expected to be
low unless the synthesis pressure is very high (> 10
GPa). Therefore, the practical problem to this solution
is to use some binders as the sintering aids which not
only make it possible to sinter at lower pressures but
also promote densification and bonding at
temperatures much lower than those required in
pressure less or hot press sintering of B4C powder.
Further, the presence of small quantity of sintering
aids not only help in filling the voids between B4C
grains but also form a strong bond with B4C particles
thereby resulting in a hard, tough and wear resistance
composite. Also presence of small quantity of binder
in B4C compact takes care of the sudden shock

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INDIAN J ENG. MATER. SCI., APRIL 2006

produced at the tool tip when it comes in contact with

the work piece during the machining conditions,
thereby increasing the life of B4C tool.

patterns and microhardness of the B4C composites

reported in this study.
References

Conclusions
Although the composites of boron carbide are
obtained using hot isostatic pressings, the high pressure
sintering is also very effective for producing these
composites as in case of diamond and cubic boron
nitride. Moreover, the microhardness of the composites
produced using high pressure sintering is very close to
the microhardness of pure boron carbide and the
process, therefore, can be used for producing
composites upto about 12 mm diameter required in
various applications. These sizes of composites are
generally used for making various cutting tools.
Acknowledgements
The authors are grateful to the Director, National
Physical Laboratory, New Delhi, for his
encouragement. Sincere thanks are due to Mr K N
Sood and Dr R P Pant and Dr Rajeev Chopra for
assistance in recording the SEM micrographs, XRD

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