Beruflich Dokumente
Kultur Dokumente
a review
A. K. Suri, C. Subramanian*, J. K. Sonber and T. S. R. Ch. Murthy
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
Published by Maney Publishing (c) IOM Communications Ltd
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
boundary between BnC and BnCzC (where 4,n,10),35 Rhombohedral unit cell, consisting of 12-atom icosahe-
synthesis of B4C without free carbon is a great challenge. dra located at the corners and C-B-C linear chain at
Carbon content of boron carbide greatly influences the the diagonal of the unit cell is shown. Within the icosa-
structure and the properties of the compound and hence hedron, six atoms reside in two polar triangles at the
the exact knowledge of B/C ratio of the phase is very opposite ends of the icosahedron and the remaining
important. But the analytical study of B-C system is six atoms occupy equatorial sites: reprinted with per-
difficult due to extreme hardness and chemical stability mission from the American Physical Society, Phy. Rev.
of boron and boron carbide phases.33 Different limits of Lett., 1999, 83, (16), Fig. 1 in p. 3230
homogeneity range are reported by researchers at the
carbon rich side of boron carbide, corresponding to Three types of three-atom chain are envisioned: C-B-
B4?3C (18?8%C),36 B4?0C (20%C),33,34 and B3?6C C, C-B-B and B-B-B. Variation in carbon concentration
(21?6%C).37 Difficulties associated with the estimation changes the distribution of three-atom chains.31 B4C
of free and combined carbon could be accountable for
(20%C) structure consists of B11C icosahedra and C-B-C
these inconsistent results.36 B-C phase diagram showing
chains. As the composition becomes rich in boron,
homogeneity range from 8?8 to 20 at.-%C, as generated
carbon of the B11C icosahedra is retained, while one of
by Bouchacourt et al.34 is presented in Fig. 1.
the carbon atoms on the C-B-C chains is replaced by
Crystal structure boron. Near the composition B13C2, the structure
consists of B11C icosahedra and C-B-B chains. On
The most widely accepted crystal structure of boron
further carbon reduction, some of the B11C icosahedra
carbide is rhombohedral, consisting of 12-atom icosahe-
dra located at the corners of the unit cell. Schematic are replaced by B12 icosahedra retaining the C-B-B
diagram of the structure of boron carbide is presented in chain.40,42 Carbon-boron bonds present in the three
Fig. 2.38 The longest diagonal of the rhombohedral unit atom chains are much stronger than boron-boron bond
cell contains three atom linear chain (C-B-C). Each end in icosahedra.40 The inter-icosahedra bonds are stiffer
member of the chain is bonded covalently to an atom of than the intra-icosahedra bonds.43
three different icosahedra.31 In general, icosahedra Conflicting views still exist concerning the nature of
consist of 11 boron atoms and one carbon atom. The site occupancies. A model based on early X-ray dif-
locations of carbon atoms within different icosahedra fraction data44,45 proposed that the B4C composition is
are not ordered relative to one another. The icosohedral made up of B12 icosahedra and C-C-C chains. However
configuration is the result of a tendency to form three- later studies38,40–42,46,47 based on improved X-ray and
centre covalent bonds due to deficiency of valence neutron diffraction, nuclear magnetic resonance studies,
electrons of boron.39 Two crystallographically in- theoretical calculations and vibrational spectra indicate
equivalent sites exist in the icosahedron. Six atoms that the structure consist of B11C icosahedra and C-B-C
reside in two polar triangles at the opposite ends of the chains. Even among those who favour B11C icosahedra
icosahedron and the remaining six atoms occupy and CBC chain model for 20 at.-% (B4C), there is
equatorial sites. The atoms at polar sites are directly disagreement on the structural changes that occur in
linked to neighbouring icosahedra via strong two-centre boron carbides, as the carbon content is decreased
bonds along the cell edges. The atoms in equatorial sites towards 13 at.-% (B13C2). Some workers46,48 propose
either bond directly to other icosahedra through three- that carbon atoms are removed from the icosahedra to
centre bonds or to chain structures.40,41 Most of the form B12 icosahedra, while others40,42,49 propose that
icosahedra have a B11C structure with the C atom placed carbon atom is replaced from three atom chains. Owing
in a polar site, and a few percent have a B12 structure or to similarity of boron and carbon in electron density and
a B10C2 structure with the two C atoms placed in two nuclear cross-section (B11 and C12), both X-ray and
antipodal polar sites.41 neutron diffraction studies are not very successful in
tent: reprinted with permission from Elsevier, Solid increases with carbon from 185 GPa for B6?5C (13%C)
State Commun., 1992, 83, Fig. 4 in p. 850 to 198 GPa for B4?3C (20%C).54 Fracture toughness and
Young’s modulus also increases with the carbon
unambiguously assigning the exact site occupancies.48 content.1
The concentration of B12 and B11C icosahedra and C-B- Heat capacity of boron carbide increases with
C and C-B-B chains vary and chainless unit cells also decrease in carbon within the homogeneity range. This
occur.50,51 Variation of structure elements B12, B11C, C- increase is due to the change in lattice vibration mode
B-C and C-B-B in boron carbide unit cell with C content produced by reduction of the stiffness of the three-atom
is shown in Fig. 3.51 The carbon rich limit of homo- chain accompanied with a change from C-B-C to C-B-
geneity range which was assumed to contain B11C B.55 Thermal conductivity of B4C (20%C) falls with
icosahedra and C-B-C chains only, also contains 19% C- temperature in the manner characteristic of crystalline
B-B chains. The composition of B6?5C which was ceramics. However, thermal conductivity of boron
attributed to be the most representative structure (B12, carbide with low carbon is relatively less and tempera-
C-B-C) and used for many model calculations has been ture independent, a behaviour more characteristic of
proved to be the least defined structure containing amorphous materials. These differences of thermal
60%B11C and 40%B12 icosahedra. These structural transport can be explained if it is assumed that, the
changes could also explain the abrupt decrease in thermal conductivity is dominated by the transfer of
thermal conductivity between B4C to B6?5C. Saal vibrational energy through the inter-icosahedral chains
et al.46 have recently applied ab initio calculations to rather than within the softer icosahedra. As the C-B-C
evolve the structure of boron carbide for the entire chains are inhomogeneously replaced by C-B-B chains a
composition range. The enthalpy of formation and transition takes place from crystal-like transport to
lattice parameters were calculated and compared with glass-like transport. Moreover thermal conductivity falls
the experimental data. For carbon rich composition because B-B bonds are much softer than C-B
(20%C), B11C-CBC structure and for 13?33%C compo- bonds.40,55,56 Gilchrist et al.57 have found that thermal
sition B12-CBC structure were found most stable. It conductivity of B4C falls from 29 W m21 K21 at room
suggests that carbon atom is gradually replaced by temperature to 12 W m21 K21 at 1000uC. Thermal
boron in icosahedra. This result is contradictory with conductivity increases when 10B isotope replaces 11B in
other researchers who suggest that carbon atom is boron carbide. This is attributed to the increase in the
replaced from chain. At boron rich end, enthalpy and bonding energy per unit mass and the phonon velocity
lattice parameters of B12 BVaC (Va denotes vacancy) as a lighter isotope is substituted for a heavier isotope.58
structure is in good agreement with the experimental Electrical conductivity in boron carbide was studied
values for boron carbide having 7?14 at.-%C. Since the by Wood et al.49 and Matusi et al.55 Charge carriers in
enthalpy of formation of B12 BVaC is positive it is boron carbide are holes which form small polarons and
predicted that B12 BVaC’s composition cannot be move by phonon assisted hoping between carbon atoms
reached by boron carbide and instead, pure boron will located at geometrically non-equivalent sites.49 The non-
precipitate out, which is in agreement with experimental equivalence arises from two sources. First, carbon atoms
phase equilibrium. Radev et al.43 have found that metal can be distributed among non-equivalent sites within
cations can replace a part of boron atoms in icosahedra B11C icosahedra. Second, only a fraction of the available
position and thus improves the stiffness, hardness and positions of inter-icosahedral chain is generally filled by
wear resistance of boron carbide. C-B-C chains. The carbon rich limit (B4C) resembles an
Recent observations by Raman spectroscopy suggest ideal crystal and therefore has the lowest electrical
structural phase transformation and the formation of conductivity.55 Electrical conductivity increases with
localised amorphous phase which is weaker than the temperature, which is the sign of behaviour of a
original crystalline phase under conditions of loading.52 semiconductor. Density of small polaron holes is
independent of temperature but the mobility of holes (vi) liquid phase reactions
increases with temperature. Within the homogeneity (vii) ion beam synthesis
range, charge carrier density and electrical conductivity (viii) VLS growth.
decreases with increase in carbon content. The tempera-
ture dependence of electrical conductivity is essentially Carbothermic reduction of boric acid
independent of carbon concentration.49 Carbon reduction of boric acid and boron trioxide is the
commercial method for the production of boron
Irradiation response carbide. The overall carbothermic reduction reaction
Neutron irradiation of boron carbide results in extensive can be presented as follows
intergranular cracking due to the formation of helium
bubble as per the following equation59–61 4H3 BO3 z7C?B4 Cz6COz6H2 O (2)
10 1 7 4 :
5 B z0 n ?3 Li z2 He z2 6 MeV (1) This reaction proceeds in the following three steps70
Formation of these cracks, which prevent heat conduc- 4H3 BO3 ?2B2 O3 z6H2 O (3)
tion and the atomic disorder resulting in high phonon
dispersion, decrease the thermal conductivity during B2 O3 z3CO?2Bz3CO2 (4)
irradiation.59 The anisotropic precipitation of helium
not only changes the microstructure but degrades the 4BzC?B4 C (5)
mechanical and physical properties as well. When grain
boundary cracking occurs, a large amount of trapped Boric acid on heating converts to B2O3 by releasing
helium is released simultaneously with the occurrence of water. The reduction of B2O3 with carbon monoxide
bulk swelling.62,63 Considerable amount of tritium is becomes thermodynamically feasible above 1400uC. The
Published by Maney Publishing (c) IOM Communications Ltd
produced in B4C by fast neutron irradiation, which is furnace temperature is usually maintained at .2000uC
retained up to 700uC even on annealing and is released to enhance the rate of overall reaction. The process is
only at temperature higher than 900uC.62,64 Copeland highly endothermic, needing 16 800 kJ mol21 B4C.71
et al.65,66 have reported that irradiation of boron carbide Three types of electric heating furnaces, namely
with neutron causes lattice strains due to the formation tubular, electric arc and Acheson type (graphite rod as
of lithium and helium as reaction product as well as resistance element) are used for the production of boron
some atomic displacements. Inui et al.67 have reported carbide. Tubular electric furnaces using graphite tubes
that a complete crystalline to amorphous transition as heating element are in use for carrying out reactions
takes place by electron irradiation with energy .2 MeV for scientific study only. These furnaces are limited in
and at temperature ,163 K. They also found that the size, dependent on the size of the availability of graphite
amorphous boron carbide remains in amorphous state tubes. Hence large scale production is not feasible using
on annealing at 1273 K. They suggested a possibility, tubular furnaces.
that, in boron carbide, the individual B12 icosahedra
Arc furnace process
themselves are not destroyed by electron irradiation but
their regular spatial arrangement in the B12C3 lattice is Electric arc furnace process for making boron carbide
perturbed and is gradually put in disorder with has been patented by Schroll et al.72 in the year 1939,
increasing electron dosage, resulting in an amorphous wherein the mixture of boric acid and petroleum coke is
state.67 Froment et al.59 have noticed that boron rich melted in an arc furnace followed by crushing the
B8C is more resistant to radiation damage compared to resultant product and mixing it with substantially the
B4C and hence becomes a possible candidate for new same quantity of boric acid and remelting the mixture a
absorbing materials. 11B4C is found to be very stable second time. The design and operation of the electric arc
after fast neutron irradiation in reactors. Dimensional furnace for the large scale production of boron carbide
changes and thermal conductivity of 11B4C are substan- has been explained by Scott.73 In the arc furnace
tially smaller than that of 10B4C.68 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
Synthesis of boron carbide product obtained is chunks of melted boron carbide,
Boron carbide was discovered in nineteenth century as a which needs subsequent laborious crushing and grinding
byproduct of reaction involving metal borides. The operations.
purity of boron carbide produced by early researchers
was less than 75% and in 1933, Ridgway69 claimed to Acheson type furnace
have produced crystalline B4C of 90% purity by Acheson type furnaces, where a graphite rod is used as
carbothermic process. Lipp4 has presented a review of heating element, surrounding which the reactants are
boron carbide production, properties and applications charged is also used for production of boron carbide.
in 1965. Spohn70 has also mentioned the synthesis routes Early patents by Ridgway69,74 give the details of the
for boron carbide production and its uses in his article. furnace and the process. Operational details of the
In this section, different routes for B4C synthesis will be Acheson furnace are explained below. Partially reacted
discussed. The methods of boron carbide synthesis are charge from the previous run is assembled around the
classified as: new graphite heating rod. Above this, the new charge
(i) carbothermic reduction mixture consisting of boric acid and carbon is added. On
(ii) magnesiothermic reduction heating, the reaction initiates near the graphite rod and
(iii) synthesis from elements carbon dioxide escapes to the atmosphere through the
(iv) vapour phase reactions charge above. As the reaction proceeds, the charge gets
(v) synthesis from polymer precursors heated by conduction as well as by the heat of the
escaping CO. Boric acid initially loses its water and Process kinetics
converts to B2O3. On further heating, B2O3 melts and Kinetics of the reaction and also the product quality is
forms a glassy film preventing the escape of CO from the strongly influenced by porosity of the charge, type of
reduction zone. The product gases form bubbles and carbon used for reduction, rate of heating and the final
grow in size near or just above the reaction site and as core temperature. Process kinetics, influence of process
the pressure increases, the bubbles burst pushing the parameters and the means of improving the product
charge above. During these bursts some of the partially quality and conversion efficiency have been investigated
reacted charge is thrown out of the furnace and boron by many researchers. Petroleum coke is found to be a
also escapes to the atmosphere in the form of boron better reducing agent than graphite, charcoal and
oxide vapours. These bubble bursts and evaporation activated charcoal.77 Boric acid to coke ratio of 3?3–
losses affect the efficiency of the process considerably. 3?5 is found optimum and at higher ratios, though boron
After completion of the run, the top is broken open carbide free of carbon could be obtained, recovery is
and the boron carbide surrounding the graphite rod is poor. Alizadeh et al.78 have optimised the boron oxide/
manually collected. Operator experience plays a major carbon (petroleum coke) ratio to yield boron carbide
role in identifying the completely reacted product so that with low (0?65%) carbon. Addition of small amount of
less amount of oxides enter the boron carbide portion. sodium chloride (1?5%) is found to be effective in
The reacted product is crushed in jaw crushers and increasing the yield.71,79 Start of formation of B4C has
further ground to finer size. Ground powder is washed been noticed by Subramanian et al.80 at 1200uC by
in water and leached in acid to remove the contamina- thermogravimetric studies on the reduction of boric acid
tion due to grinding media and also the accompanying by petroleum coke in vacuum. Figure 480 shows the
unreduced or partially reduced oxides of boron from the weight change of the charge with temperature up to
reduced product. In each run, only a small portion of the 1400uC. Formation of boron carbide by carbothermic
charge gets converted to carbide and the balance reduction is highly dependent on the phase changes of
material is recirculated in further runs. Some quantity reactant boron oxide from solid to liquid to gaseous
of boron oxides escapes to the atmosphere along with boron sub oxides and the effect of reaction environment
carbon monoxide. Hence in this process, conversion in (heating rate and ultimate temperature).81 Slow heating
each run is low and boron loss is high. As the raw (,100 K s21) of the charge results in the formation of
materials used are cheap and the process is simple, this boron carbide by a nucleation and growth mechanism as
process has been adopted for commercial production. the reaction proceeds through a liquid boron oxide path.
Though the method of raw material charging and Intermediate heating rates (103 to 105 K s21) result in
collection of reacted product could be different in arc the formation of both large and small crystallites,
furnace and Acheson processes, the reaction sequence is indicating the reaction of carbon with both liquid boron
very similar. oxide and gaseous boron suboxides. Rapid heating rates
As temperature is an important process parameter in (.105 K s21) result in smaller crystallite size, indicating
carbothermic reduction process and the heat transfer the occurrence of reaction through gaseous boron
plays an important role in the formation of boron suboxides.
carbide Rao et al.75,76 have devised a method of core Dacic et al.82 have studied the thermodynamics of gas
temperature measurement in boron carbide manufactur- phase carbothermic reduction of boron anhydride. B2O2
ing process. They have analysed the heat transfer and BO are formed by carbothermic reduction of B2O3
process inside the reactor and the effect of it on the according to reactions (6) and (7) and then reduced to B
formation of boron carbide based on the recorded data. or B4C.
Fig. 2 in p. 200
when the reaction takes place in gas phase or the
product could be nanocrystalline B4C. Presence of some
B2 O3 zC?B2 O2 zCO (6) 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
B2 O3 zC?2BOzCO (7)
route is adopted as commercial method mainly because
The effect of the feed composition and temperature on of the simple equipments and cheap raw materials which
the product composition in carbothermic reduction is make this route the most economical. This route is not
shown in Fig. 5.82 A decrease in the partial pressure of only useful for commercial powder production but also
CO facilitates synthesis of B4C by boosting the for the production of nanocrystalline B4C. Details of
generation of B2O2 and BO. experimental studies on carbothermic reduction, giving
Production of boron carbide by carbothermy has been charge composition, processing conditions and product
essentially a batch process. Tumanov83 has reported the quality of boron carbide obtained by various researchers
development of a continuous process for the production are summarised in Table 1.69,72,77–79,83–85,92
of boron carbide, by direct inductive heating of a charge
made of boron oxide and carbon black. An alternate Magnesiothermic reduction of B2O3
reduction method patented by Rafaniello84 explains the An alternate method for the production of boron
process for producing submicrometre size boron carbide carbide is by magnesiothermic reduction of boron
powders. The type of carbon used, method of prepara- anhydride in presence of carbon as given below
tion of the charge mixture and the fast heating rates (70–
10 000uC min21) are responsible in obtaining fine 2B2 O3 z6MgzC?B4 Cz6MgO (8)
powders. Weimer et al.85,86 have designed a vertical This reaction takes place in two steps:
apparatus comprising of cooled reactant transport step 1
member, reaction chamber, heating element and cooling
chamber for the continuous production of submicro- 2B2 O3 z6Mg?4Bz6MgO (9)
metre B4C powder. Modelling of carbothermic reduc-
tion process for the production of boron carbide has not step 2
been attempted by anybody so far.
Preparation of dense articles need fine boron carbide 4BzC?B4 C (10)
powders in micrometre size. The product of conven-
tional process has to undergo series of size reduction The reaction is exothermic (DH51812 kJ mol21) in
processes to obtain such powders. Such grinding opera- nature. As the vapour pressure of magnesium is high
tions contaminate the product necessitating additional at the reaction temperature of .1000uC, a cover gas
purification steps. Availability of nanosized powders will such as argon or hydrogen is used and also the system
not only avoid the grinding operations but also reduce pressure maintained high. The products of the reaction
the temperature of densification substantially. are processed by aqueous methods to remove magne-
sium oxide from boron carbide. The carbide is still
Nanocrystalline boron carbide contaminated with magnesium borides formed as stable
Preparation of nanosized particles of boron carbide is of compounds. This reduction technique yields very fine
recent interest. B4C particles in the nanosize range amorphous powder, which is well suited for use in the
(260 nm) can be prepared by reduction of B2O3 vapour fabrication of sintered products. One method of
by carbon black at 1350uC.87 Above this temperature, controlling the temperature and the particle size of the
yield is low due to loss of B2O3 from reaction mixture. product is by choosing the right size of the reactants.
Addition of cobalt as catalyst is found to be helpful in Post reductive sintering at temperatures 200–300uC
higher than the reaction temperature increases the at 1650–1700uC. Addition of metallic sulphates as catalyst
particle size of the product. Seeding of the charge with has been found to reduce the reaction temperature to
a small quantity (1–2%) of boron carbide has been found 700uC.95 The heat of magnesiothermic reaction is sufficient
to increase the growth of B4C particles and the yield enough for self high temperature synthesis route.
significantly.93 Formation of ultra fine B4C powder from the stoichio-
An early patent by Gray94 explains the process for the metric mixture of H3BO3, Mg and C by self-propagating
production of boron carbide powders by magnesiothermic high temperature synthesis (SHS) has been studied by
reduction of B2O3 or alkali Na2B4O7 in presence of carbon 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 magne-
sium 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 magne-
siothermic 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 293–99 presents a summary of studies
on synthesis of boron carbide by magnesiothermic
7 a perfect icosahedral B4C particle and b rod shaped reduction.
twinned particles by carbothermic reduction of B2O3
(scale bars: 10 mm):91 reprinted with permission from Synthesis from elements
American Chemical Society, J. Phys. Chem. B, 2004, Synthesis of boron carbide from its elements is
108B, Fig. 4 in p. 7653 considered uneconomical due to the high cost of
Table 1 Charge composition, processing conditions and product quality on synthesis of boron carbide by carbothermic
reduction*
Serial
no. Reactants Process type Process parameters Product quality Ref. (year)
elemental boron and hence employed for specialised Mechanical alloying of B–C mixtures followed by
applications101,102 only, such as B10 enriched or very heat treatment is one of the methods being investigated
pure boron carbide. For synthesis of enriched boron for the synthesis of boron carbide. Room temperature
carbide, carbothermic reduction is not suitable due to milling is carried out in planetary mills for prolonged
loss of boron as well as boron hold-up in the furnace duration to activate the powders and the alloyed mixture
and hence this process is the only suitable economical is then annealed to obtain boron carbide. Spark plasma
method. Although formation of boron carbide from its synthesis is a new technique, in which a pulsed high dc
elements is thermodynamically possible at room tem- current is passed through the charge mixture contained
perature, the heat of reaction (239 kJ mol21) is not in a cavity along with the application of uniaxial
sufficient to carry out in a self-sustaining fashion.103 pressure. In this process, the start and completion of
Formation of boron carbide layer slows down further formation has been noted at 1000 and 1200uC respec-
reaction, due to slow diffusion of reacting species tively. Combination of mechanical alloying followed by
through this layer, thus necessitating high temperature spark plasma sintering has been studied by Hian et al.106
and longer duration for complete conversion of the to obtain 95% pure boron carbide.
elements into the compound. For synthesis from Shock wave technique has also been attempted for
elements, boron and carbon are thoroughly mixed to boron carbide synthesis from amorphous boron and
form uniform powder mixture, which is then pelletised graphite powder107 using trimethyl enetrinitramine as
and reacted at high temperatures of .1500uC in vacuum detonator. The resultant product exhibited several
or inert atmosphere. The partially sintered pellet of different morphologies, such as filaments, distorted
boron carbide is then crushed and ground to get fine ellipsoid, plates and polyhedron particles of nanosize.
B4C powder. To achieve a high purity product of B4C, In this technique reactants are kept inside a steel
high purity elemental boron powder produced by fused container which is placed in plastic tube. A detonator
salt electrolytic process104,105 is often used. is placed between container and the plastic tube.
Table 2 Charge composition, processing conditions and product quality on synthesis of boron carbide by
magnesiothermic reduction*
Serial
no. Reactants Process type Process parameters Quality of B4C Ref. (year)
Initiation of explosive detonation was carried out by an desired temperature, pressure and atmosphere.
electric detonator. After the shock treatments, samples Generally hydrogen is present in the atmosphere, which
were recovered by shaving off the container with a lathe. reacts with the halogen forming hydrogen chloride as
In this technique very high heating and cooling rates are per the following reactions
achieved along with high pressure. The chemical
reaction is completed in micro to milliseconds. Hence 4BCl3 zCCl4 z8H2 ?B4 Cz16HCl (11)
this is suitable for the preparation of crystals of various
morphology and non-equilibrium phases which are hard 4BCl3 zCz6H2 ?B4 Cz12HCl (12)
to be produced in thermal equilibrium conditions.
A few attempts have been noticed on the preparation 4BCl3 zCH4 z4H2 ?B4 Cz12HCl (13)
of nanostructure boron carbide from its elements. Wei
et al.108 have prepared boron carbide nanorods by The flow of reactants and other process parameters
reacting carbon nanotubes (CNT) with boron powder at decide the composition and structure of the product
1150uC under argon atmosphere. Chen et al.109 have formed.
synthesised boron carbide nanoparticles by reacting One such set-up for vapour phase reaction is
multiwall CNT with magnesium diboride at 1150uC for described by Bourdeau in his patent.114 The process of
3 h in vacuum. At this temperature, magnesium diboride producing boron carbide by reacting a halide of boron
decomposes and gives elemental boron. Recently Chang in vapour phase with hydrocarbon in the temperature
et al.110 has attempted the preparation of boron carbide range 1500–2500uC has been explained. Clifton et al.115
nanoparticles (200 nm) by direct reaction between described a process for producing boron carbide
amorphous boron and amorphous carbon at 1550uC. whiskers in the size range of 0?05 to 0?25 mm by the
The crystals obtained had a high density twin structures reaction of B2O3 vapours with the hydrocarbon gas
Published by Maney Publishing (c) IOM Communications Ltd
with variation of B/C ratio from particle to particle. between 700 and 1600uC. James et al.116 have patented a
Table 3106–108,110–113 gives a comparative summary of process for the production of boron carbide whiskers
studies reported on the synthesis of B4C from its and the use of catalytic elements to enhance the yield
elements. Synthesis of boron carbide from its elements of the gas phase reaction process. Dieter et al.117 have
is suitable for the production of pure B4C. Though the described a process for the production of boron carbide
cost of production is high due to the high cost of powder of fine size with a surface area >100 m2 g21.
elemental boron, for specialised applications such as in MacKinnon et al.118 have reported that when boron
nuclear industry this method is preferred. trichloride is reacted with CH4–H2 mixture in a radio
frequency argon plasma, boron carbides of variable B/C
Vapour phase reaction ratios are obtained as submicrometre powders, the
Synthesis of boron carbide by carrying out reaction product stoichiometry depending on the reactant
between boron and carbon containing gaseous species composition.
has been extensively studied. This method is gainfully
adopted for the formation of boron carbide coatings and Chemical vapour deposition (CVD)
synthesis of powders and whiskers in submicrometre Deposition of different types of boron carbide films
sizes. Boron halides such as BCl3, BBr3 and BI3 are (B13C2, B4C, metastable phases, highly strained struc-
suitable boron source but BCl3 is the most preferred due tures, etc.) by CVD techniques has been reported in
to its ready availability and low cost. Apart from literature. The actual deposition is controlled by mass
halides, borane (B6H6) and oxide (B2O3) are also useful transfer and surface kinetics, which affects the stoichio-
boron sources. Hydrocarbon gases such as CH4, C2H4, metry and properties of the boron carbide phases grown.
C2H6, C2H2 and carbon tetra chloride (CCl4) are Graphite, single crystal silicon, carbon fibre and boron
employed as carbon source. Synthesis of boron carbide are the substrate materials used for thin film synthesis.
takes place in the reaction chamber, which is kept at a 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)
temperature range of 450 to 1450uC. Substrate tempera- mechanical properties and thermal stability. These
ture has strong influence on the process and product attributes are the result of deposition occurring one
quality. High substrate temperature results in poor atom at a time. Deposition rates in LCVD techniques
adhesion whereas deposition rate is low at low are orders of magnitude higher than that in traditional
temperature. Amorphous boron carbide coating can be CVD. The deposition rate and surface microstructure
obtained at a low temperature of y500uC whereas strongly depend on laser power and hydrogen content in
crystalline film is obtained at higher temperatures the gas phase.127 Control of laser power density allows
.1100uC. Amorphous boron carbide coatings on SiC for codeposition of r-(B4C) and disordered graphite,
have been obtained by CVD from CH4–BCl3–H2–Ar which can be beneficial for tailoring the thermal and
mixtures at low temperature (900–1050uC) and reduced electronic properties of boron carbide.128 The reactive
pressure (10 kPa).119 atmosphere composition is the most important para-
Preparation of boron carbide fibres by the reaction of meter in laser CVD. When the relative amount of
boron halides with woven cloth of carbonisable material carbon to boron in the gas phase is high, a disordered
in hydrogen atmosphere has been patented by Wainer graphitic phase is deposited along with boron carbide
et al.120,121 Jaziehpour et al.122 have prepared boron and when the carbon is low, tetragonal and metastable
carbide nanorods on graphite substrate at 1400uC by boron rich phase, B25C is codeposited with boron
CVD using charge mixture of boron oxide, activated carbide.129 Patterned deposits can be obtained by direct
carbon and sodium chloride. Shu-Fang et al.123 have writing process, in which a pattern of thin lines
grown novel boron carbide nanoropes by CVD using o- deposited on the substrate by moving the substrate
carborane (C2H12B10) as precursor and ferrocene perpendicular to the axis of the laser beam. Fibre
(C10H10Fe) as catalyst. Karaman et al.124 have studied depositions are also possible by moving away the
the kinetics of CVD of B4C on tungsten substrate using substrate parallel to the laser beam axis at a rate equal
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BCl3–CH4–H2 gas mixture. They proposed that two to the deposition rate of the fibre. Direct writing and
major reactions take place during the process fibre growth methods can be combined to produce three-
1 dimensional structures.148
BCl3 ðgÞz CH4 ðgÞzH2 ðgÞ?
4 Plasma enhanced CVD
1 In PECVD chemical reaction takes place after the
B4 C ðsÞz3HCl ðgÞ (14)
4 creation of plasma of reacting gases. The plasma is
generally created by radio frequency (ac) or dc discharge
BCl3 ðgÞzH2 ðgÞ?BHCl2 ðgÞzHCl ðgÞ (15) between two electrodes, the space between which is filled
Reaction rate of boron carbide formation is lower than with the reacting gases. The necessary energy for the
that of dichloroborane formation over the entire range chemical reaction is not introduced by heating the whole
of temperatures (1000 to 1400uC) studied. Schouler reaction chamber but just by heated gas or plasma. The
et al.125 obtained BCx (x>3) phase having whisker-like deposition takes place at lower temperature as compared
morphology by reacting BCl3 and B6H6 at 1000uC on to traditional CVD. Since the formation of the reactive
quartz substrate in presence of hydrogen and nickel. and energetic species in the gas phase occurs by collision
Sezer and Brand126 have written a comprehensive review in the gas phase, the substrate can be maintained at a
on CVD of boron carbide. The mechanical, thermal and low temperature. Hence, film formation can occur on
electrical properties of CVD boron carbides are compar- substrates at a lower temperature than is possible in the
able to other important refractory materials and promise conventional CVD process, which is a major advantage
a wide range of application areas, particularly in the of PECVD.149
nuclear industry. They have also discussed the thermo- Plasma enhanced CVD has been used by many
dynamic modelling used by many researchers and have researchers for the fabrication of boron carbide (B-C)
concluded that the process takes place far from diodes which could accurately detect single neutrons,
equilibrium and that, thermodynamic modelling is not giving very high efficiencies. These diodes have been
sufficient to represent experimental deposition condi- used to fabricate the first real time, solid state neutron
tions. Table 4114–118,127–147 presents a summary of detectors which are more efficient and reliable than any
studies reported on vapour phase reaction synthesis of other neutron detecting semiconductor reported to
boron carbide. date.150 Lee et al.25,151 have fabricated photoactive p-n
Many modifications such as laser CVD (LCVD), hetrojunction diode by PECVD of boron carbide thin
plasma enhanced CVD (PECVD), hot filament CVD films from nido-pentaborane (B5H9) and methane(CH4)
(HFCVD), etc. have been tested for the formation of on Si (111). A B5C/Si(111) hetrojunction diode by a
boron carbide films. synchrotron radiation induced decomposition of ortho-
carborane fabricated by Byun et al.152 has been found to
Laser CVD be comparable with PECVD diodes. Hwang et al.153
In this technique the energy of a laser beam is used to have successfully fabricated and tested a boron carbide/
heat the surface of a substrate to the temperature boron diode on aluminium substrates and a boron
required for chemical deposition. It allows superb carbide/boron junction field affect transistor.
spatial resolution (y5 mm) because the chemical reac- Robertson et al.154 have fabricated real time solid
tions are restricted to the heated zone created by the state neutron detector by PECVD using closo-1,2-
focused laser spot, in contrast to the traditional CVD dicarbadodecaborane. Adenwalla et al.155 have reported
furnace which heats the entire surface of the sub- the fabrication and characterisation of boron carbide/
strate.148 Laser CVD results in deposits with high purity, silicon carbide hetrojunction diodes by PECVD. The
high degree of crystallinity, low porosity, excellent literature is abundant on various possible combinations
of source, method of fabrication, uses, etc. and only a chemical kinetic modelling in understanding the process
few examples are given above. chemistry. Hot filament CVD systems are based on
thermal catalytic cracking of the precursors on the
Hot filament CVD surface of a high temperature filament usually ranging
Hot filament CVD is an attractive technique due to its from 1000 to 2500uC. The substrate materials are usually
simple design and its amenability to fundamental 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. Process Reactants Process parameters Product quality Ref. (year)
1 Vapour phase BCl3zCH4 1900uC; vacuum: Boron carbide crystals 114 (1967)
reaction 5 mm of Hg
2 Vapour phase B2H6zC2H2 Exothermic reaction Amor. porous boron 117 (1977)
reaction and needs to be carbide powder of
ignited only by spark submicrometre size
plug
3 Vapour phase B2O3zCH4 1075uC, 18 h Whiskers length: 115 (1970)
reaction 0.5–4 inch; diameter:
0.05–0.25 mm
4 Vapour phase BCl3zCH4zH2 1650uC, 5 h; vacuum Whiskers length: 50 mm; 116 (1969)
reaction catalyst: VCl4 diameter: 10 mm
5 RF plasma BCl3zCH4zH2 Ar plasma Submicrometre size powder 118 (1975)
assisted synthesis
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6 CVD BCl3zCH4zH2 1350uC; Sub.: carbon Crystalline B4C coating 130 (1996)
fibre
7 CVD BCl3zCH4zH2 1127–1227uC; Sub.: Metastable phases, highly 131,132 (1989)
boron coated Mo, strained microstructure
vacuum
8 CVD BCl3zCCl4zH2 1550uC, 4–5 h, Sub.: Pure long crystalline B4C; 133 (1965)
graphite hardness: 41¡2.7 GPa
9 CVD BCl3zC3H8zH2 850–1000uC, 3–6 h; Amor. coating 134 (1981)
Sub.: graphite cloth;
vacuum: 15–25 torr
10 CVD BCl3zCH4zH2 1300uC,6 h; Sub.: B4C coating 135 (1968)
graphite; vacuum:
10 mm of Hg
11 CVD BCl3zCH4zH2 1300uC, 3 h; Sub.: B4C coating (B: 74 to 76%) 136 (1974)
tungsten, graphite specific gravity of 2.32 gm cm23
12 CVD BCl3zCH4zH2 800–1050uC, vacuum Amor. boron carbide 137 (2006)
13 CVD BCl3zCH4zH2 1000–1400uC; Sub.: Crystalline B4C 124 (2006)
tungsten
14 Laser CVD BCl3zCH4zH2 Laser: CO2; Sub.: Crystalline B4C 128 (1999)
fused silica; Ar pressure:
atmospheric
15 Laser CVD BCl3zCH4zH2 Laser: CO2; Sub.: Crystalline B4C 138 (1996)
fused silica
16 Laser CVD BCl3zCH4/ Laser: CO2 Ultra fine and crystalline B4C 139 (1990)
C2H4zH2
17 Laser CVD BCl3zC2H4 Laser: CO2; Sub.: fused Adherent, crystalline B4C, 127 (2002)
silica, Ar 15–22%C
18 Laser CVD BCl3zCH4zH2 Laser: CO2; Sub.: fused Crystalline B4C and B25C 129 (1997)
silica,
19 Pulsed laser C6H6zBCl3 Nd:YAG laser 14 to 33 nm B4C crystals 140 (1999)
induced CVD encapsulated in graphite
20 Plasma enhanced C2B10H12 1100–1200uC; Sub.: B4C nanowires diameter: 141 (1999)
CVD (orthocarborane) Si (100) 18–150 nm; length: 13 mm
21 Microwave plasma BBr3zCH4zH2 500–600uC; Sub.: Amor. boron carbide large 142 (1990)
assisted CVD graphite composition range (0 to
40 at.-%C
22 Supersonic plasma BCl3zCH4 500–600uC; Sub.: Si Microcrystalline film hardness: 143 (1998)
jet CVD (100), ArzH2 22–32 GPa
23 Thermal CVD BCl3zCH4zH2 1600uC, 3–6 h BCl3: Various composition between 144 (1992)
6–15 mL min21; CH4: B4C and B13C2
2–5 mL min21; H2:
500 mL min21
24 Hot wall CVD BCl3zCH4zH2 1000 to 1400uC; Sub.: Crystalline B13C2, long columnar 145 (1998)
graphite, vacuum grains
25 Hot filament activated BCl3zCH4zH2 2100uC (filament) Amor. boron carbide, high purity 146 (1994)
CVD 450uC (substrate); and good adhesion
Sub.: Si (100), vacuum
26 Electron beam BzC Room temperature; Thin films of crystalline boron 147 (2008)
evaporation Sub.: Si (100) carbide
*CVD: chemical vapour deposition; Sub.: substrate; Amor.: amorphous; RF: radio frequency.
substrate surface temperature is usually ,500uC.146 The by heating ‘amine treated B2O3 fibre’ in inert atmo-
deposition is carried out under high vacuum conditions sphere at 2000–2350uC. Cihangir et al.160 have devel-
to avoid oxygen contamination of the boron carbide oped a method based on sulphuric acid dehydration of
phase. Deshpande et al.146 have obtained adhesive sugar to synthesise a precursor material which on
coating of boron carbide on silicon substrate and the heating to temperature between 1400 and 1600uC
wear resistance of the coated surface was found to be yields crystallised B4C and B4C/SiC composites.
extremely high when tested using a WC/Co ball as the Table 5156–159,161–167 gives the comparative summary of
pin. studies reported on the synthesis of B4C using polymer
Vapour phase synthesis methods are suitable for thin precursors.
film coating of boron carbide and preparation of fine
powder, fibres, whiskers, etc. However the powders Liquid phase reaction
produced by this process are generally non- Synthesis of ultra fine boron carbide powder using liquid
stoichiometric and not suitable for fabrication of dense precursors has been attempted by a few. This method is
products. These methods are best suited for laboratory also known as solvothermal process or coreduction
studies. method. Unlike conventional methods, this can be
operated at much lower temperatures to yield boron
Synthesis from polymer precursors carbide of desired properties. Shi et al.168 have studied
As an alternative to high temperature reaction techni- the formation of ultra fine boron carbide powders by
ques, there is great interest in development of polymer coreduction of boron tri bromide and carbon tetra-
precursors to produce ceramic materials at lower tem- chloride using sodium as reducing agent as per the
peratures. Some of the boron loaded organic com- following reaction
pounds such as carborane (C2BnHnz2), triphenylborane,
Published by Maney Publishing (c) IOM Communications Ltd
Table 5 Charge composition, processing conditions and product quality on synthesis of boron carbide using polymer
precursor
independently controlled, could be advantageously used above. Thakkar et al.176 have synthesised high purity
for obtaining the preferred composition and nature of ultra fine boron carbide powders by reacting B2O3 with
the boron carbide film. Ronning et al.170 have grown methane in a non transferred arc dc thermal plasma
thin film of boron carbide (BxC) by direct ion beam reactor. A recent article177 explains the process of
deposition on silicon using an ion energy of 100 eV at making boron carbide–carbon eutectic containing
room temperature. Todorovic et al.171 have observed the 39 wt-%C by melting B2CN in graphite crucible at
formation of amorphous boron carbide (BxC) by 2600uC.
bombardment of Bz and B3z ions on fullerene. Beam Boron carbide powder is either utilised directly or
energies were in the range of 15 keV for Bz to 45 keV consolidated to dense bodies. Various methods of
for B3z and fluences were between 261014 and densification, the mechanisms involved and the product
261016 cm22. quality are discussed in the following pages. Densi-
fication techniques can be broadly classified as pressure-
Vapour liquid solid (VLS) growth less sintering and pressurised sintering. Atmospheric/
Boron carbide whiskers can be grown by carbothermal reaction/microwave and thermal plasma sintering are
VLS growth mechanism. This mechanism involves the termed as pressureless sintering techniques. The nuances
transport of boron and carbon as gas phase species to a of densification of powder compacts, complexity and the
liquid catalyst metal (Fe, Ni or Co) in which whisker reasons for incomplete densification by pressureless
constituents get dissolved. When the catalyst becomes sintering are discussed in detail by Lange.178
supersaturated with boron and carbon, boron carbide Pressurised sintering can be classified as solid and gas
whiskers precipitate out of the metal droplets. Carlsson compaction methods. Solid compaction methods are hot
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 50–200 nm to 10–30 nm.
Scanning electron micrograph of the nanowires is shown
in Fig. 10.175 A comparative study of various methods 10 Boron carbide nanowires prepared by VLS growth
of boron carbide synthesis is presented in Table 6. with help of iron addition:175 reprinted with permission
Some of the attempts to produce boron carbide from American Chemical Society, Chem. Mater., 2002,
cannot fall into any of the classifications discussed 14, Fig. 5(b) in p. 4405
pressing, spark plasma sintering and super high pressure densification 1870–2010uC and a slow down in densifi-
sintering. Gas compaction methods are hot isostatic cation rate 2010–2140uC. The surge in densification
pressing and high pressure gas reaction sintering. 1870–2010uC 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
Densification of boron carbide evolving oxide gases (BO and CO). Slower densification
In spite of its high temperature strength, application of at temperatures above 2010uC is attributed to evapora-
B4C is rather limited, in real life, due to difficulties in tion and condensation of B4C. Figure 11183 shows the
densification, low fracture toughness and low oxidation changes in weight, dimension and grain size while
resistance beyond 1000uC. Consolidation of B4C is sintering of boron carbide.
complicated due to its high melting point, low self- Densification of boron carbide without deterioration
diffusion coefficient and high vapour pressure. Very high of mechanical properties can be achieved either by using
sintering temperatures are required for densification due a suitable sintering aid and/or applying the external
to the presence of predominantly covalent bonds in B4C. pressure (e.g. hot pressing, hot isostatic pressing).
Boron carbide particles generally have a thin coating of Selection of the additive and the method of consolida-
surface oxide layer which hinders the densifications tion are generally dictated by the end use of the product
process. At temperatures ,2000uC, surface diffusion and the properties that are required. The additive by
and evaporation condensation mechanism occur, which itself or due to in situ reaction with boron carbide would
results in mass transfer without densification. Densi- form a non volatile second phase aiding in densification
fication is achieved only at temperatures .2000uC, by and property enhancement. Hence, selection of the
grain boundary and volume diffusion mechanisms. At additive should be directed towards the formation of a
higher temperature exaggerated grain growth also takes suitable structure providing the correct properties for
Published by Maney Publishing (c) IOM Communications Ltd
place resulting in poor mechanical properties. One more use. Recent or advanced techniques such as microwave/
observation at temperatures .2150uC is volatilisation of spark plasma sintering, explosive compaction, etc. help
non-stoichiometric boron carbide, leaving minute car- to obtain dense products without microstructural
bon behind at the grain boundaries. coarsening. These techniques are presently limited to
Dole et al.179 have observed the microstructure of B4C laboratory scale only. Detailed literature survey on
compacts fired above 2000uC to be highly porous pressureless sintering with or without sintering aids, hot
interconnected structure with clusters of grains con- pressing, hot isostatic pressing, spark plasma and
nected by small neck like regions and separated by large, microwave sintering of boron carbide are presented in
channelled porosity. Grabchuk et al.180–182 have found the following sessions.
that shrinkage starts at 1500uC, recrystallisation above
1800uC and rapid grain growth above 2200uC. At Pressureless sintering
temperatures above 2250uC, the sintered body contains Pressureless sintering is a simple and economic process
,5% residual porosity. Lee et al.183,184 have observed to produce dense compacts. This operation is carried out
the start of densification at 1800uC, rapid increase in in two steps. In the first step green compacts with
Carbothermic reduction H3BO3 or B2O3 PC, graphite, Cheap raw material, High boron losses,
activated carbon suitable for commercial obtained in lump form,
production need grinding for powder
production
Magnesiothermic reduction B2O3 or Na2B4O7 PC, graphite, Fine powder, exothermic Product contaminated
activated carbon reaction, suitable for SHS with Mg, MgB2
process
Synthesis from elements Boron PC, graphite, No loss of boron, good High cost of elemental
activated carbon control over purity and boron
carbon content of product
Vapour phase synthesis BCl3, BBr3, BI3, CH4, C2H4, C2H6, Suitable for thin films, fine
Difficult to produce B4C
B6H6, B2O3 C2H2, CCl4 powder, fibers, whiskers powder suitable for
densification, not amenable
for large scale production
Synthesis from polymer Boric acid, B2O3, Polyvinyl alcohol, Low temperature process High free carbon content,
precursors polyvinyl pentaborane, citric acid, hydroxyl still in laboratory stage
polyvinyl borate, ethyl benzyl alcohol,
decaborane sugar, ethylene
glycol
Liquid phase reaction BBr3, boron CCl4 Low temperature process, Need of reactive metal
suitable for nanoparticles such as Na or Li, new
method of synthesis
Ion beam synthesis Boron Carbon Suitable for BxC Only for thin films, of
academic interest only
Vapour liquid solid growth B2O3 Carbon black Suitable for whisker Need of molten metal
catalyst, of academic
interest only
*PC: petroleum coke; SHS: self-propagating high temperature synthesis.
11 Sintering of boron carbide compact: change in weight, dimension, grain size and coefficient 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
Published by Maney Publishing (c) IOM Communications Ltd
sufficient handling strength are prepared by uniaxial die vanish during high temperature annealing. Vickers
compaction. These green pellets are then fired at chosen hardness and flexural strength of the pressureless
high temperatures in controlled atmosphere. A recently sintered boron carbide samples are in the range 18–
developed new technique, combustion driven compact 24 GPa and 120–200 MPa respectively, which are lower
process, yields much higher green density and strength than theoretical values. One can conclude that, with
than the normal die compaction.185 In this process, high pure B4C, a densification .90% TD is possible only at
pressure generated by ignition of a combustion gas very high sintering temperatures of y2300uC. Such
mixture which raises the pressure in the chamber compacts have a coarse grained microstructure of
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 7.179,183,186–204
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 pressure-
less sintering of 0?8 mm median diameter powders at
2300 and 2375uC are presented in Fig. 12.193 Grain sizes
are in the range 40–100 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 12 Microstructure of pressureless sintered boron carbide
be heated to a temperature where densification can take (0?8 mm) at a 2300uC and b 2375uC showing grains in
place before the microstructure becomes highly coar- range 40–100 mm indicating large grain growth:193 rep-
sened.179,183,188,205 Appearance of twins in the grains is rinted with permission from Elsevier, Ceram. Int.,
characteristic of boron carbide. These twins slowly 2006, 32, Fig. 2(b) and (g) in p. 230–231
Table 7 Powder details, sintering parameters and characteristics of sintered boron carbide by pressureless sintering*
1 B4C FC: 2–4.9; D5052.0 to 10.5 2170 to 2230uC, 15 min, 94.0–95.6 12.0–25.5 2.91–3.19 160–180 186 (1988)
Ar
2 B4C Starck make B/C53.7 to 3.8; 2190uC, 1 h, Ar (up to 94–95 … … … … 188 (2004)
D5050.8; SS: 15–20 2000uC in vacuum)
3 B4C 2250uC 65% Coarse … … … 179 (1989)
B4C D5051 2300uC 70–72% Coarse
B4Cz6 wt-%C SS: 12 2300uC .95% Fine
4 B4C D50(1 2150uC, 15 min, Ar 78 B4C: 6 … … … 189 (1981)
B4Cz3 wt-%C (phenolic resin) SS: 22 96 B4C: 4 3.2 353
5 B4C D50,5 2175uC, 15 min, Ar … B4C: 105 190 (1987)
B4Cz(polycarbosilanez SS: 10.5 95 B4C: 28
phenolic resin510%)
B/C: 4.32 SiC: ,3
6 B4C D50(0.84 2250uC 91.3–92.7 B4C: 2.58– 3.11 … … … 183 (2003)
B4Cz3 wt-%C (phenolic resin) SS: 18.8 2250uC 98.4–98.6 B4C: 2.26–2.4 … … …
B/C53.76
7 B4C 2200uC, 1 h 78.6 B4C: 28 174 191 (2003)
B4C 2250uC, 1 h 82.5 B4C: 50 …
B4Cz3 wt-%C SS: 2.53 2250uC, 1 h 92 B4C: 13 350
B4Cz5 wt-%C 2250uC, 1 h 93 …
B4Cz7.5 wt-%C 2250uC, 1 h 89 …
B4Cz9 wt-%C 2250uC, 1 h 86 …
8 B4C D50<3 2250uC, 2 h,Ar 95.5 19–21 … … 192 (2005)
B4Cz4%C SS: 18.8; O: 1.23%; N: 0.4% 2250uC, 2 h, Ar 97.7 19–21 … …
B4Cz4%B Carbon black: D50520 nm; 2250uC, 2 h,Ar 87.0 18–20 … …
SS: 120
Suri et al.
2010
B4Cz15 wt-%TiB2 96 … 31 2.85 360
B4Cz20 wt-%TiB2 96 B4C: 14 29 2.9 320
B4Cz25 wt-%TiB2 98 … 26 3.05 280
VOL
B4Cz30 wt-%TiB2 98.5 B4C: 10 23 3.4 270
55
1NO
Synthesis and consolidation of boron carbide: a review
19
Published by Maney Publishing (c) IOM Communications Ltd
20
Suri et al.
Table 7 Continued
2010
B4Cz30 wt-% talc 2150uC, 1 h, inert 98 23 2.7
12 B4C 2275uC, 1 h, vacuum 86.63 B4C 26.85 221 (2008)
B4Cz2.5 wt-%ZrO2 B4C: D50<1 89.56 B4C, ZrB2 …
VOL
B4Cz5 wt-%ZrO2 B/C54.09 93.86 B4C, ZrB2 31.68
55
B4Cz10 wt-%ZrO2 ZrO2 reactor grade 95.3 B4C, ZrB2 31.18
95.5 30.19
Synthesis and consolidation of boron carbide: a review
NO
B4Cz20 wt-%ZrO2 93.08 B4C, ZrB2 30.95
1
B4Cz25 wt-%ZrO2 95.82 B4C, ZrB2 31.71
B4Cz30 wt-%ZrO2 92.34 B4C, ZrB2 31.07
B4C, ZrB2
13 B4C 2050uC, 1 h, Ar 72 19 2.0 190 196 (2006)
B4C 2150uC, 1 h, Ar 75 22 2.1 200
B4Cz5 wt-%ZrO2 D5051 2150uC, 1 h, Ar 79 25 2.2 205
B4Cz10 wt-%ZrO2 SS: 14 2150uC, 1 h, Ar 86 27 2.6 210
B4Cz15 wt-%ZrO2 ZrO2z3 wt-%Y2O3 2150uC, 1 h, Ar 97 28 2.9 220
B4Cz20 wt-%ZrO2 D5050.8 2150uC, 1 h, Ar 97 29 3.0 235
B4Cz25 wt-%ZrO2 SS: 16 2150uC, 1 h, Ar 97 27 3.0 260
B4Cz30 wt-%ZrO2 2150uC, 1 h, Ar 98 26 3.1 340
14 B4C 2190uC, 1 h, Ar 62 50 197 (1999)
B4Cz5 wt-%Ti 2190uC, 1 h, Ar 67 …
B4Cz10 wt-%Ti 2190uC, 1 h, Ar 73 …
B4Cz15 wt-%Ti D50 ,1 2190uC, 1 h, Ar 78 …
B4Cz20 wt-%Ti SS: 9–17 2190uC, 1 h, Ar 86 …
TiO2: D50,2 (up to …
1500uC: vacuum)
B4Cz5 wt-%TiO2 2160uC, 1 h, Ar 72 B4C: 10 200
B4Cz10 wt-%TiO2 2160uC, 1 h, Ar 77 TiB2: 5–7 300
B4Cz15 wt-%TiO2 2160uC, 1 h, Ar 88 350
B4Cz20 wt-%TiO2 2160uC, 1 h, Ar 95 420
15 B4C 2190uC, 1 h, Ar (up 71 120 187 (2000)
to 1500uC: vacuum)
B4Cz10 wt-%TiO2 D5055 to 7 73 B4C: 10 200
B4Cz20 wt-%TiO2 SS: 17 75 TiB2: 5 300
B4Cz30 wt-%TiO2 TiO2: D100(2 80 330
B4Cz40 wt-%TiO2 93 400
Published by Maney Publishing (c) IOM Communications Ltd
Table 7 Continued
16 B4Cz0 to 30 wt-%TiO2z1 B4C: D5050.639 1900–2050uC, 1 h, Ar Up to 99% B4C: 22¡2 … 3.2–3.71 350–513 216 (1996)
to 6 wt-%C
SS: 19.8 TiB2: 6–10
Purity: 99.89%
TiO2 and C: submicrometre
17 B4C D5051.6 (B/C53.9) 2180uC, 2 h, Ar 83 … … 198 (2007)
B4Cz22 vol.-%ZrO2 O2: 1.7% 98 27–31 350
B4Cz28 vol.-%TiO2 ZrO2: submicrometre 98 28–33 375
B4Cz8 vol.-%Y2O3 TiO2: submicrometre 97.5 27–30 180
Y2O3: submicrometre
18 B4C 2150uC, 15 min, Ar 85 B4C: 3.63 199 (1992)
B4Cz1 wt-%Al2O3 D50<0.9 (B/C53.9) 92 B4C: 5.35
B4Cz2 wt-%Al2O3 (1 wt-%O2 and 0.4% N2) 93
B4Cz3 wt-%Al2O3 Al2O3: 99.99% pure 96 B4C: 7.07
B4Cz4 wt-%Al2O3 88
B4Cz5 wt-%Al2O3 86 B4C: 8.92
19 B4Cz1.5%TiC D100: submicrometre 2175uC, 2 h, Ar 96.3 B4C: 12, TiB2 4.0 286 200 (1998)
B4Cz1.5%TiC SS: 15.0 2200uC, 2 h, Ar 94.9 B4C: 18, TiB2 31 3.7 266
B4Cz3.0%TiC O2: 0.98%; N2: 0.32% 2200uC, 2 h, Ar 96.6 B4C: 11, TiB2, C 29
B4Cz4.5%TiC FC: 0.64% 2200uC, 2 h, Ar 98.1 B4C: 8, TiB2, C 28
B4Cz6.0%TiC TiC: D5051.5 2200uC, 2 h, Ar 98.4 B4C: 5, TiB2, C 28
O: 0.53%; N: 0.10%
20 B4C D5050.08 2260uC, 15 min, Ar–N2 71.9 201 (1977)
Suri et al.
2010
Al: 50 ppm
CrB2: D5053.5
VOL
*FC: free carbon in B4C; D50: mean particle diameter, mm; SS: specific surface area, m2 g21.
55
1NO
Synthesis and consolidation of boron carbide: a review
21
Suri et al. Synthesis and consolidation of boron carbide: a review
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
Published by Maney Publishing (c) IOM Communications Ltd
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 undergoes normal sintering and nearly full density can
poor flexural strength (y200 MPa). be achieved. Much of the carbon remains in the B4C
microstructure as graphite particle. Phenolic resin as
Carbon as sinter additive carbon addition is found better than carbon black and
Various sinter additives have been tested to increase the glucose.191 With 3 and 5 wt-%C the density obtained
rate of densification, control grain growth and improve was 92 and 93% TD respectively. With higher amounts
mechanical properties of boron carbide. Carbon has of carbon (>7?5%C), a reversal in densification was
been found to be very effective, primarily in reducing the observed. Yin et al.206 have studied the sintering kinetics
oxide layer of the boron carbide powders, there by of pure and carbon doped boron carbide with 0?42 mm
promoting sintering and hindering grain growth. sized B4C powders in the temperature range 1900–
Carbon, well distributed between the particles reacts 2200uC and a period of 5–45 min. They have deduced,
with B2O3 coating according to the reaction the main sintering mechanisms to be volume and grain
boundary diffusion for pure boron carbide and grain
2B2 O3 z6C?B4 Cz6CO (18)
boundary diffusion for carbon doped boron carbide
Removal of oxide layer allows direct contact between showing activated sintering. Schwetz et al.189,207 have
B4C particles, permitting sintering to initiate at sig- obtained compacts of 97–98% TD with the addition of
nificantly lower temperature (y1350uC). In addition, 1–3% phenolic type of carbon using a powder of large
carbon at the grain boundaries enhances diffusion, surface area (22 m2 g21). A fine grained (7–8 mm)
facilitating accelerated solid state sintering. Various compact with superior mechanical properties (flexural
types of carbon such as petroleum coke, carbon black, strength: 351–353 MPa and fracture toughness:
graphite, glucose and phenolic resin (e.g. phenol 3?3 MPa m1/2) was obtained.
formaldehyde) can be used as sintering aid. If carbon Very fine powders in the range of nanosizes would
in solid form such as coke, graphite or carbon black is increase the rate of sintering due to very large surface
chosen, it is mandatory that very fine size is used and the area and particle to particle contact. Zorzi et al.192 have
mixing carried out thoroughly, in mixtures such as used carbon black of 20 nm size (specific surface area:
planetary mill/attritor to form an intimate contact such 120 m2 g21) with boron carbide powder of surface
as a fine coating on boron carbide particles. An additive area18?8 m2 g21 to obtain 97?7% TD compacts having
such as phenol formaldehyde resin plays two roles; Knoop hardness in the range 19–21 GPa by sintering at
namely as binder while cold pressing and as carbon 2250uC for 2 h. While studying the densification
precursor which is uniformly distributed on the surface behaviour of nanosized boron carbide, it has been
of the grains. Any carbon which is not consumed by the found that solid state sintering (1500 to 1850uC) starts
reduction reaction is left in the compact as excess only after the evaporation of B2O3. The formation of
carbon. High densities of 98?65% TD with a fine grain eutectic (B4C-C) liquid droplets appears on the surface
size of 2?34 mm have been achieved by the addition of of graphite coated B4C particles above 1920uC, which
3%C in the form of phenolic resin.183 Compacts form the weaker regions in the sintered product.208
exhibiting a finer, less faceted grain structure with Sample sintered at 2300uC, showed the grain boundary
smaller and more uniformly distributed pores were to be free from carbon and the excess carbon present as
prepared by the addition of 6 wt-%C (in the form of a fine graphite crystals at the triple point resulting in
thermoset resin).179 Carbon addition inhibits the coar- excellent mechanical properties (Fig. 13a).209 High
sening process, thereby preventing the formation of resolution TEM image of the sample shows no
large unsinterable pores. As a result, carbon doped B4C boundary or amorphous layer (Fig. 13b).209 Large,
complex boron carbide shapes of density .94% are densities of 99% could be achieved without pressure at
fabricated by slip casting method using a binder and temperatures of 2050–2100uC.214,215 Metallographic
sintering at 2280uC for 2 h.210 examination revealed a two phase microstructure with
Thermosetting phenolic types of resins are most B4C grains of 10 and TiB2 of 5–7 mm size. Grain size
suitable as carbon precursors as they give a complete of B4C was found inversely proportional to the quantity
uniform coating of carbon on the surface of carbide of carbon in the sample. Increase in volume fraction of
particles. Carbon can be replaced by boron to react with TiB2 led to an increase in flexural strength and fracture
surface oxide layer of B4C to achieve similar effects. In toughness to a maximum of 513 MPa and 3?7 MPa m1/2
addition boron will also react with free carbon of B4C to respectively at 15 vol.-%.216,217 The observed increase in
form carbide.192 strength and fracture toughness are due to the interac-
Addition of a small amount (3–5 wt-%) of carbon to tion between the propagating crack front and local
B4C plays an important role in eliminating the surface thermal mismatch stress associated with TiB2 particles.
oxide layer, thereby achieving higher densities (y97% Titanium carbide also reacts with boron carbide to
TD) with fine grains and improved mechanical proper- form TiB2 as per the reaction
ties (hardness: 19–25 GPa; flexural strength: 160–
B4 Cz2TiC?3Cz2TiB2 (20)
350 MPa). The quantity and the method of carbon
addition have to be carefully chosen to avoid free carbon The amount of second phase TiB2 and excess carbon
in the sintered body. play a distinct role in sintering. Densities higher than
95% TD were obtained by sintering at temperatures
Role of carbide/boride additives above 2150uC.200 As the carbon content increased from
In addition to carbon, other grain refinement agents for 1?5 to 6?0%, the grain size of B4C decreased from 10 to
B4C are Si and Al. Although the strength can be signi- 3 mm, flexural strength increased from 292 to 502 MPa,
Published by Maney Publishing (c) IOM Communications Ltd
ficantly improved by grain size reduction, the toughness and toughness decreased from 4?2 to 2?9 MPa m1/2.
remains low. Addition of carbides and borides have been Addition of various transition metal (Ti, Zr, Hf, V,
found to increase the flexural strength and fracture Nb and Ta) carbides/borides for preparing dense boron
toughness of B4C by grain refinement and crack pro- carbide pellets have been patented.218,219 Boron carbide
pagation influencing mechanisms such as crack deflec- is reacted at approximately 1500uC with the transition
tion, micro crack interaction and crack impediment.211 metal oxide/carbide to form a mixture of boron
Carbides/borides can either be directly added or formed carbidezmetallic carbide/boride, which is sintered at
by in situ reaction with B4C while sintering. Faber temperatures .2000uC to obtain densities .95%.
and Evans212 have predicted that fracture toughness Goldstein et al.198 have studied the reaction between
increases due to crack deflection around second phase B4C and MeO mixtures (MeO–TiO2, ZrO2, V2O5,
particles in two-phase ceramic materials. The ideal Cr2O3, Y2O3 and La2O3) fired up to 2180uC for 2 h in
second phase, in addition to maintaining chemical argon. The main solid reaction products are found to be
compatibility, should be present in amounts of 10 to borides. Such composites exhibited a sintering aptitude
20 vol.-%. Greater amounts may diminish the toughness higher than that of monolithic B4C, increasing with the
increase due to overlapping particles. Particles with high amount of metal oxide in the initial mixture. The
aspect ratios are most suitable for maximum toughening hardness and strength of composite were comparable to
especially particles with rod shaped morphologies. that of hot pressed B4C. Khazai et al.220 have patented a
Zorzi et al.192 have reported that addition of process for the preparation of boron carbide/titanium
4 wt-%TiB2 to B4C lead to good results in final density, diboride composite with uniform distribution of both.
hardness and wear resistance. Baharvandi and Baharvandi et al.196 have studied the effect of addition
Hadian213 have reported the addition of TiB2 on of Yttria doped zirconia on sintering behaviour
sinterability and mechanical properties of B4C. Density (between 2050 and 2150uC in argon for 1 h) and
and fracture toughness values were found to increase mechanical properties of B4C. Densities of 97% TD
with TiB2 fraction in the entire range of 0 to 30%, were obtained in samples with >15%ZrO2 addition.
whereas bending strength and hardness improve to Boron carbide reacts with ZrO2 during sintering to form
certain amount (15%TiB2) and then start decreasing. ZrB2 as per the following reaction
With 30%TiB2 the highest density and fracture tough-
ness of 98?5% TD and 3?4 MPa m1/2 were achieved B4 Cz2ZrO2 ?2ZrB2 zB2 O3 zCO: (21)
respectively. At 15%TiB2 the highest hardness of 31 GPa Fracture toughness and flexural strength of the com-
and flexural strength of 360 MPa were obtained. TiB2 pacts increased from 2?1 to 3?1 MPa m1/2 and 200 to
also acted as a grain growth inhibitor. TiB2 is formed by 340 MPa respectively with the increase of ZrO2 content
reaction sintering of boron carbide with titanium oxide from 0 to 30%. Processing in vacuum and higher
at y1500uC as per the following reaction temperature (2275uC) increased the hardness to
B4 Cz2TiO2 z3C?2TiB2 z4CO: (19) .30 GPa.221 Figure 14 presents the variation in hard-
ness of pressureless sintered B4C with ZrO2 addition.
197
Levin et al. have found that TiO2 is reduced by Hardness in the entire range of composite is y30 GPa
carbon originated from the carbide phase. This leads to compared to 27 GPa for pure B4C. Backscattered image
the formation of substoichiometric boron carbide, which of this sample shows a white phase containing up to
is responsible for increased rate of sintering. Addition of 1?2%Zr distributed in B4C matrix (Fig. 15).
40 wt-%TiO2 to B4C powder (17 m2 g21 specific area) Fractography (Fig. 16)221 shows the mode of fracture
gives a compact of 95% TD after sintering for 1 h at to be a combination of transgranular and intergranular.
2160uC.187,197 Presence of TiB2 results in lowering of The in situ reactions for the formation of carbide/
activation energy for sintering and hence very high boride consume some of the carbon from boron carbide,
strength and fracture toughness on account of strength- alumina talc (26?62Al2O3–47?78SiO2–25?6MgO) powder
ening effect of the high aspect ratio of the second phase as a sintering aid. The sample sintered at 2050uC for 1 h
particles. The dynamic strength and the dynamic showed the formation of MgB2, SiC and Al2O3. The
fracture toughness K1d are significantly higher than the mechanism of sintering is due to the formation of liquid
corresponding static properties and are insensitive to the phase anstatite at 2000uC and its reaction with B4C to
residual silicon fraction and to the strain rate (up to form SiC, MgB2 and Al2O3. Though the density (78–
5103 s21). Properties of the B4C material prepared by 98%) and fracture toughness (2–2?8 MPa m1/2) of the
this method are given as: density, 2?57 g cm23; young’s compact increased with the quantity of talc in the charge
modulus, 382 GPa; flexural strength, 278 MPa and up to 30%, microhardness attained a peak value of
fracture toughness, 5?0 MPa m1/2. Organosilicon poly- 26 GPa at 25% and then fell down.
A US patent236 explains a process wherein boron
mers such as polycarbosilane,190 polysiloxanes, poly-
carbide powder is mixed with aqueous sodium silicate
silazanes, polysilanes, metallopolysiloxanes and
(to give SiO2 equivalent of 0?75–1?5 wt-%B4C) and
metallopolysilanes,234 which upon pyrolysis yield SiC
alumina (1–3 wt-%), compacted and sintered at 2100uC
and free carbon have been found to be very effective in
to give compacts exceeding 90% TD. As per another US
pressureless sintering of boron carbide. Weaver202 has
patent by Prochazka201 addition of 0?5–3 wt-%BeC to
patented a process where in a mixture of boron carbide
boron carbide helps in achieving a density of 85–94%
and silicon carbide are mixed in an aluminium mill to a
TD by sintering at 2200–2280uC. Weaver in his patent202
composition of 87B4C–10SiC–3Al which is sintered at
has mentioned a process to obtain refractory bodies
1800–2300uC to densities up to 94% TD.
composed of 60–98 wt-% boron carbide, 2–40 wt-%
Chromium boride forms a eutectic liquid phase with
silicon carbide and 0–10 wt-% aluminium with densities
B4C at a temperature of 2150uC. The fractured surface
exceeding 94% TD by cold pressing followed by a
of the B4C specimen with 20 mol.-%CrB2 prepared at
pressureless heat treatment.
2000uC showed the CrB2 particles to be partially Low melting metals/alloys such as Al and Al–Si have
melted and wetted with the adjacent B4C particles been used to bind boron carbide particles to different
(Fig. 17).203,204,235 There was no significant growth of shapes for neutron absorber applications. Liquid phase
B4C grains and the densification was mainly attributed sintering of boron carbide is carried out by in situ
to B4C particles rearrangement caused by the CrB2–B4C reaction with alumina, silica, BeC, CrB2, etc. This
eutectic liquid formation. However at temperatures reduces the sintering temperature by a few hundred
above 2200uC, abnormal grain growth of B4C occurred. degrees and the sintered product has a fine microstruc-
Specimen with 98?1% TD (20 mol.-%CrB2, sintered at ture and moderate mechanical properties. Silicon is
2030uC) showed a high flexural strength of 525 MPa and found to be an excellent additive which is introduced
a moderate fracture toughness of 3?7 MPa m1/2. The into a sintered porous body of B4C by infiltration
improvement in fracture toughness is due to the technique. This helps in two ways: by liquid phase
formation of microcracks and the deflection of propa- sintering and by SiC formation which greatly improves
gating cracks due to the thermal mismatch of CrB2 and the mechanical properties. Owing to fine grain structure
B4C. and high fracture toughness of the end product, this is
Addition of alumina improves the densification of the method chosen for the manufacture of B4C based
boron carbide with the formation of liquid phase armour shields.
AlB12C2 by the reaction between B4C and Al2O3.
Maximum density of 96% TD was achieved by the Hot pressing
addition of 3 wt-% alumina doped B4C sintered at In conventional sintering, the rate of densification is
2150uC for 15 min.199 Exaggerated grain growth was very slow. Though higher densification can be achieved
observed in the specimen containing .4% alumina. at higher temperatures, it is difficult to prevent grain
Table 8 Powder details, sintering parameters and characteristics of sintered boron carbide by hot pressing*
1 B4C FC: 1.4% 34.4 MPa, 2.7 ks, heating rate: 1775 K 65.1 6.0 … … … 240 (1983)
330 K ks21; cooling rate:
1665 K ks21
D5052.9 1975 K 72.4 7.0
SS: 0.24–6.2 2175 K 80.2 12.1
2325 K 98.5 13.5
2375 K 98.4 15.2
2475 K 99.6 16.4
2 B4C D5051.5 synthesis from the 2200uC, 22 MPa, 10 min 98 .5, a large number … … … 239 (1979)
elements of twins
3 B4C D5051; SS: 12 2100uC, 40 MPa, 30 min, Ar .95 2–3 … … … 179 (1989)
4 B4C D50,3 2150uC, 36 MPa, 60 min 95.5 4–8 32.5 2.5–3.0 300–400 250 (2005)
5 bBzC D5052.0; SS: 1.27 1950uC, 30 MPa 87 … … … … 241 (2000)
Amorphous BzC D5050.2; SS: 12.76 1800uC, 30 MPa 99
aBzC D5052.74; SS: 0.89 1800uC, 30 MPa 91
6 B4C B4C: D50510; O: 0.1–1.0 wt-% 2200uC, 34.5 MPa, 1 h, HR: 2.5 g cc21 10–50 240 242 (1979)
0.5 K s21, CR: 1.7 K s21
B4Cz5%B B: D50520 2.49 g cc21 … 190
B4Cz15%B 2.42 g cc21 10–40 200
7 B4CzTiO2zC B4C: D5050.50; SS: 21.5 2000uC, 50 MPa, 1 h, Ar 100 B4C: 3.8, TiB2 … 3.1 870 243 (2005)
TiO2: D50, nanosize B4C: D5050.44; SS: 15.5 100 B4C: 3.4, TiB2 2.8 720
B4C: D550.41; SS: 22.5 100 B4C: 3.9, TiB2 3.2 815
8 B4CzTiO2zC 2100uC, 35 MPa, 8 min .95 0%TiB2 27 3.1 200 257 (1990)
5% TiB2 30 4.0 350
10%TiB2 32 5.0 500
Suri et al.
2010
to 2; Mo: D5051 to 3
B4Cz5.3%Mo 1950uC, 35 MPa, 50 min, Ar 96.5 1–2 … … …
1950uC, 35 MPa, 50 min, Ar 99.1 1–2 22 3.40 550
VOL
B4Cz5%TiCz5%Mo
B4Cz10%TiCz4.7%Mo 1950uC, 35 MPa, 50 min, Ar 99.2 1–2 25 4.25 695
55
B4Cz15%TiCz4.5%Mo 1950uC, 35 MPa, 50 min, Ar 99.0 1–2 24.5 3.75 625
B4Cz20%TiCz4%Mo 1950uC, 35 MPa, 50 min, Ar 98.5 1–2 23.5 3.60 550
1NO
Synthesis and consolidation of boron carbide: a review
27
Published by Maney Publishing (c) IOM Communications Ltd
28
Suri et al.
Table 8 Continued
12 B4C: 29.5–57%; B: 18.3– D50,1 66 MPa, 3 min, heating rate: 1620uC 3.5 g cc21 B4C–TiB2–W2B5 12 … 550 245 (1986)
35.5%; Si: 3.8–7.5%; WCz 40 K min21; cooling rate: 1670uC 3.6 g cc21 26 620
TiC: 0–45.3%; Co: 0–2.8% 100 K min21 1720uC 3.59 g cc21 30 710
1820uC 3.5 g cc21 28 830
2010
B4Cz10%CrB2 CrB2: D5053.5 86 2.2 350
B4Cz15%CrB2 94 2.5 500
VOL
B4Cz20%CrB2 95 2.8 550
55
B4Cz22.5%CrB2 96 3.2 620
B4Cz25%CrB2 98 3.2 684
Synthesis and consolidation of boron carbide: a review
95 3.2 660
1NO
14 B4C B4C: D5050.43 1900uC, 50 MPa, 1 h, Ar 99.0 2.5 675 248 (2003)
B4Cz5%CrB2 CrB2: D5053.5 99.6 2.6 551
B4Cz10%CrB2 99.7 2.7 580
B4Cz15%CrB2 99.0 2.8 630
B4Cz20%CrB2 99.0 3.5 630
B4Cz25%CrB2 98.6 3.4 580
15 B4Cz50%SiC B/C54.1; B: D5051.5; O: ,4% 1900uC, 30 MPa, 30 min, Ar; HR: 2.50 g cc21 B4C, SiC … … … 273 (1993)
15–150uC min21
21
SizBzC C, SS: 80; Si: D10055 2.74 g cc B4C, SiC
16 B4Cz8 to 13% siloxane/ 2275uC, 28 MPa, 1 h, Ar 97–99.7 B4C, SiC/C … … … 234 (1996)
phenolic
17 B4Czsodium silicatez B4C: D5050.1 to 1 1750uC, 24 MPa, 10 min to 4 h 45–68 … 25 … … 249 (1974)
magnesium nitratezFe3O4
45–98.4
18 B4C B4C: D5053.5; BN: D50, nanosized 1850uC, 30 MPa, 1 h, N2 99.5 B4C, nano-h-BN 21 5.4 410 254 (2008)
B4Cz10 wt-% BN 99.2 15 6.0 420
B4Cz20 wt-% BN 99.0 11 5.2 410
B4Cz30 wt-% BN 98.5 8 5.0 360
B4Cz40 wt-% BN 98.1 7 4.3 310
19 B4Cz60%Al2O3 B4C: D5051.0 1700uC, 35 MPa, 1 h, Ar 3.53 … 28 4.2¡0.7 530¡30 258 (2005)
B4Cz70%Al2O3 Al2O3: D5050.2 3.65 3.0 27 4.2¡0.4 560¡30
B4Cz80%Al2O3 3.77 3.2 23 4.3¡0.5 600¡70
B4Cz90%Al2O3 3.86 3.4 21 3.5¡0.5 550¡45
20 B4CzAl2O3 (B4C/Al2O3518 : 1) 2150uC, 35 MPa, 65 min, Ar 95.5 B4C: 2–5 22.4¡1.2 3.2¡0.5 300¡34 271 (2008)
B4CzAl2O3z5%TiC B4C: D5053 to 5, .95% 1950uC, 35 MPa, 60 min, Ar 98.7 B4C, TiB2 24.1¡1.1 4.1¡0.5 430¡31
B4CzAl2O3z10%TiC Al2O3: D5051 to 2, .99% 1950uC, 35 MPa, 60 min, Ar 98.9 B4C: 0.5–1.5, TiB2 24.7¡1.0 4.7¡0.4 445¡30
B4CzAl2O3z15%TiC TiC: D5051 to 2, .99% 1950uC, 35 MPa, 60 min, Ar 98.7 B4C, TiB2 24.3¡1.0 4.5¡0.4 386¡29
B4CzAl2O3z20%TiC 1950uC, 35 MPa, 60 min, Ar 98.5 B4C, TiB2 23.2¡1.0 4.2¡0.4 323¡32
Suri et al. Synthesis and consolidation of boron carbide: a review
Reference (year)
251 (2008)
194 (1978)
253 (1999)
hardness, toughness, strength,
Indentation Flexural
156.76
MPa m1/2 MPa
…
3.0–3.9
…
…
97 HRA
Vickers
25–27
GPa
*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. 20 Microstructure of hot pressed boron carbide showing
Microstructure,
transgranular.
Fabrication of boron carbide shapes by hot pressing
92.5
81.9
73.6
pure compacts.
1% BN/AlNzrest RE
90 to 99%B4Cz0 to
21
22
23
24
particles uniformly distributed in a fine grained B4C max.245 US patent by Petzow et al.263 describes a process
matrix is responsible for the increase in fracture for the preparation of boron carbide/transition metal
toughness and strength. B4C–15 vol.-%TiB2 composite boride moulded articles comprising of B4C, Si, WC and/
with a flexural strength of 621 MPa and fracture or TiC and Co by hot pressing between 1550 and
toughness of 6?1 MPa m1/2 have been prepared by hot 1850uC. Effect of variation of TiC addition on hot
pressing at 2000uC and a pressure of 20 MPa in argon pressing of B4C/TiB2/Mo composite has been studied by
atmosphere for 1 h by Skorokhod et al.244 They have Jianxin et al.247 and the maximum values of fracture
observed that factors for the increased strength are due toughness, flexural strength and hardness reported are
to the healing of the cracks during sintering and the 4?3 MPa m1/2, 695 MPa and 25?0 GPa respectively.
presence of TiB2 particle which force the crack to During ball milling/mixing of B4C with additives, the
propagate in a non-planar fashion thus enhancing the powders get contaminated and the microstructure of the
energy dissipation at the crack tip. An US patent243 composite appears very complicated after hot pressing
explains a process to prepare boron carbide composites due to the diffusion of W, Co, Ni, Cr, etc. either into the
containing 5 to 30 mol.-% titanium diboride with very TiB2 grains to form (Ti,M)B2 or (Ti,M)B2 coated grains,
high flexural strength (870 MPa) and fracture toughness and Ti, Fe, Co, Ni, and Cr into W2B5 to form boron rich
(3?4 MPa m1/2). Addition of Fe in small amounts (0?5%) boride or the interfacial layer.264
has been found to be effective in increasing the final
densities of B4C–TiB2 composite due to the formation of Role of carbides/nitrides
Fe–Ti rich liquid phase at the grain junctions.262 Li et al.265 have prepared a composite containing B4C,
SiC, TiB2 and BN by reactive hot pressing of B4C,
Role of mixed borides Si3N4, a-SiC and TiC powders and the hardness,
As seen in the previous lines addition of TiO2 has bending strength, fracture toughness and relative density
brought down the hot pressing temperature of B4C by of the composite were 88?6 HRA, 554 MPa,
>100uC. Further attempts to reduce the sintering tem- 5?6 MPa m1/2 and 95?6% respectively. Microstructure
perature without compromising the strength are given analysis showed the presence of laminated structure and
below. Reaction sintering of B4C with 30 wt-%(W,Ti)C a clubbed frame dispersion phase and bunchy dispersion
at 1850uC for 30 min showed increase in fracture phase among the matrix. Fractography and crack
toughness and flexural strength up to 50 wt-%(W,Ti)C propagation suggested that crack deflection and brid-
content. Fine grains of (0?5–2 mm) TiB2 and W2B5 were ging are the possible toughening mechanisms.
seen in the microstructure. The sintering temperature of Han et al.266 have synthesised a high strength (400–
this composite is 300uC lower than that of monolithic 570 MPa, 6–9?5 MPa m1/2) B4C–TiB2–SiC–graphite
B4C. Flexural strength and fracture toughness for composite by reactive hot pressing using B4C, TiC and
composite with 40 to 50% additive were 700 MPa and SiC powders. The crack deflection at the phase
4?5 MPa m1/2. The increase in fracture toughness is boundary between B4C matrix and dispersions consist-
attributed to the residual stresses generated by differ- ing of SiC and TiB2, which occur by residual stresses due
ences in the thermal expansion coefficient between B4C, to the differences in thermal expansion coefficients of
TiB2 and W2B5. The effect of TiB2/W2B5 on the path of B4C, TiB2 and SiC while cooling from the fabrication
crack and deflection in the composite is shown in temperature is responsible for the enhanced fracture
Fig. 21.246 Further reduction in sintering temperature toughness values. Similar very high strength material
was achieved by the addition of B, Si and Co to the (four point bend strength: 850 MPa; fracture toughness:
above referred mixture. Reaction sintering of B4C with 6?1 MPa m1/2) has been prepared by the addition of
WC, TiC, B, Si and Co by attrition milling followed by 5–30 vol.-%Mo to B4C/(W,Mo)B2 by hot pressing at
hot pressing at 1720uC for 2 h gave a compact with three 1900uC.267 Fractography of this sample showing the
distinct phases of B4C, W2B5, and TiB2, hardness in the crack propagation path is depicted in Fig. 22.267 When
by reaction synthesis with hot pressing has been found fabricated by hot pressing microsized B4C particles
to exhibit high hardness and bending strength suitable coated with amorphous nanosized BN particles.254 The
for application as wear and shock resistance compo- hardness of composite decreased with increase content
nents.269 Cr and V carbides are also found to be effective of BN while the machinability improved significantly. A
in obtaining high densities and fine grained structure.270 composite with .20 wt-%BN content exhibited excel-
A process in which a preceramic organosilicon polymer lent machinability.272 The surface hardness and wear
which on pyrolysis yields SiC and free carbon has been resistance of this composite has been improved by
patented for preparation of dense bodies of boron silicon infiltration process.255 Combination of SHS tech-
carbide (.97% TD) by hot pressing in inert atmosphere nique with hot pressing (called combustion hot pressing)
at a temperature of 2275uC and a pressure of 28 MPa.234 has been used to prepare a composite, containing B4C
and SiC formed by reaction among Si, B and C, in the
Reaction sintering of boron carbide with the addition
form of interlocked matrices with very low porosity and
of oxides/carbides/nitrides has been successfully
uniform microstructure.273 Graded porosity B4C mate-
employed to obtain a microstructure of fine particles
rials can be produced by a layering approach using
of reaction product (borides/carbides/nitrides) in B4C
different size distributions of B4C powders in the green
matrix. These additions lower the sintering temperature
state, and then densifying the layered assembly by hot
than that of monolithic B4C. Flexural strength and
pressing at 1900uC.274 Cobalt as sinter additive has also
fracture toughness of these composites are very high due
been attempted for hot pressing of boron carbide
to the residual stresses generated by differences in the
powders with 5 wt-%TiC at temperatures ,1500uC
thermal expansion coefficient between B4C and reaction
and a high pressure of 5–6 GPa.275
products, crack bridging and deflection mechanisms at
the interface, etc. Small quantities of B, Si, Ti, Fe, Co, Hot isostatic pressing (HIP)
Ni, Cr, W, etc. either intentionally added or accidentally The HIP process, originally known as gas pressure
acquired during the grinding/mixing operations are also bonding, uses the combination of elevated temperature
found to be effective in marginally reducing the sintering and high pressure to form/densify raw materials or
temperature and improving the flexural strength/fracture preformed components. The application of the pressure
toughness due to the formation of complex boride is carried out inside a pressure vessel, typically using an
phases and multi interfaces. inert gas as the pressure transmitting medium with or
without glass encapsulation of the part. A resistance
Liquid phase sintering heated furnace inside the vessel is the temperature
Addition of CrB2 aids in lowering the hot pressing source. Parts are loaded into the vessel and pressurisa-
temperature due to the formation of CrB2–B4C eutectic tion occurs usually simultaneously with the heating. The
at 2150uC. B4C–20 mol.-%CrB2 composite fabricated high pressure provides a driving force for material
by hot pressing at 1900uC shows a high strength of transport during sintering which allows the densification
630 MPa and a modest fracture toughness of to proceed at considerably lower temperature in
3?5 MPa m1/2. The very fine grained microstructure is comparison to that of traditional sintering. In addition,
responsible for high flexural strength and residual particularly during the initial stages of the process, the
stresses caused by thermal expansion mismatch of high pressure induces particle rearrangement and high
CrB2 and B4C for increasing toughness.243,248,256 stresses at the particle contact points. A virtually pore
Similarly addition of Al2O3 enhances the sintering free product can be produced at a relatively low
kinetics of boron carbide due to a liquid phase temperature. The pressure level used in the HIP process
formation at 1950uC.249 Jianxin and Junlong271 have typically is 100–300 MPa, as compared to 30–50 MPa in
studied the effect of TiC content on the micro- uniaxial hot pressing, and the isostatic mode of
structure, mechanical properties and sand erosion rate application of pressure is generally more efficient than
1 h under a pressure of 160 MPa. Addition of boron was minimise expensive machining, the powder densification
found effective in reducing the pores and graphite process must be capable of near net shaping. One such
inclusions and improved particle erosion resistance. process and the apparatus for rapid bonding of ceramic
Boron carbide (100% TD) could be obtained by a materials have been patented by Yoo et al.287 The
combination of pressureless sintering and post-HIP at materials to be consolidated are placed in a graphite die
2150uC for 125 min under 310 MPa of argon pres- and punch assembly. The driving force for densification
sure.279,280 The combination of pressureless sintering is provided by passing current directly through the
and post-HIP is gaining importance for fabrication of particle material, with simultaneously applying high
dense bodies with higher densities, lower graphite shear and high pressure in separate steps. High shear
contents and significantly higher Vickers hardness than force in combination with pulsed electric power is
commercially hot pressed B4C.279–281 Elimination of initially applied to the particle material to generate
residual porosity and significant improvements in electrical discharge that activates the particle surface by
flexural strength, elastic constants and wear resistance evaporation of oxide film, impurities and moisture.
were observed with the addition of 1 and 3 wt-%C in the Subsequently bonding is accomplished by resistance
above process.282 Fully dense and very fine grained heating at the contact points between the activated
boron carbide has been prepared by the fabrication particles in the presence of high pressure. The time and
route, injection moulding/pressureless sintering (2175uC)/ temperature required for consolidation is lowered as
post-HIP (200 MPa, Ar) from B4C doped with 4 wt-% high current density is applied in addition to high shear
carbon black.283 Near net shape with full density can be and high pressure (up to 2000 MPa) which leads to
achieved by HIP.284–286 Figure 23279 shows the micro- localised heating and plastic deformation at interparticle
structure of post hipped boron carbide to full theoretical contact areas. The rapid sintering which preferably lasts
density. Equiaxed uniform size grains and thin grain for less than a few minutes prevents grain growth and
boundary are the special features of this material with allows the particles to retain their microstructure. Spark
very high hardness.279–281 A patented process explains plasma sintering (SPS), plasma activated sintering,
the preparation of boron carbide shapes containing plasma pressure consolidation/P2C and instrumented
metallic diborides (of Ti, Zr, Hf, V, Nb and Ta), sintered pulse electrodischarge consolidation are the different
in the temperature 2100 to 2200uC to give a density of names given for the same process.
2?47 g cc21, which on further hot isostatic pressing at Ghosh et al.52 have consolidated submicrometre sized
2100uC under an argon pressure of 200 MPa to achieve commercial boron carbide to near theoretical densities
a theoretical density of 2?56 g cc21.219 using plasma pressure compaction technique. The
Porosity severely degrades the ballistic properties of densities obtained at 1750uC by the application of
ceramic armour as it acts as a crack initiator. Sintering 88 MPa pressure in 2 and 5 min were 96 and 99?2% TD
aids generally degrade hardness and ballistic properties. respectively. The average grain size of these compacts
Therefore, boron carbide protective inserts for personal was 1?6 and 2 mm. Optical micrograph (Fig. 24)52
armour is hot pressed to minimise porosity (y98% reveals nearly equiaxed fine grained microstructure.
relative density), yielding acceptable performance. Post- The hardness and fracture toughness values were in
hipping of pressureless sintered boron carbide is gaining the range of 25?41 to 27?45 GPa and 3?22 to
importance for this purpose. This will not only yield 3?61 MPa m1/2 under static testing conditions.
lighter weight armour but also enable forming of Addition of graphite and TiB2 do not aid in consolida-
complex shapes. tion of B4C by this method. Addition of small amounts
Major equipments needed for pressureless sintering of Al2O3 and Fe has been found to be effective in
are cold compaction press and sintering furnace. For hot achieving higher densities by SPS of B4C due to
pressing, a graphite die is assembled between the rams of formation a liquid phase.288–290
Influence of temperature on synthesis and consolidation wave systems. The sample size and shape, the
has been studied by Tamburini et al.113 Formation of distribution of the microwave energy inside the cavity,
B4C commences at y1000uC and is complete by 1200uC, and the magnetic field of the electromagnetic radiation
with a hold time of 10 min. Significant densification are all important in heating and sintering.296 Literature
occurs above 1600uC, but the material shows evidence of on microwave sintering of boron carbide is scarce. One
extensive crystallographic disorder due to twins which of the recent articles describes the behaviour of B4C/SiC/
however decrease at higher temperatures. Kodera Al mixtures during microwave heating in air. A dense
et al.291 while heating B-C powders by SPS have composite with B4C skeleton and the voids filled with
observed that, formation of B4C starts at 1300uC, the reaction products of Al and B4C were obtained. SiC
consolidation with twins initiates at 1600uC and 98% was not attacked by oxygen and was able to contribute
density obtained at 1900uC. Heian et al.106 have also to matrix toughness. This material with low specific
noted similar structural defects in the material prepared gravity and high hardness is attractive for use in
by mechanical activation followed by field assisted lightweight armour.297 One can expect more research
combustion. Wang et al.292 have noticed that B and C using microwave heating as and when bigger size units
begin to react from 1300uC and the product was B rich with higher power ratings become available in the
boron carbide (B4zxC) and free C. With increasing market.
temperature C atoms diffused into B4zxC lattice, A novel floating zone method has been adopted for
resulting in the reduction of free carbon content and preparing directionally reinforced B4C–TiB2 compo-
decrease in lattice parameters of B4zxC. Densification of site.298 Temperature dependence of the bending strength
the synthesised boron carbide occurred from 1700 to of this composite was evaluated in the temperature
1900uC. Simultaneous synthesis and densification of range 25–1600uC. With increasing temperature, its value
B3?5C, B4C and B4?5C by spark plasma sintering has decreases to 120 MPa at 800uC and then increased to
shown that carbon free boron rich compounds are 230 MPa at 1000–1400uC. Even at 1600uC, the bending
formed in the temperature range 1300–1600uC and strength was as high as 200 MPa.298 The development of
consolidation occurs above 1700uC.293 non-aqueous gel casting process for preparation of B4C–
Fabrication of functionally graded B4C cermets Al composites has been reported by Zhang et al.299
Continuous functionally graded boron carbide alumi-
nium cermets have been prepared by spark plasma Conclusions
sintering of B4C from boron and carbon followed by
infiltration of aluminium.294 This processing route The understanding of the crystal structure of boron
results in a material with very promising properties carbide has been evolving over the years and even today
and interesting microstructural features. Hardness pro- cannot be said to be fully elucidated. Carbothermic
file of functionally graded material before and after Al reduction of boric acid has been the commercial method
melt infiltration is shown in Fig. 25.294 A B4C/Cu graded for the production of boron carbide in spite of the
composite as plasma facing component for fusion shortcomings. Need of the hour in carbothermic reduc-
reactors with performance better than nuclear grade tion is process modelling, which will greatly help in
graphite has been prepared by rapid self-resistance tuning the process to achieve improved productivity and
sintering under ultra high pressure.295 uniform quality. Though a continuous method has been
established for the production of SiC,300 a similar
Microwave processing method has to be adopted for B4C also. Sol–gel method
Microwave sintering has the advantages of uniform and appears to be a promising technique for production of
rapid heating since the energy is directly coupled into the suitable fine boron carbide powders for direct consoli-
specimen rather than being conducted into the specimen dation. Vapour phase synthesis, still in laboratory scale,
is an attractive process for the preparation of submicro- 2. In the long run, usage of tailor made powders
metre sized powders, whiskers, etc. Though thermo- (complex composition, compositional gradient in parti-
dynamic models based on Gibbs free energy cle, well defined particle shape) and reliable usage of
minimisation have been used to predict experimental nanoscale powders will become more important.
conditions, models based on mass transfer and kinetics 3. Techniques for near net shape forming should be
in addition are needed to understand the deposition considered a field for fruitful further activity.
mechanism and the growth process. Boron carbide All these points are truly applicable to boron carbide
based coatings by CVD methods for various semicon- also.
ducting applications such as diode, transistor, thermo-
electric converter, thermocouple, neutron sensors, etc.
are gaining importance and the use of boron carbide in
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