Int.

Journal of Refractory Metals and Hard Materials 42 (2014) 185–192

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Int. Journal of Refractory Metals and Hard Materials

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

Influence of spark plasma sintering parameters on densification and

mechanical properties of boron carbide
K. Sairam a,⁎, J.K. Sonber a, T.S.R.Ch. Murthy a, C. Subramanian a, R.K. Fotedar a, P. Nanekar b, R.C. Hubli a
a
Materials Processing Division, Bhabha Atomic Research Centre, Mumbai, India
b
Atomic Fuels Division, Bhabha Atomic Research Centre, Mumbai India

a r t i c l e i n f o a b s t r a c t

Article history: The densification behavior of boron carbide without sintering additives is reported for temperatures in the range
Received 4 July 2013 of 1100 °C to 1800 °C by spark plasma sintering (SPS) technique together with the sintering parameters (Holding
Accepted 5 September 2013 Time and Pulsed DC). The influence of porosity on mechanical properties (hardness, fracture toughness and elas-
tic modulus) of boron carbide prepared by SPS is measured. Pulsed DC current is found to play a dominant role in
Keywords:
the densification of boron carbide and in achieving near theoretical density at lower sintering temperature com-
Boron carbide
Spark plasma sintering
pared to conventional sintering techniques. Hardness, fracture toughness and elastic modulus of fully dense B4C
Pulsed DC are measured as 37.2 GPa, 2.8 MPa.m1/2 and 570 GPa respectively. Microstructural analysis indicates the pres-
Joules heating ence of deformation twins in boron carbide grains.
Mechanical properties © 2013 Elsevier Ltd. All rights reserved.
Microstructure

1. Introduction SPS over conventional sintering techniques are (1) faster heating rate,
which avoids those mass transport mechanisms that do not contribute
Boron carbide (B4C) is one of the candidate materials for many high to densification (2) shorter dwell time, that retains finer microstructures
performance applications due to its combination of attractive properties and (3) DC pulse voltage that contributes for enhanced mass transport
like low density, high hardness, high elastic modulus, high melting through electro-migration [17–22]. The present work was aimed at bet-
point, high neutron absorption cross-section, good thermo-electric prop- ter understanding of processing conditions (time, temperature and
erties and chemical inertness. However, the application of this material is
limited by its poor sinterability due to the existence of high degree of co-
valence of bonds between B and C atoms in B4C. High sintering tempera-
tures close to the melting point of boron carbide is required to achieve a
complete densification of B4C. This high sintering temperature in turn re-
sults in grain coarsening and residual porosities that deteriorate the ma-
terial's performance [1–6]. Under these circumstances, several attempts
have been made to develop high dense compacts by pressure-assisted
compaction techniques like hot-pressing or hot-isostatic pressing with
and without addition of sintering aids [1–3,7–16]. Sintering aid additions
are reported to lower the consolidation temperatures of B4C ceramics,
but at the expense of purity of final product. Purity is of prime concern
for applications in nuclear industries [1,2]. Thus, there is a need of new
sintering techniques which would alleviate the sintering conditions for
attaining dense B4C ceramics without sinter additions. Spark plasma
sintering (SPS) or Plasma Pressure Compaction is one such technique
for densifying any class of materials, especially for materials that are dif-
ficult to sinter with conventional techniques. The presence of plasma in
spark plasma sintering system is still unproven. Specific advantages of

⁎ Corresponding author. Tel.: +91 22 2559 2422; fax: +91 22 2559 5151.
E-mail address: sairamk@barc.gov.in (K. Sairam). Fig. 1. XRD of starting B4C powder and SPS processed full dense B4C pellet.

0263-4368/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijrmhm.2013.09.004
186 K. Sairam et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 185–192

Pulsed DC) in the densification and on mechanical properties of mono-

lithic B4C ceramic by spark plasma sintering technique.

2. Experimental procedure

2.1. Characterization of starting material

Boron carbide synthesized in-house, (B4C, Particle size D50 = 2.4 μm)
was used as a starting powder in the present study. The method adopted
to produce powders was direct elemental reaction of B and C at 1800 °C
under high vacuum condition, its detailed synthesis procedure is re-
ported elsewhere [23]. The B4C powders were characterized for phase
identification by XRD (Cu–Kα, XRG3000, Inel, France) (Fig. 1) and particle
size analysis by Laser Scattering Particle Size Analyzer (1064 liquid, Cilas,
France) (Fig. 2). The chemical composition of the starting material was
analyzed as 77.7 wt.% B, 22 wt.% C and 0.2 wt.% O.

Fig. 2. Particle size distribution of starting B4C powder (tri-modal). 2.2. SPS operation

Fig. 3. Schematic of Pulsed DC waveform showing 5–5 (ms–ms) pulse sequence during the
holding period.
Boron carbide powder was placed in a high density graphite die of in-
ternal diameter 17 mm. A piece of grafoil sheet (0.45 mm thick) was
lined internally in the graphite die and also placed in between powder
and plunger in order to avoid the interaction with the graphite material.
The die set filled with the B4C powder was then placed inside the SPS
processing chamber. A minimum load of 2 kN was applied at the start,
in order to ensure the firm contact of electrodes with the plunger/sam-
ple/die set up. Standard DC pulse ON–OFF sequence (5 ms-5 ms) was
chosen for all the experiments and the pulse was considered as square
waveform type (Fig. 3). The densification was performed in vacuum
chamber between 1100 °C and 1800 °C with an interval of 100 °C and
a soaking time of 15 min at the set temperature. The heating rate
above 1000 °C was maintained as 100 °C/min. Sintering temperature
was measured by focusing the optical pyrometer at the graphite plunger
which is in direct contact with the powder compact as shown in Fig. 4. A
maximum load of 12.5 kN (50 MPa) was applied at a rate of 0.25 kN/s
when the temperature reached the set point. Holding time was
maintained for 5, 10 and 15 min at that temperature. After completion
of experiment, furnace was allowed to cool down to room temperature
and the pellets were ejected from the die. The ejected pellets were
cleaned on both the edges and circumference by removing the grafoil
sheets.

Fig. 4. Schematic of Spark Plasma Sintering (SPS) Facility showing the location of temperature measurement by optical pyrometer.
 K. Sairam et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 185–192 187

Table 1a
Processing conditions and mechanical properties of spark plasma sintered monolithic boron carbide.

Temperature Holding time Pressure ON–OFF pulse sequence Relative density Hardness, HV Elastic modulus, E Fracture toughness, KIC
(°C) (minutes) (MPa) (milliseconds) (%) (GPa) (GPa) (MPa.m1/2)

1100 15 50 5–5 65 0.2 19 –

1200 65.8 0.2 39 –
1300 66.5 0.4 45 –
1400 70.5 0.9 74 –
1500 71.8 2.4 105 –
1600 81.8 6.7 138 –
1700 94.4 32 418 4.3
1800 5 91 25.7 403 5.8
1800 10 96 33.3 447 3.1
1800 15 100 37.2 570 2.8

Note: Every single data point reported in this work represents measurements made from single specimen sintered per processing condition.

Table 1b and scanning electron microscopes (SEM; MB 2300 CT/100, CAMSCAN,

Influence of pulse rate on densification of boron carbide.
UK) respectively. All the reported data points represent the average of
Temperature Holding time Pressure ON–OFF pulse sequence Relative density five measured values.
(°C) (minutes) (MPa) (milliseconds) (%)

1600 15 50 100-1 81
1600 50-1 81.5 3. Results and discussion
1600 10-1 82.7
1600 5-5 81.8
3.1. Effect of processing parameters on densification of B4C

2.3. Characterization of sintered compacts
The density of sintered compacts was measured by Archimedes prin-
ciple based on water displacement technique. Samples were polished
down to 1 μm finish using series of diamond suspensions ranging from
15 μm–1 μm grades (Struers, Denmark). The elastic modulus of the
sintered compacts was measured by ultrasonic pulse-echo technique
(UT 340 pulser receiver system, UTEX Scientific Instrument Inc.,
Canada) using 15 MHz normal beam probe. Hardness and fracture
toughness were measured based on Vickers indentation technique
using 4.904 N load for 15 s (Duramin 2, Struers, Denmark). Anstis meth-
odology [24] was adopted for fracture toughness calculations. Measured
elastic modulus values were incorporated in the fracture toughness cal-
culations. Sintered compacts were chemically etched using a modified
Murakami's solution (15 g K3FeCN6 and 15 g KOH in 60 ml of water)
at 100 °C for about 30 min. Etched and fractured samples were charac-
terized for microstructures using optical (DMI 5000, Leica, Germany)
3.1.1. Temperature
Tables 1a and 1b show the relative densities of various monolithic
B4C samples that were analyzed after interrupted sintering at tempera-
tures varying from 1100 °C to 1800 °C with steps of 100 °C. The sinter-
ability of boron carbide increases with an increase in temperature and
reaches near theoretical density at 1800 °C. Fig. 5 represents the plot
of shrinkage measured in spark plasma sintered B4C samples as a func-
tion of processing temperature. Three different stages were observed in
the densification within the temperature range 1100 °C–1800 °C
(Fig. 5). Densification behavior of B4C was found to be sluggish up to
1500 °C which represents the first stage of sintering. A sudden increase
in density at 1500 °C implies the onset temperature for rapid densifica-
tion of B4C which is in good agreement with the reported literature
data [22]. The second stage (1500 °C–1700 °C) was found to play a
dominant role in the densification of B4C as the slope of densification
plot is steeper which infers higher shrinkage. 94.4%ρth density was
obtained at 1700 °C. The third or final stage of densification was associ-
ated with the elimination of residual porosities and the sample reaches

1800 deg C–15 min

Fig. 6. Scanning electron micrograph of fully dense B4C compact processed at 1800 °C for
Fig. 5. Relative density and shrinkage of spark plasma sintered B4C samples as a function of 15 min showing partially melted structures (indicated by arrow marks) and also reveals
processing temperatures. the presence of twin structures.
188 K. Sairam et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 185–192
Fig. 7. Ram displacement observed at different processing temperatures is plotted as a
function of SPS operation sequence (holding period and cooling). *Note that these curves
do not represent the path of displacement; it is plotted by considering the initial and end
position of Ram at different temperatures with respect to operation sequence.
full density at 1800 °C but at a rate slower than that observed in the
second stage. Passing of high current of the order of 800–1500A causes
direct heating of the powders based on Joule's heating [21]. The contact
1400°C
1600°C
Fig. 8. (a)–(b) (a) Scanning electron micrographs of B4C processed at 1400 °C show open porosities and neck-like regions between the particles and (b) micrograph of B4C processed at
1600 °C indicates discrete densified regions with interconnected porosities.
points between the particles offer high resistance to the current flow
and contribute for increased heating. The temperatures at those local-
ized heating zones would exceed the melting temperature of the
material and the cumulative effect from all such zones results in in-
creased densification at comparatively lower sintering temperatures
and shorter duration than conventional sintering techniques. Micro-
structural analysis (Fig. 6) of sintered B4C reveals the partially melted
structures which are direct evidences for localized heating mechanism
that governs and dominates during spark plasma sintering process.
Kalyanaraman et.al and Dipankar et.al. referred about the contribution
of rapid localized heating in lowering the sintering temperature associ-
ated with the plasma pressure compaction technique [25,26], which is
in good agreement with the present observations.
Ram displacement of SPS was tracked throughout the experiment,
which also indicates three stages of displacement which is in correlation
with that of the densification plot (Fig. 5). As the top ram is static, any
relative displacement of bottom ram along positive or negative direc-
tion from its initial position corresponds to contraction or expansion
of the material, respectively. The net displacement observed during pro-
cessing of B4C samples includes shrinkage from loaded powders and ex-
pansion of graphite plunger due to heating. The calibration experiment
was performed under identical processing conditions using full dense
B4C pellet instead of powder. The true shrinkage behavior of B4C sam-
ples was determined by subtracting the effects that arise from the ther-
mal expansion of graphite plungers. Fig. 7 shows representative ram
displacements corresponding to the SPS operation sequence for the
temperatures 1400 °C, 1600 °C and 1800 °C. The operation sequence
was classified as (a) holding and (b) cooling periods. The B4C powder
 K. Sairam et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 185–192 189

sample sintered at 1800 °C reveals the linear ram displacement in pos-

itive direction that represents continuous shrinkage behavior during
the soaking period. The net relative displacement at 1800 °C was
3.49 mm that represents the shrinkage observed for fully dense B4C
sample. The net shrinkage observed for B4C sample sintered at
1400 °C was found to be very small, which is 0.25 mm that corresponds
to the sample of relative density 70.5%ρth. Fig. 8(a)–(b) shows the rep-
resentative scanning electron microstructures of B4C sintered at
1400 °C and 1600 °C. SEM micrograph of B4C sintered at 1400 °C clearly
indicates the predominance of open porosities and the neck-like regions
between particles. Formation of neck regions indicates the beginning of
densification process that comprises the first stage of sintering. The mi-
crostructure of B4C processed at 1600 °C show the discrete densified re-
gions bounded with interconnected porosities. As discussed, Joules
heating results in rapid rise in temperatures at localized regions that
would contribute towards the formation of dense regions. This fact rep-
resents the methodology or evolution of densification process in spark
plasma sintering.

3.1.2. Holding time

Fig. 9 represents the evolution of B4C densification at 1800 °C with
respect to holding time (5, 10 and 15 min). The density was found to in-
crease rapidly with increasing holding time of sintering operation. It
was observed that within 5 min duration, the density increased to
91%ρth from 80%ρth (Table 1a). This increase in sinterability is due to
faster sintering kinetics under the influence of electric field. The
electro-migration of ions is a prime driving mode behind enhancing
the kinetics of the diffusion process [27]. On further holding to
10 min, density was found to reach up to 96.6%ρth but at a slower
rate, as it involves the closure of intergranular porosities. Fully dense
B4C was attained at the end of 15 min holding at 1800 °C by spark plas-
ma sintering. The density variation with respect to time at 1800 °C is in
good agreement with the net sample displacement observed (Fig. 9). D.
Jianxin et.al. have obtained B4C of relative density 95.5%ρth at 2150 °C by
hot-pressing for 1 h [28]. C. Subramanian et al. carried out pressureless
sintering of monolithic B4C and achieved a density close to 93%ρth at
2375 °C after 2 h [29].

3.2. Microstructural characterization of spark plasma sintered B4C

Fig. 10(a)–(b) shows the optical microstructures of etched B4C and

Fig. 10. (a) Optical microstructures of fully dense B4C (15 min) and b) 96.6% dense B4C
shows the average grain size of the order of 2–6 μm which is close to compact sintered at 1800 °C (10 min) showing the presence of twin boundaries.

Fig. 9. Relative density and shrinkage of B4C sintered at 1800 °C at different holding period
(5, 10 and 15 min).
mean particle size diameter (2.4 μm) of the starting powders. This
clearly indicates that there is no grain coarsening during spark plasma
sintering. Close observation of optical and scanning electron micro-
graphs indicates the presence and predominance of twin structures (de-
formation twins) (Figs. 6 and 10). Scanning electron microscopy image
of fractured B4C surface indicates the transgranular mode of fracture
and also confirms the presence of deformation twins (Fig. 11). Twining
in B4C is reported to occur along rhombohedral planes of the types
{1011} and {1015} [30,31]. In the present study, almost 70% of grains
are found to exhibit twin structures, which are significantly high com-
pared to hot pressed B4C [7]. Recently A. Mukhopadhyay et al. have re-
ported the formation of a second phase TiB in spark plasma sintered TiB2
ceramics. The reason for phase instability was explained by an acceler-
ated reaction kinetics attained by the electric field in SPS [32]. We did
not observe any phase instability in B4C. XRD results (Fig. 1) confirmed
the presence of only B4C peaks in both powder and final compacts. The
increased twin density in the present study is explained by considering
the spark plasma sintering operation. In SPS, the electric field acceler-
ates the densification process and the simultaneous application of load
during the holding period assists in promoting diffusion and also causes
190 K. Sairam et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 185–192

Fig. 11. Scanning electron micrograph of 96.6% dense B4C fractured surface showing
transgranular mode of fracture and also the presence of twin boundaries (indicated by
arrow marks).

particle rearrangement and deformation. This deformation causes the

displacement of atoms from its initial positions and contributes towards
the formation of deformation twins. B4C sintered by SPS at 1800 °C for
10 and 15 min found to exhibit deformation twins in it, whereas no no-
ticeable twins were observed on B4C sample processed for 5 min at
1800 °C. During the initial period (5 min) of sintering, the energy
imparted to the system was consumed for densification process rather
than on deformation, but further increase of holding period (10 and
15 min) causes the deformation. This infers the effect of processing
Fig. 13. Hardness, elastic modulus and fracture toughness of B4C compact sintered at
time on the evolution of twin structures. In the present study, the sam- 1800 °C with different holding periods (5,10 and 15 min.) are plotted with respect to its
ples with relative density greater than 94%ρth show twin boundaries. sample density obtained.
Twin boundaries possess comparatively lower energy interface than
the grain boundaries and were believed to act as an effective obstacle cleavage crack and contribute for material strengthening [33]. The ab-
to the crack displacement. It was reported that the twins in pore free sence or limited twin density observed in hot-pressed B4C could be
hot-pressed B4C acting as an effective barriers for the development of mainly due to the annealing effect arising during longer holding period.

Fig. 12. Elastic modulus and hardness of spark plasma sintered B4C compacts plotted as a function of relative density.
 K. Sairam et al. / Int. Journal of Refractory Metals and Hard Materials 42 (2014) 185–192
Fig. 14. Optical microstructures of fully dense and around 6% porous compacts showing the differences in the crack propagation pattern.
3.3. Mechanical properties of spark plasma sintered B4C
Hardness of spark plasma sintered B4C is reported in Fig. 12. Fully
dense B4C obtained at 1800 °C shows a maximum hardness of 37.2 GPa
which is close to the value (36.4 GPa) reported by B.M. Moshtaghioun
et al. for spark plasma sintered B4C [34]. An abrupt decrease in hardness
from 32 GPa to 6.7 GPa was observed when density decreases from
94.4%ρth to 81.8%ρth. The decrease in density increases the porosity
which in turn is responsible for the decrease in hardness. Hardness mea-
sured for the B4C samples that are processed at 1800 °C for 5, 10 and
15 min were 25.7 GPa, 33.3 GPa, and 37.2 GPa respectively (Fig. 13).
Hardness of B4C measured in the present study (37.2GPa) is compara-
tively higher than the hardness of compacts that were obtained by hot-
pressing (32.5 GPa) and pressureless sintering (25GPa) techniques,
mainly due to its increased sample density [28,29]. This also implies the
benefit of spark plasma sintering over conventional sintering techniques.
Fracture toughness can be determined based on the radial cracks
that are arising from the corners of the indented locations by consider-
ing it as a strength limiting flaws in ceramics [35,36]. Fracture toughness
of fully dense B4C sample was measured as 2.8 MPa.m1/2 and it in-
creases up to 4.3 MPa.m1/2 corresponding to 94.4%ρth density. The
maximum fracture toughness value measured for 91%ρth B4C sample
is 5.8 MPa.m1/2 which is higher than the value reported in the literature.
B.M. Moshtaghioun et al. have reported fracture toughness of
4.8 MPa.m1/2 corresponding to 90.3%ρth B4C sample [34]. This increase
in fracture toughness can be explained based on the differences that
were observed in crack propagation behavior between fully dense and
6% porous compacts (Fig. 14). In dense compact, the crack propagation
is observed to be a straight line path whereas in case of porous compacts
crack propagates in a zig-zag fashion due to crack tip deflection at the
pores. Further increase of pore content hinders crack formation along
the corners of the indent. A slight increase in toughness was observed
with respect to increase in porosity up to 4%, whereas further increase
of porosity does not result in significant improvement in toughness.
Toughness values corresponding to samples containing porosities
around 9% show a maximum, which is close to the values that are
widely reported for B4C with additives [16,36,37].
The elastic modulus of sintered B4C was found to increase with rela-
tive density of the sample (Fig. 12). The presence of porosity in the sam-
ple decreases the inherent strength of the material and thus contributes
for reducing the elastic modulus of the material. Elastic modulus of spark
plasma sintered full dense B4C was measured as 570 ± 20 GPa which is
greater than the elastic modulus of hot-pressed B4C (~96%ρth) 470 GPa
reported in the earlier study [16]. The reason for the difference in elastic
modulus lies in the differences in their relative density [38].
4. Summary
(a). Near theoretical dense boron carbide compacts were obtained
by Spark Plasma Sintering at comparatively lower temperature
191
(1800 °C) and holding time (15 min) than conventional sintering
techniques.
(b). Microstructural observations revealed locally melted structures
at the contact point between the particles, which is a direct evi-
dence for the dominance of Joules heating effect in spark plasma
sintering. Microstructures also show a large presence of deforma-
tion twins in the boron carbide grains.
(c). The sinterability of boron carbide increases with increasing the
temperature. The rapid rise in densification of boron carbide is
observed at 1500 °C.
(d). Increase in holding time increases the density of the boron carbide.
(e). Grain size of sintered boron carbide is measured to be in the range
of 2–6 μm which implies no grain coarsening in the spark plasma
sintered compacts.
(f). Hardness increases from 0.2 GPa to 37.2 GPa as a function of in-
creasing density of boron carbide from 65%ρth to near theoretical
density.
(g). Near theoretical dense B4C exhibits a fracture toughness of
2.8 MPa.m1/2 and it increases with decreasing density with a
maximum of 5.8 MPa.m1/2 corresponding to 91%ρth dense boron
carbide.
(h). Elastic modulus increases as a function of density and reaches
a maximum of 570 GPa corresponding to full dense boron
carbide.
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