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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
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
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
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.
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
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
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
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, 4BBr3 zCCl4 z16Na?B4 Cz4NaClz12NaBr (16)
polyvinyl pentaborane and borazines on pyrolysis yield
B4C. Generally this process is carried out in the tem- The reaction was carried out in an autoclave at 450uC.
perature range 1000–1500uC in vacuum or inert atmo- B4C crystals obtained were composed of uniform
sphere. A US patent156 describes a process for making a spherical (80 nm dia) and rod-like (200 nm diameter
free flowing boron carbide powder from boric acid and and 2?5 mm long) particles (Fig. 8).168 Gu et al.169 have
sugar. The mixture dissolved in ethylene glycol is dried observed the formation of nanocrystalline B4C by
in air at 180uC and then heated in hydrogen at 700uC. solvothermal reduction of CCl4 using lithium in
This reaction product is ground and fired at 1700uC for presence of amorphous boron powder in an autoclave
7 h to yield fine boron carbide powder. Mondal et al.157 at 600uC.
describe a low temperature synthetic route in which a
polymeric precursor is synthesised by the reaction of 4BzCCl4 z4Li?B4 Cz4LiCl (17)
boric acid and polyvinyl alcohol, which on pyrolysis at Hexagonal B4C crystals with a particle size of approxi-
400/800uC gives crystalline boron carbide. Sinha et al.158 mately 15–40 nm diameters were obtained.
have presented a process in which, a stable gel is formed
from aqueous solution of boric acid and citric acid. This Ion beam synthesis
gel is further processed to yield a precursor which on Boron carbide thin films can be grown by direct
heating under vacuum to 1450uC produces B4C. deposition of Bz and Cz ions. In this process,
Economy et al.159 have prepared boron carbide fibre parameters such as ion energy, ion flux ratio of different
Table 5 Charge composition, processing conditions and product quality on synthesis of boron carbide using polymer
precursor
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
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
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
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
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
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
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,
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,
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
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
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
References
this field will increase manifold in the coming years. In 1. F. Thevenot: ‘Boron carbide – a comprehensive review’, J. Eur.
Ceram. Soc., 1990, 6, 205–225.
addition to the established uses, the future of boron
2. M. L. Bauccio: ‘ASM engineered materials reference book’, 2nd
carbide will depend on the possible production of edn; 1994, Materials Park, OH, ASM International.
micrometre/nanosized powders, whiskers and advanced 3. S. R. Murthy: ‘Elastic properties of boron carbide’, J. Mater. Sci.
coating techniques to meet the varying demands. Lett., 1985, 4, 603–605.
On consolidation, the research so far has been focused 4. A. Lipp: ‘Boron carbide: production properties and application’,
Technische Rundschau, 1965, 14, 28, 33 and 1966, 7.
on reducing the sintering temperature, inhibit grain 5. V. I. Matkovich: ‘Boron and refractory borides’; 1977,
growth and improve the mechanical properties. Carbon Heidelberg/New York, Springler-Verlag Berlin.
has been the chief architect of these improvements. Addi- 6. D. Jianxin: ‘Erosion wear of boron carbide ceramic nozzles by
tives based on carbides/borides/nitrides are also found to abrasive air jets’, Mater. Sci. Eng. A, 2005, A408, 227–233.
be effective in obtaining a fine grained structure with 7. A. Gatti, R. Cree, J. B. Higgins and E. Feingold: ‘Boron carbide
continuous filaments’, Technical report. Jul 64–Jun 65,
higher fracture toughness/flexural strength. Hot pressing Philadelphia, PA, Missile and Space Div., General electric Co.,
and HIP have remained the main densification methods 1965, available at: http://www.ntis.gov/
for production of pore free pure boron carbide due to their 8. Y. Chen, Y. W. Chung and S. Y. Li: ‘Boron carbide and boron
ability to achieve near theoretical density without grain carbonitride thin films as protective coatings in ultra-high density
hard disk drives’, Surf. Coat. Technol., 2006, 200, 4072–4077.
coarsening. The process of silicon impregnation into a
9. K. E. Lee, J. Y. Lee, M. J. Park, J. H. Kim, C. B. Lee and C. O.
sintered porous boron carbide body produces a very high Kim: ‘Preparation of boron carbide thin films for HDD
dense compact with improved mechanical properties due protecting layer’, J. Magn. Magn. Mater., 2004, 272–276, 2197–
to the presence of fine SiC particles. Post-hipped pres- 2199.
sureless sintering is gaining importance for manufacture 10. P. Dunner, H. J. Heuvel and M. Horle: ‘Absorber materials for
control rod systems of fast breeder reactors’, J. Nucl. Mater.,
of complex shapes with fine grains especially for armour 1984, 124, 185–194.
material. Production of nanosized particles followed by 11. C. Dominguez, N. Cocuaud, D. Drouan, A. Constant and
SPS for consolidation will revolutionise the method of D. Jacquemain: ‘Investigation on boron carbide oxidation for
B4C component manufacture. The mechanism, micro- nuclear reactor safety: experiments in highly oxidizing conditions’,
J. Nucl. Mater., 2008, 374, 473–481.
structure and properties of compacts by SPS technique are
12. N. Seiler, F. Bertrand, O. Marchand, G. Repetto and S. Ederli:
yet to be fully understood. Various available methods of ‘Investigations on boron carbide oxidation for nuclear reactors
powder production and consolidation techniques have safety – general modeling for ICARE/CATHARE code applica-
been exploited for fabrication of boron carbide compo- tions’, Nucl. Eng. Design, 2008, 238, 820–836.
nents with tailor made properties. 13. A. Riyas, K. Divan, M. Alagon and P. Mohanakrishnan: ‘A new
physics design of control safety rods for prototype fast breeder
B4C to be considered as high temperature structure reactor’, Ann. Nucl. Energ., 2008, 35, 1484–1491.
material should have good thermal and oxidation 14. D. Emin and T. L. Aselage: ‘A propeosed boron-carbide-based
resistive properties. Detailed investigations on oxidation solid-state neutron detector’, J. Appl. Phys., 2005, 97, 013529?1–
characteristics of B4C at high temperatures have been 013529?3
15. O. Gebhardt and D. Gavillet: ‘SIMS imaging analyses of in-
carried out by Steinbruck et al.301,302 and others.303,304
reactor irradiated boron carbide control rod samples’, J. Nucl.
Higher oxidation stability of B4C with the addition of Mater., 2000, 279, 368–371.
Zr, Cr and W borides have also been reported by Radev 16. http://www.iaea.org/inisnkm/nkm/aws/fnss/fulltext/0884_15.pdf
et al.305 Serious efforts on oxidation prevention of boron 17. V. D. Risovany, A. V. Zakharov, E. P. Klochkov, A. G.
carbide at high temperatures and improvement of Osipenko, N. S. Kosuling and G. I. Mikhailichenko:
‘Reprocessing of the irradiated boron carbide enriched by
thermal properties have not been attempted. It may be boron-10 isotope and its reuse in the control rods of the fast
worthwhile to investigate composites with silicides and breeder reactors’, Proc. Techn. Committ. Meet. on ‘absorber
RE borides. With excellent dielectric properties, thermal materials, control rods and designs of backup reactivity shutdown
and chemical stability, and erosion resistance in high systems for breakeven cores and burner cores for reducing
plutonium stockpiles’, Obninsk, Russia, July 1995, International
intensity laser beams, BN–B4C composite materials Atomic Energy Agency, IAEA-TECDOC--884, Vols. 3–7, 214–
could find a unique place for high temperature applica- 219.
tions.306 From the point of view of application, boron 18. R. Jimbou, M. Saidoh, K. Nakamura, M. Akiba, S. Suzuki,
carbide has established as the material for abrasive Y. Gotoh, Y. Suzuki, A. Chiba, T. Yamaki, M. Nakagawa,
applications, neutron absorber and armour material. Its K. Morita and B. Tsuchiya: ‘New composite composed of boron
carbide and carbon fiber with high thermal conductivity for first
use in electronic industry and high temperature applica- wall’, J. Nucl. Mater., 1996, 233–237, 781–786.
tions will see a higher growth in the coming years. 19. P. Valentine, P. W. Trester, J. Winter, J. Linke, R. Duwe,
A recent study regarding road map for advanced E. Wallura and V. Philips: ‘Boron carbide based coatings on
ceramics provides guide lines for future investments.307 graphite for plasma-facing components’, J. Nucl. Mater., 1994,
212–215, 1146–1152.
1. Development of innovative process technologies to 20. R. Jimbou, K. Kodama, M. Saidoh, Y. Suzuki, M. Nakagawa,
transfer new knowledge on functional and structural K. Morita and B. Tsuchiya: ‘Thermal conductivity and retention
properties into ceramic materials and devices. characteristics of composites made of boron carbide and carbon
fibers with extremely high thermal conductivity for first wall 45. T. M. Duncan: ‘The distribution of carbon in boron carbide: a 13C
armour’, J Nucl. Mater., 1997, 241–243, 1175–1179 nuclear magnetic resonance study’, J. Am. Chem. Soc., 1984, 106,
21. J. G. V. D. Laan, G. Schenedecker, E. V. V. Osch, R. Duwe and 2270–2275.
J. Linke: ‘Plasma sprayed boron carbide coating for first wall 46. J. E. Saal, S. Shang and Z. K. Liu: ‘The structural evolution of
protection’, J. Nucl. Mater., 1994, 211, 135–140. boron carbide via ab initio calculations’, App. Phys. Lett., 2007,
22. D. Gosset and B. Provot: ‘Boron carbide as a potential inert 91, 231915-1–3.
matrix: an evaluation’, Prog. Nucl. Energy, 2001, 38, (3–4), 263– 47. A. H. Silver and P. J. Bray: ‘Nuclear magnetic resonance study of
266. boron carbide’, J. Chem. Phys., 1959, 31, (1), 247.
23. M. W. Mortensen, P. G. Sorensen, O. Bjorkdahl, M. R. Jensen, 48. M. M. Balkrishnarajan, P. D. Panchratna and R. Hoffman:
H. J. G. Gundersen and T. Bjornholm: ‘Preparation and ‘Structure and bonding in boron carbide: the invincibility of
characterization of boron carbide nanoparticles for use as a novel imperfections’, New J. Chem., 2007, 31, 473–485.
agent in T cell-guided boron neutron capture therapy’, Appl. 49. C. Wood and D. Emin: ‘Conduction mechanism in boron
Radiat. Isotopes, 2006, 64, 315–324. carbide’, Phys. Rev. B, 1984, 29B, (8), 4582.
24. S. Sasaki, M. Takeda, K. Yokoyama, T. Miura, T. Suzuki, 50. R. Schmechel and H. Werheit: ‘Structural defects of some
H. Suematsu, W. Jiang and K. Yatsui: ‘Thermoelectric properties icosahedral boron-rich solids and their correlation with the
of boron carbide thin film and thin film based thermoelectric electronic properties’, J. Solid State Chem., 2000, 154, 61–67.
device fabricated by intense-pulsed ion beam evaporation’, Sci. 51. U. Kuhlmann and H. Werheit: ‘On the microstructure of boron
carbide’, Solid State Commun., 1992, 83, 849–852.
Technol. Adv. Mater., 2005, 6, 181–184.
52. D. Ghosh, G. Subhash, T. S. Sudarshan, R. Radhakrishnan:
25. S. Lee and J. Mazurowski: ‘Characterization of boron carbide
‘Dynamic indentation response of fine-grianed boron carbide’,
thin films fabricated by plasma enhanced chemical vapour
J. Am. Ceram. Soc., 2007, 90, (6), 1850–1857.
deposition from boranes’, J. Appl. Phys., 1992, 72, (10), 4925–
53. X. Q. Yan, Z. Tang, L. Zhang, J. J. Guo, C. Q. Jin, Y. Zhang,
4932.
T. Goto, J. W. McCauley and M. W. Chen: ‘Depressurization
26. M. Bouchacoart and F. Thevenot: ‘The correlation between the
amorphization of single-crystal boron carbide’, Phys. Rev. Lett.,
thermoelectric properties and stoichiometric properties and
2009, 102, 075505-1–4.
stoichiometry in the boron carbide phase B4C-B10?5C’, J. Mater. 54. D. Lezhava, G. Darsavelidze, D. Gabunia, O. Tsagareishvili,
Sci., 1985, 20, 1237–1247. M. Antadze and V. Gabunia: ‘Influence of carbon content on
27. H. Zhao, Y. He and Z. Jin: ‘Preparation of zirconium boride physicomechanical characteristics of boron carbide’, J. Solid State
powder’, J. Am. Ceram. Soc., 1995, 78, (9), 2534–2536. Chem., 2006, 179, 2934–2938.
28. C. Subramanian, T. S. R. Ch. Murthy and A. K. Suri: ‘Synthesis 55. T. Matsui, Y. Arita, K. Naito and H. Imami: ‘High temperature
and consolidation of titanium diboride’, Int. J. Refract. Met. Hard heat capacities and electrical conductivities of boron carbides’,
Mater., 2007, 25, 345–350. J. Nucl. Mater., 1991, 186, 7–12.
29. T. S. R. Ch. Murthy, B. Basu, R. Balasubramanian, A. K. Suri, 56. C. Wood, D. Emin and P. E. Gray: ‘Thermal conductivity of
C. Subramanian and R. K. Fotedar: ‘Processing and properties of boron carbides’, Phys. Rev. B, 1985, 31B, (10), 6811.
TiB2 with MoSi2 sinter additive: a first report’, J. Am. Ceram. 57. K. E. Gilchrist and S. D. Preston: ‘Thermophysical property
Soc., 2006, 89, (1), 131–138. measurements on some neutron absorbing materials’, High Temp.
30. C. C. Klepper: ‘Sintered boron as high-strength lightweight High Press., 1979, 11, 643–651.
structural material for aerospace vehicles’, available at: http:// 58. G. S. Karumidze and L. A. Shengelia: ‘Isotopic effect of boron
optics.nasa.gov/tech_days/tech_days_2005/ carbide thermal conductivity’, Diamond Relat. Mater., 1993, 3,
31. D. Emin: ‘Unusual properties of icosahedral boron-rich solids’, 14–16.
J. Solid State Chem., 2006, 179, 44–51. 59. K. Froment, D. Gosset, M. Guery, B. Kryger and C. Verdeau:
32. M. Bouchacourt and F. Thevenot: ‘The properties and structure ‘Neutron irradiation effects in boron carbides: evolution of
of the boron carbide phase’, J. Less Comm. Met., 1981, 82, 227– microstructure and thermal properties’, J. Nucl. Mater., 1992,
235. 188, 185–188.
33. M. Bouchacourt and F. Thevenot: ‘Analytical investigations in 60. F. J. Homan: ‘Performance modelling of neutron absorbers’,
the BC system’, J. Less Comm. Met., 1981, 82, 219–226. Nucl. Technol., 1972, 16, (1), 216–225.
34. M. Bouchacourt and F. Thevenot: ‘The melting of boron carbide 61. Ph. Dunner, H. J. Heuvel, M. Horle: ‘Absorber materials for
and the homogeneity range of the boron carbide phase’, J. Less control rod systems of fast breeder reactors’, J. Nuc. Mater., 1984,
Comm. Met., 1979, 67, 327–331. 124, (C), 185–194.
35. D. Gosset and M. Colin: ‘Boron carbides of various compositions: 62. T. Maruyama and T. Iseki: ‘Irradiation response and tritium
an improved method for x-ray characterisation’, J. Nucl. Mater., release behaviour of boron carbide’, J. Nuc. Mater., 1985, 133–
1991,183, 161–173. 134, 727–731.
36. K. A. Schwetz and P. Karduck: ‘Investigations in the boron 63. G. W. Hollenberg, W. V. Cummings: ‘Effect of fast neutron
carbon system with the aid of electron probe microanalysis’, irradiation of the structure of boron carbide’, J. Am. Ceram. Soc.,
J. Less Comm. Met., 1991, 175, 1–11. 1977, 60, (11–12), 520–525.
37. M. Beauvy: ‘Stoichiometric limits of carbon-rich boron carbide 64. T. Kaito, T. Maruyama, S. Onose and H. Horiuchi: ‘Irradiation
behavior of boron carbide neutron absorber’, available at:
phases’, J. Less Comm. Met., 1983, 90, 169–175.
www.iaea.or.atinisawsfnssfulltext0884_17.pdf
38. R. Lazzari, N. Vast, J. M. Besson, S. Baroni and A. D. Corso:
65. G. I. Copeland, C. K. H. Dubose, R. G. Donnelly and W. R.
‘Atomic structure and vibrational properties of icosahedral B4C
Martin: ‘Transmission electron microscopy of irradiated boron
boron carbide’, Phys. Rev. Lett., 1999, 83, (16), 3230–3233.
carbide’, J. Nucl. Mater., 1972, 43, 126–132.
39. Y. Feng, G. T. Seidler, J. O. Cross, A. T. Macrander and J. J.
66. G. L. Copeland, R. G. Donnelly and W. R. Martin: ‘Irradiation
Rehr: ‘Role of inversion symmetry and multiple effects in non-
behavior of boron carbide’, Nulc. Technol., 1972, 16, (1), 226–237.
resonant X-ray raman-scattering from icosahedral B4C’, Phys.
67. H. Inui, H. Mori and H. Fujita: ‘Electron irradiation induced
Rev. B, 2006, 69B, 125402-1–8.
crystalline to amorphous transition in boron carbide’, Scr.
40. D. R. Tallant, T. L. Aselage, A. N. Campbell and D. Emin: Metall., 1988, 22, 249–254.
‘Boron carbide structure by Raman spectroscopy’, Phys. Rev. B, 68. Y. Morohashi, T. Maruyama, T. Donomae, Y. Tachi and
1989, 40B, (8), 5649–5656. S. Onose: ‘Neutron irradiation effect on isotopically tailored
41. F. Mauri, N. Vast and C. J. Pickard: ‘Atomic structure of 11
B4C’, J Nucl. Sci. Technol., 2008 45, (9), 867–872
icosahedra B4C boron carbide from a first principles analysis of 69. R. R. Ridgway: ‘Boron carbide and the method of making the
NMR spectra’, Phys. Rev. Lett., 2001, 87, (8), 085506-1–4. same’, US patent no. 1897214, 1933.
42. G. H. Kwei and B. Morosin: ‘Structures of boron rich boron 70. M. T. Spohn: ‘Boron carbide’, Am. Ceram. Soc. Bull., 1993, 72,
carbides from neutron powder diffraction: implications for the (6), 88.
nature of the Inter-icosahedral chains’, J. Phys. Chem., 1996, 100, 71. G. Goller, C. Toy, A. Tekin and C. K. Gupta: ‘The production of
8031–8039. boron carbide by carbothermic reduction’, High Temp. Mater.
43. D. D. Radev, B. Mihailova and L. Konstantinov: ‘Raman Proc., 1996, 15, (1–2), 117–122.
spectroscopy study of metal containing boron carbide based 72. F. Schroll and A. Vogt: ‘Electrothermic production of boron
ceramics’, Solid State Sci., 2002, 4, 37–41. carbide’, US patent no. 2 163 293, 1939.
44. H. K. Clark and J. L. Hoard: ‘The crystal structure of boron 73. J. J. Scott: ‘Arc furnace process for the production of boron
carbide’, J. Am. Chem. Soc., 1943, 65, 2115. carbide’, US patent no. 3 161 471, 1964.
74. R. R. Ridgeway: ‘Methods of making abrasive metal carbides’, 100. L. J. Berchmans, V. Mani and K. Amalajyothi: ‘Synthesis of
US patent no. 2 155 682, 1939. boron carbide by calciothermic reduction process’, Int. J. Self-
75. M. P. L. N. Rao, G. S. Gupta, P. Manjunath, S. Kumar, A. K. propagat. High Temp. Synth., 2009, 18, (1), 60–63.
Suri, N. Krishnamurthy and C. Subramanian: ‘Temperature 101. I. A. Bairamashvili: ‘Experience in production of articles from
measurements in the boron carbide manufacturing process – a hot boron carbide for fast reactor control rods’, Proc. Techn.
model study’, Int. J. Refract. Met. Hard Mater., 2009, 27, (3), Committ. Meet. on ‘absorber materials, control rods and designs
621–628. of backup reactivity shutdown systems for breakeven cores and
76. M. P. L. N. Rao, G. S. Gupta, P. Manjunath, S. Kumar, A. K. burner cores for reducing plutonium stockpiles’, Obninsk, Russia,
Suri, N. Krishnamurthy and C. Subramanian: ‘Core temperature July 1995, International Atomic Energy Agency, IAEA-TEC
measurement in carbothermal reduction process’, Thermochim. DOC--884, 220–224.
Acta, 2009, 482, 66–71. 102. X. Guangshan, Z. Ruxian, W. Yonglan and L. Shikun: ‘Control
77. D. K. Bose, K. U. Nair and C. K. Gupta: ‘Production of high assembly to be used in CEFR’, Proc. Techn. Committ. Meet. on
purity boron carbide’, High Temp. Mater. Proc., 1986, 7, (2–3), ‘absorber materials, control rods and designs of backup reactivity
133–140. shutdown systems for breakeven cores and burner cores for
78. A. Alizadeh, E. T. Nassaj, N. Ehsani and H. R. Baharvandi: reducing plutonium stockpiles’, Obninsk, Russia, July 1995,
‘Production of boron carbide powder by carbothermic reduction International Atomic Energy Agency, IAEA-TECDOC--884,
from boron oxide and petroleum coke or carbon active’, Adv. 47–52.
Appl. Ceram., 2006, 105, (6), 291–296. 103. A. W. Weimer: ‘Carbide, nitride and boride materials, synthesis
79. A. Alizadeh, E. T. Nassaj and N. Ehsani: ‘Synthesis of boron and processing’, 89–95; 1997, London, Chapman & Hall.
carbide powder by a carbothermic reduction method’, J. Eur. 104. K. U. Nair, D. K. Bose and C. K. Gupta: ‘The production of
Ceram. Soc., 2004, 24, 3227–3234. elemental boron by fused salt electrolysis’, Miner. Proc. Extract.
80. C. Subramanian and A. K. Suri: ‘Development of boron based Metall. Rev., 1992, 9, 283–291.
neutron absorber materials’, Met. Mater. Process., 2004, 16, (1), 105. A. Jain, S. Anthonysamy, K. Ananthasivan, R. Ranganathan,
39–52. V. Mittal, S. V. Narsimhan and V. Mittal: ‘Charecterization of
81. A. W. Weimer W. G. Moore R. P. Roach, J. E. Hitt, R. S. Dixit electrodeposited elemental boron’, Mater. Charact., 2008, 59,
and S. E. Pratsinis: ‘Kinetics of carbothermal reduction synthesis 890–900.
of boron carbide’, J. Am. Ceram. Soc., 1992, 75, (9), 2509–2514. 106. E. M. Heian, S. K. Khalsa, T. Yamamoto and M. Ohyanagi:
82. B. Z. Dacic, V. Jokanovic, B. Jokanovic and M. D. Dramicanin: ‘Synthesis of dense, high-defect-concentration B4C through
‘Thermodynamics of gas phase carbothermic reduction of boron- mechanical activation and field assisted combustion’, J. Am.
anhydride’, J. Alloys Compd, 2006, 413, 198–205. Ceram. Soc., 2004, 87, (5), 779–783.
83. Yu. N. Tumanov: ‘The synthesis of boron carbide in a high 107. K. Yamada: ‘Boron carbide articles formed from an amorphous
frequency electromagnetic field’, J. Less Comm. Met., 1979, 67, boron/graphite powder mixture using a shock wave technique’,
521–529. J. Am. Ceram. Soc., 1996, 79, (4), 1113–1116.
84. W. Rafaniello and W. G. Moore: ‘Producing boron carbide’, US 108. J. Wei, B. Jiang, Y. Li, C. Xu and D. Wu: ‘Straight boron carbide
patent no. 4 804 525, 1989. nanorods prepared from carbon nanotubes’, J. Mater. Chem.,
85. A. W. Weimer, W. G. Moore and R. P. Roach: ‘Method for 2002, 12, 3121–3124.
producing uniform, fine boron containing ceramic powders’, US 109. S. Chen, D. Z. Wang, J. Y. Huang and Z. F. Ren: ‘Synthesis and
patent no. 5 194 234, 1993. characterization of boron carbide nanoparticles’, Appl. Phys. A,
86. A. W. Weimer, W. G. Moore and R. P. Roach: ‘Apparatus for 2004, 79A, (7), 1757–1759.
producing uniform fine ceramic powders’, US patent no. 5 110 110. B. Chang, B. L. Gersten, S. T. Szewczyk and J. W. Adams:
565, 1992. ‘Characterization of boron carbide nanoparticles prepared by a
87. S. Herth, W. J. Joost, R. H. Doremus and R. W. Siegel: ‘New solid state thermal reaction’, Appl. Phys. A, 2007, 86A, 83–
approach to the synthesis of nanocrystalline boron carbide’, 87.
J. Nanosci. Nanotechn., 2006, 6, (4), 954–959. 111. S. T. Benton and R. David: ‘Methods for preparing boron carbide
88. B. Chang, B. L. Gersten, S. T. Szewczyk and J. W. Adams: articles’, US patent no. 3 914 371, 1975.
‘Towards the preparation of boron carbide nanorods by 112. A. S. Ramos, S. P. Taguchi, E. C. T. Ramos, V. L. Arantes and
carbothermal reaction method’, NSTI Nanotech 2006 Techn. S. Ribeiro: ‘High energy ball milling of powder B-C mixture’,
Proc., 2006, 1, 369–372. Mater. Sci. Eng. A, 2006, 422A, (1–2), 184–188.
89. R. Ma and Y. Bando: ‘High purity single crystalline boron 113. U. A. Tamburini, Z. A. Munir, Y. Kodera, T. Imai and
carbide nanowires’, Chem. Phys. Lett., 2002, 364, 314–317. M. Ohyanagi: ‘Influence of synthesis temperature on the defect
90. L. H. Bao, C. Li, Y. Tian, J. F. Tian, C. Hui, X. J. Wang, C. M. structure of boron carbide: experimental and modeling studies’,
Shen and H. J. Gao: ‘Synthesis and photoluminescence property J. Am. Ceram. Soc., 2005, 88, (6), 1382–1387.
of boron carbide nanowires’, Chin. Phys. B, 2008, 17B, (12), 4585– 114. R. G. Bourdio: ‘Process of preparing boron carbide from boron
4591. halide and a hydrocarbon’, US patent no. 3 334 967, 1967.
91. F. F. Xu and Y. Bando: ‘Formation of two-dimensional 115. R. A. Clifton: ‘Production of boron carbide whiskers’, US patent
nanomaterials of boron carbides’, J. Phys. Chem. B, 2004, 108B, no. 3 525 589, 1970.
7651–7655. 116. E. W. James: ‘Catalyst for growth of boron carbide crystal
92. C. H. Jung, M. J. Lee and C. J. Kim: ‘Preparation of carbon free whiskers’, US patent no. 3 423 179, 1969.
B4C powder from B2O3 oxide by carbothermal reduction process’, 117. J. F. Ditter, F. J. Gerhart and R. E. Williams: ‘Boron carbide’, US
Mater. Lett., 2004, 58, 609–614. patent no. 4 017 587, 1977.
93. A. Aghai, C. Falamaki, B. E. Yekta and M. S. Afarani: ‘Effect of 118. I. M. MacKinnon and B. G. Reuben: ‘The synthesis of boron
seeding on the synthesis of B4C by the magnesiothermic reduction carbide in an RF plasma’, J. Electrochem. Soc., 1975, 122, (6),
route’, Ind. Ceram., 2002, 22, (2), 121–125. 806–811.
94. E. G. Gray: ‘Process for the production of boron carbide’, US 119. B. Zeng, Z. Feng, S. Li, Y. Liu, L. Cheng and L. Zhang:
patent no. 2 834 651, 1958 ‘Microstructure and deposition mechanism of CVD amorphous
95. A. Muta and T. Geja: ‘Method for producing boron carbide’, US boron carbide coatings deposited on SiC substrates at low
patent no. 3 338 679, 1967 temperature’, Ceram. Int., 2009, 35, 1877–1882.
96. T. A. Zhang Z. H. Dou, H. Yang and Q. L. Ding: ‘Preparation of 120. E. Wainer, S. Heights and M. S. Vukasovich: ‘Preparation of
boron carbide by magnesium reducing – SHS’, J. North Eastern carbide structures’, US patent no. 3 269 802, 1966.
Univ., 2003, 24, (10) 935–938. 121. J. Economy, R. Y. Lin and W. D. Smith: ‘High strength yarn
97. A. K. Khanra and M. M. Godkhindi: ‘Synthesis of boron carbide consisting of boron carbide fibers’, US patent no. 4 238 547, 1980.
by self –propagating high temperature synthesis’, J. Aust. Ceram. 122. M. Jazirehpour and A. Alizadeh: ‘Synthesis of boron carbide
Soc., 2005, 41, (1), 30–35. core- shell nanorods and a qualitative model to explain the
98. F. Deng, H. Y. Xie and L. Wang: ‘Synthesis of submicron B4C by formation of rough shell nanorods’, J. Phy. Chem., 2009, 113,
mechanochemical method’, Mater. Lett., 2006, 60, (13–14), 1771– 1657–1661.
1773. 123. M. Shu Fang, L. Jian, Z. Jun-Fu, S. Xiao-Xia and X. Bing-She:
99. L. L Wang, Z. A. Munir and J. B. Holt: ‘The feasibility of ‘Effect on graphite substrate to formation of boron carbide/
synthesis of B4C fiber –MgO composites by combustion’, Scr. carbon composite nanoropes’ Chn J. Inorg. Chem. 2009, 25, (6),
Metall. Mater., 1994, 31, (1), 93–97. 1050–1054.
124. M. Karaman, N. A. Sezgi, T. Dogu and H. O. Ozbelge: ‘Kinetic Int. Symp. on ‘Circuits and systems’, Island of Kos, Greece, May
investigation of chemical vapour depositionof B4C on Tungsten 2006, IEEE, 1179–1182.
substrate’, AIChE J., 2006, 52, (12), 4161–4166. 151. S. Lee and P. A. Dowben: ‘The properties of boron carbide/silicon
125. M. C. Schouler, M. C. Cheynet, K. Sestier, J. Garden and hetrojunction diodes fabricated by plasma-enhanced chemical
P. Gadelle: ‘New filamentous deposites in the boron-carbon vapor deposition’, Appl. Phys. A, 1994, 58A, 223–227.
system’, Carbon, 1997, 35, (7), 993–1000. 152. D. Byun, S. D. Hwang, P. A. Dowben, F. K. Perkins, F. Filips
126. A. O. Sezer and J. I. Brand: ‘Chemical vapor deposition of boron and N. J. Ianno: ‘Heterojunction fabrication by selective area
carbide’, Mater. Sci. Eng. B, 2001, B79, 191–202. chemical vapor deposition induced by synchrotron radiation’,
127. M. J. Santos, A. J. Silvestre and O. Conde: ‘Laser-assisted Appl. Phys. Lett., 1994, 64, (15), 1968–1970.
deposition of r-B4C coatings using ethylene as carbon precursor’, 153. S. D. Hwang, D. Byun, N. J. Ianno, P. A. Dowben and H. R.
Surf. Coat. Technol., 2002, 151–152, 160–164. Kim: ‘Fabrication of boron–carbide/boron hetrojunction devices’,
128. J. C. Oliveira, P. Paiva, M. N. Oliveira and O. Conde: ‘Laser- Appl. Phys. Lett., 1996, 68, (11), 1495–1497.
assisted CVD of boron carbide at atmospheric pressure’, Appl. 154. B. W. Robertson, S. Adenwalla, A. Harken, P. Welsch, J. I.
Surf. Sci., 1999, 138–139, 159–164. Brand, P. A. Dowben, and J. P. Classen: ‘A class of boron –rich
129. J. C. Oliveira and O. Conde: ‘Deposition of boron carbide by laser solid state neutron detectors’, Appl. Phys. Lett., 2002, 80, (19),
CVD: a comparison with thermodynamic predictions’, Thin Solid 3644–3646.
Films, 1997, 307, 29–37. 155. S. Adenwalla, P. Welsch, A. Harken, J. I. Brand, A. Sezer and
130. H. Vincent, C. Vincent, M. P. Berthet, J. Bouix and G. Gonzalez: B. W. Robertson: ‘Boron carbide/n-silicon carbide heterojunction
‘Boron carbide formation from BCl3–CH4–H2 mixtures on carbon diodes’, Appl. Phys. Lett., 2001, 79, (26), 4357–4359.
substrates and in a carbon fibre reinforced Al composite’, Carbon, 156. G. L. Harris and D. S. Parsons: ‘Method of producing boron
1996, 34, (9), 1041–1055. carbide from water alcohol solution of carbon source’, US patent
131. M. Olsson, S. Soderberg, B. Stridh and J. O. Carlsson: ‘Chemical no. 3 885 022, 1975.
vapour deposition of boron carbide: morphology and micro- 157. S. Mondal and A. K. Banthia: ‘Low temperature synthetic route
structure’, Thin Solid Films, 1989, 172, (1), 95–109. for boron carbide’, J. Eur. Ceram. Soc., 2005, 25, 287–291.
132. U. Jansson, J. O. Carlsson, B. Stridh, S. Soderberg and M. Olsson: 158. A. Sinha, T. Mahata and B. P. Sharma: ‘Carbothermal route for
‘Chemical vapor deposition of boron carbides: phase and preparation of boron carbide powder from boric acid-citric acid
chemical composition’, Thin Solid Films, 1989,172, (1),81–93. gel precursor’, J. Nucl. Mater., 2002, 301, 165–169.
133. S. Mierzejewska and T. Niemyski: ‘Preparation of crystalline 159. J. Economy and I. Matkowich: ‘Boron carbide fiber production’,
boron carbide by vapour phase reaction’, J. Less Comm. Met., US patent no. 3 825 469, 1974.
1965, 8, 368–374.
160. S. Cihangir, C. Ergun, S. Yilmaz and F. C. Sahin: ‘Synthesis of
134. R. E. Riley, L. R. Newkirk F. A. Valencia,S, Wallace and B4C/SiC composite from sugar based precursor’, Diffus. Defect
C. Terry: ‘Preparation and uses of amorphous boron carbide Data A, 2008, 283–286A, 268–272.
coated substrates’, US patent no. 4 287 259, 1981.
161. I. Yanase, R. Ogawara and H. Kobayashi: ‘Synthesis of boron
135. R. L. Heetstand and C. F. Leitten: ‘Boron carbide article and
carbide powder from polyvinyl borate precursor’, Mater. Lett.,
method of making’, US patent no. 3 367 826, 1968.
2009, 63, 91–93.
136. J. G. Donaldson, J. B. Stephenson and A. A. Coachran: ‘Boron
162. A. M. Hadian and J. A. Bigdeloo: ‘The effect of time, temperature
and boron carbide by vapor deposition’, Electrodepos. Surf.
and composition on boron carbide synthesis by sol-gel method’,
Treat., 1973/1974, 2, 149–163.
J. Mater. Eng. Perform., 2008, 17, (1), 44–49.
137. J. Berjonneau, G. Chollon and F. Langlais: ‘Deposition process
163. H. Konno, A. Sudoh, Y. Aoki and H. Habazaki: ‘Synthesis of
for amorphous boron carbide from CH4/BCl3/H2 precursor’,
C/B4C composites from sugar–boric acid mixed solutions’, Mol.
J. Electrochem. Soc., 2006, 153, (12), C795–C800.
Cryst. Liq. Crys. A, 2002, 386A, (1), 15–20.
138. J. C. Oliveira, M. N. Oliveira and O. Conde: ‘Structural
164. I. Hasegawa, Y. Fujii, T. Takayama and K. Yamada: ‘Phenolic
characterization of B4C films deposited by laser assisted CVD’,
resin–boron oxide hybrids as precursors for boron carbide’,
Surf. Coat. Technol., 1996, 80, 100–104.
J. Mater. Sci. Lett., 1999, 18, 1629–1631.
139. A. K. Knudsen and C. A. Langhoff: ‘Process for the preparation
of submicron sized boron carbide powders’, US patent no. 4 895 165. M. G. L. Mirabelli and L. G. Sneddon: ‘Synthesis of boron
628, 1990. carbide via Poly vinylpentaborane precursors’, Am. Chem. Soc.,
140. T. Oyama and K. Takeeuchi: ‘Gas-phase synthesis of crystalline 1988, 110, (10), 3305–3307.
B4C encapsulated in graphite particles by pulsed-laser irradiation’, 166. H. Wada, S. Ito, K. Kuroda and C. Kato: ‘The synthesis of boron
Carbon 1999, 37, 433–436. nitride and boron carbide by pyrolysis of boric acid/1,2,3-
141. D. Zhang, D. N. Mcilroy, Y. Geng and M. G. Norton: ‘Growth prpanetriol condensation product’, Chem. Lett., 1985, 14, (6),
and charactrization of boron carbide nanowires’, J Mater. Sci. 691–692.
Lett., 1999, 18, 349–351. 167. J. G. Joseph: ‘Process for depositing boron carbide’, US patent
142. V. Cholet, R. Herbin and L. Vandenbulcke: ‘Chemical vapour no. 3 480 467, 1969.
deposition of boron carbide from BBr3–CH4–H2 mixtures in a 168. L. Shi, Y. Gu, L. Chen, Y. Qian, Z. Yang and J. Ma: ‘A low
microwave plasma’, Thin Solid Films, 1990, 188, 143–155. temperature synthesis of crystalline B4C ultrafine powders’, Solid
143. O. Postel and J. Heberlein: ‘Deposition of boron carbide thin film State Commun., 2003, 128, 5–7.
by supersonic plasma jet CVD with secondary discharge’, Surf. 169. Y. Gu, L. Chen, Y. Qian, W. Zhang and J. Ma: ‘Synthesis of
Coat. Technol., 1998, 108–109, 247–252. nanocrystalline boron carbide via a solvothermal reduction of
144. K. Kunihito, S. Tsutomu, P. C. Hoon and Y. Hiroaki: ‘CVD CCl4 in the presence of amorphous boron powder’, J. Am. Ceram.
synthesis and thermoelectric properties of boron carbide’, Soc., 2005, 88, (1), 225–227.
J. Ceram. Soc. Jpn, 1992, 100, (1162), 853–857. 170. C. Ronning, D. Schwen, S. Eyhusen, U. Vetter and H. Hofsass:
145. T. S. Moss, L. W. Jack and K. L. More: ‘Chemical vapour ‘Ion beam synthesis of boron carbide thin films’, Surf. Coat.
deposition of B13C2 from BCl3–CH4–H2–argon mixtures’, J. Am. Technol., 2002, 158–159, 382–387.
Ceram. Soc., 1998, 81, (12), 3077–3086. 171. B. M. Todorovic, I. Draganic, D. Vasiljevic-Radovic,
146. S. V. Deshpande, E. Gulari, S. J. Harris, A. M. Weiner and N. Romdevic, M. Romccevic, M. Dramicanin and Z. Markovic:
M. Anita: ‘Filament activated chemical vapor deposition of boron ‘Synthesis of amorphous boron carbide by single and multiple
carbide coating’, Appl. Phys. Lett., 1994, 65, (14), 1757–1759. charged boron ions bombardment of fullerene thin films’, Appl.
147. I. Caretti, R. Gago, J. M. Albella and I. Jimenez: ‘Boron carbides Surf. Sci., 2007, 253, 4029–4053.
formed by coevaporation of B and C atoms: ‘Vapor reactivity, 172. M. Carlsson, F. J. G. Garcia, M. Johnsson: ‘Synthesis and
BxC12x composition, and bonding structure’, Phys. Rev. B, 2008, characterization of boron carbide whiskers and thin elongated
77B, 174109-1. platelets’, J. Cryst. Growth, 2002, 236, 466–476.
148. W. J. Lackey, D. Rosen, C. E. Duty, D. L. Jean, S. N. Bondi and 173. R. V. Krishnarao and J. Subrahmanyam: ‘Studies on the
T. N. Elkhatib: ‘Laser CVD system design operation, and formation of whiskers and platelets of B4C and BN’, J. Mater.
modeling’, Ceram. Eng. Sci. Proc., 2002, 23, (4), 23–33. Sci., 2004, 39, 6263–6269.
149. H. O. Pierson: ‘Handbook of chemical vapor deposition: 174. X. An, H. Zhai, H. Zhai, C. Cao and H. Zhu: ‘Synthesis and
principles, technology and application’; 1992, Park Ridge, NJ, characterization of boron carbide nanobelts’, Key Eng. Mater.,
Noyes Publications. 2007, 336–338, (III), 2166–2168.
150. K. Osberg, N. Schemm, S. Balkir, J. I. Brand, S. Hallbeck and 175. R. Ma and Y. Bando: ‘Investigation on the growth of boron
P. Dowbent: ‘A hand-held neutron detection sensor system’, Proc. carbide nanowires’, Chem. Mater., 2002, 14, 4403–4407.
176. N. R. Thakkar and R. G. Reddy: ‘Thermal plasma processing of 204. S. Yamada, K. Hirao, Y. Yamachi and S. Knzaki: ‘Sintering
boron carbide fine powders’, Mater. Sci. Technol. 2003 Meet., behaviour of B4C-CrB2 ceramics’, J. Mater. Sci. Lett., 2002, 21,
2003, 23, 47–60 1445–1447.
177. J. L. He: ‘Carbon rich boron carbide in the eutectic product 205. R. F. Speyer and H. Lee: ‘Improved pressureless densification of
synthesized by resistance heating of B2CN in graphite’, J. Alloys B4C’, Ceram. Trans., 2003, 151, 71–82.
Compd, 2007, 437, 238–246. 206. B. Y. Yin, L. S. Wang and Y. C. Fang: ‘Sintering mechanism of
178. F. F. Lange: ‘Densification of powder compacts: an unfinished pure and carbon-doped boron carbide’, J. Chin. Ceram. Soc.,
story’, J. Eur. Ceram. Soc., 2008, 28, (7), 1509–1516. 2001, 29, (1), 68–71.
179. L. S. Dole, S Prochazka and R H. Doremus: ‘Microstructural 207. K. A. Schwetz, G. Vogt and K. S. Mang: ‘Process for the
coarsening during sintering of boron carbide’, J. Am. Ceram. Soc., production of dense sintered shaped articles of polycrystalline
1989, 72, (6), 958–966. boron carbide by pressureless sintering’, US patent no. 4 195 066,
180. M. A. Kuzenkova, P. S. Kisly, B. L. Grabchuk and N. I. 1980.
Bodnaruk: ‘Structure and properties of sintered boron carbide’, 208. N. Cho, K. G. Silver, Y. Berta, R. F. Speyer, N. Vanier and C. H.
Powder Metall. Int., 1980, 12, (1), 11–13. Hung: ‘Densification of carbon-rich boron carbide nanopowder
181. M. A. Kuzenkova, P. S. Kislyi, B. L. Grabchuk and N. I. compacts’, J. Mater. Res., 2007, 22, (5), 1354–1359.
Bodnaruk: ‘The structure and properties of sintered boron 209. A. Matsumoto, T. Goto and A. Kawakami: ‘Slip casting and
carbide’, J. Less Comm. Met., 1979, 67, 217–223. pressureless sintering of boron carbide and its application to the
182. B. L. Grabchuk and P. S. Kislyi: ‘Some features of the sintering nuclear field’, J. Ceram. Soc. Jpn, 2004, 112, (5), S399–S402.
behavior of pure and technical boron carbide’, Sov. Powder 210. R. N. J. Taylor: ‘Novel powder processing of sintered boron
Metall., 1976, 15, (9), 675–678. carbide’, Key Eng. Mater., 2004, 45–48, 264–268.
183. H. Lee and R. F. Speyer: ‘Pressureless sintering of boron carbide’, 211. R, Telle and G. Petzow: ‘Strengthening and toughning of boride
J. Am. Ceram. Soc., 2003, 86, (9), 1468–1473. and carbide hard material composites’, Mater. Sci. Eng. A, 1988,
184. R. F. Speyer and J. Lee: ‘Advances in pressureless densification of A105/106, 97–104.
boron carbide’, J. Mater. Sci., 2004, 39, 6017–6021. 212. K. T. Faber and A. G. Evans: ‘Crack deflection processes –
185. X. Zhu, K. Lu and K. Nagarathnam: ‘Compaction of different I. Theory’, Acta Metall. 1983, 31, (4), 565–576.
boron carbide powders using uniaxial die compaction and 213. H. R. Baharvandi and A. M. Hadian: ‘Pressureless sintering of
combustion driven compaction’, J. Mater. Sci., 2009, 44, 414–421. TiB2–B4C ceramic matrix composite’, J. Mater. Eng. Perform.,
186. F. Thevenot: ‘Sintering of boron carbide and boron carbide- 2008, 17, (6), 838–841.
silicon carbide two-phase materials and their properties’, J. Nucl.
214. VI. V. Skorokhod and V. D. Krstic: ‘Processing, microstructure
Mater., 1988, 152, 154–162.
and mechanical properties of B4C–TiB2 particulate sintered
187. L. Levin, N. Frage and M. P. Dariel: ‘A novel approach for the
composites. I. Pressureless sintering and microstructure evolu-
preparation of B4C-based cermets’, Int. J. Refract. Met. Hard
tion’, Powder Metall. Met. Ceram., 2000, 39, (7–8), 414–423.
Mater., 2000, 18, 131–135.
215. V. V. Skorokhod, M. D. Vlajic and V. D. Krstic: ‘Pressureless
188. N. Frage, L. Levin and M. P. Dariel: ‘The effect of the sintering
sintering of B4C–TiB2 ceramic composites’, Mater. Sci. Forum,
atmosphere on the densification of B4C ceramics’, J. Solid State
1998, 282–283, 219–224.
Chem., 2004, 177, 410–414.
216. V Skorokhod, M. D. Vlajic and V. D. Krstic: ‘Mechanical
189. K. A. Schwetz and W. Grellner: ‘The influence of carbon on the
properties of pressureless sintered boron carbide containing TiB2
microstructure and mechanical properties of sintered boron
phase’, J. Mater. Sci. Lett., 1996, 15, 1337–1339.
carbide’, J. Less Comm. Met., 1981, 82, 37–47.
217. V. Skorokhod and V. D. Krstic: ‘Processing, microstructure and
190. M. Bougoin and F. Thevenot: ‘Pressureless sintering of boron
mechanical properties of B4C–TiB2 particulate sintered compo-
carbide with an addition of polycarbosilane’, J. Mater. Sci., 1987,
sites. II. Fracture and mechanical properties’, Powder Metall.
22, (1), 104–109.
Met. Ceram., 2000, 39, (9–10), 504–513.
191. B. Y. Yin and L. S. wang: ‘Studies on activated sintering of jet
218. M. D. Vlajic and V. D. Kristic: ‘Process for the production of
milled B4C powders’, Atom. Energy Sci. Technol., 2003, 37,
(Suppl.), 70–72, 76. dense boron carbide and transition metal borides’, US patent
no. 5 720 910, 1998.
192. J. E. Zorzi, C. A. Perottoni and J. A. H. da Jornada: ‘Hardness
and wear resistance of B4C ceramics prepared with several 219. L. Sigl, H. Thaler and K. A. Schwetz: ‘Process for producing
additives’, Mater. Lett., 2005, 59, 2932–2935. bodies based on boron carbide by pressureless sintering’, US
193. T. K. Roy, C. Subramanian and A. K. Suri: ‘Pressureless sintering patent no. 5 505 899, 1996.
of boron carbide’, Ceram. Int., 2006, 32, 227–233. 220. B. Khazai and W. G. Moore: ‘composition and method for
194. A. K. Suri and C. K. Gupta: ‘Studies on the fabrication of producing boron carbide/titanium diboride composite ceramic
aluminum bonded boron carbide rings’, J. Nucl. Mater., 1978, 74, powders using a boron carbide substrate’, US patent no. 5 108
297–302. 962, 1992.
195. H. R. Baharvandi, A. M. Hadian, H. Abdizade and N. Ehsani: 221. C. Subramanian, T. K. Roy, T. S. R. Ch. Murthy, P. Sengupta,
‘Investigation on addition of talc on sintering behavior and G. B. Kale, M. V. Krishnaiah and A. K. Suri: ‘Effect of Zirconia
mechanical properties of B4C’, J. Mater. Eng. Perform., 2006, 15, addition on pressureless sintering of boron carbide’, Ceram. Int.,
(3), 280–283. 2008, 34, 1543–1549.
196. H. R. Baharvandi, A. M. Hadian, A. Abdizadeh and N. Ehsani: 222. Q. Lin, P. Shen, F. Qiu, D. Zhang and Q. Jiang: ‘Wetting of
‘Investigation on addition of ZrO2-3 mol% Y2O3 powder on polycrystalline B4C by molten Al at 1173–1473 K’, Scr. Mater.,
sintering behavior and mechanical properties of B4C’, J. Mater. 2009, 60, 960–963.
Sci., 2006, 41, 5269–5272. 223. C. H. Danny, J. P. Aleksander, A. A. Ilhan and E. S. William:
197. L. Levin, N. Frage and M. P. Dariel: ‘The effect of Ti and TiO2 ‘Processing of boron carbide-aluminum composites’, J. Am.
additions on the pressureless sintering of B4C’, Metall. Mater. Ceram. Soc., 1989, 72, (5), 775–780.
Trans. A, 1999, 30A, 3201–3210. 224. P. Kewu, W. Wenyuan, X. Jingyu, T. Ganfeng and N. Fuhu:
198. A. Goldstein, Y. Yeshurun and A. Goldenberg: ‘B4C/metal boride ‘Study on mechanical properties and fracture mechanisms of B4C–
composites derived from B4C/metal oxide mixtures’, J. Eur. CeB6/Al composites’, J. Rare Earth., 2007, 25, (suppl.), 77–81.
Ceram. Soc., 2007, 27, (2–3), 695–700. 225. K. M. Taylor, N. Falls and R. J. Palicka: ‘Dense carbide
199. C. H. Lee and C. H. Kim: ‘Pressureless sintering and related composite for armor and abrasives’, US patent no. 3 765 300,
reaction phenomena of Al2O3-doped B4C’, J. Mater. Sci., 1992, 1973.
27, (23), 6335–6340. 226. S. Hayun, A. Weizmann, M. P. Dariel and N. Frage: ‘The effect
200. L. S. Sigl: ‘Processing and mechanical properties of boron carbide of particle size distribution on the microstructure and the
sintered with TiC’, J. Eur. Ceram. Soc., 1998, 18, 1521–1529. mechanical properties of boron carbide based reaction bonded
201. S. Prochazka and B. Lake: ‘Dense sintered boron carbide composites’, Int. J. Appl. Ceram. Technol., 2009, 6, (4), 492–500.
containing beryllium carbide’, US patent no. 4005235, 1977. 227. D. Mallick, T. K. Kayal, J. Ghosh, O. P. Chakrabarti, S. Biswas
202. G. Q. Weaver: ‘Sintered high density boron carbide’, US patent and H. S. Maiti: ‘Development of multi-phase B–Si–C ceramic
no. 4 320 204, 1982. composite by reaction sintering’, Ceram. Int., 2009, 35, (4), 1667–
203. S. Yamada, K. Hirao, Y. Yamauchi and S. Kanzaki: 1669.
‘Densification behaviour and mechanical properties of pressure- 228. Z. F. Chen, Y. C. Su and Y. B. Cheng: ‘Formation and sintering
less-sintered B4C-CrB2 ceramics’, J. Mater. Sci., 2002, 37, 5007– mechanisms of reaction bonded silicon carbide–boron carbide
5012. composites’, Key Eng. Mater., 2007, 352, 207–212.
229. J. Y. Liu, C. P. Zou, W. S. Zha, G. H. Liu, J. Lan and Q. H. Feng: 255. T. Jiang, Z. Jin, J. Yang and G. Qiao: ‘Wear resistance of silicon
‘Effect of sintering temperature on microstructure and compres- infiltrated B4C/BN composites’, Mater. Lett., 2008, 62, 4559–
sive strength of B4C–AlSi eutectic alloy’, Nucl. Power Eng., 2008, 4562.
29, (2), 58–60, 104. 256. S. Yamada, K. Hirao, Y. Yamauchi and S. Kanzaki: ‘Mechanical
230. M. Aizenshtein, I. Mizrahi, N. Froumin, S. Hayun, M. P. Dariel and electrical properties of B4C–CrB2 ceramics fabricated by
and N. Frage: ‘Interface interaction in the B4C/(Fe–B–C) system’, liquid phase sintering’, Ceram. Int., 2003, 29, 299–304.
Mater. Sci. Eng. A, 2008, A495, 70–74. 257. M. S. Koval’chenko, Yu. G. Tkachenko, V. V. Koval’chuk, D. Z.
231. I. Mizrahi, A. Raviv, H. Dilman, M. Aizenshtein, M. P. Dariel Yurchenko, S. V. Satanin and A. I. Kharlamov: ‘Structure and
and N. Frage: ‘The effect of Fe addition on processing and properties of hot-pressed boron carbide base ceramics’, Sov.
mechanical properties of reaction infiltrated boron carbide-based Powder Metall. Met. Ceram., 1990, 29, (7), 523–526.
composites’, J. Mater. Sci., 2007, 42, 6923–6928. 258. C. H. Jung and S. J. Lee: ‘Machining of hot pressed alumina-
232. M. K. Aghajanian, A. L. McCormick, B. N. Morgan and A. F. boron carbide composite cutting tool’, Int. J. Refract. Met. Hard
Liszkiewicz: ‘Boron carbide composite bodies, and methods for Mater., 2005, 23, 171–173.
making same’, US patent no. 0 169 128 A1, 2006. 259. B. Y. Yin and L. S. Wang: ‘Study on mechanical strength of the
233. S. Hayun, D. Rittel, N. Frage and M. P. Dariel: ‘Static and hot-pressing sintered boron carbide’, Atom. Energy Sci. Technol.,
dynamic mechanical properties of infiltrated B4C–Si composites’, 2004, 38, (6), 522–525.
Mater. Sci. Eng. A, 2008, 487, 405–409. 260. www.atozofmaterials.com
234. G. T. Burns, G. A. Zankm and J. A. Ewald: ‘Preparation of high 261. B. Matchen and D. Robertson: ‘Boron carbide ballistic armour
density boron carbide ceramics with preceramic polymer binders’, modified with chromium and/or boron’, US patent no. 3 729 372,
US patent no. 5 545 687, 1996. 1973.
235. K Hirao, S. Sakaguchi, Y Yamauchi, S Kanzaki and S Yamada: 262. S. Tuffe, J. Dubois, G. Fantozzi and G. Barbier: ‘Densification,
‘Boron carbide based sintered compact and method for prepara- microstructure and mechanical properties of TiB2-B4C based
tion thereof’, US patent no. 0063583, 2008. composites’, Int. J. Refract. Met. Hard Mater., 1996, 14, 305–310.
236. P. F. Jahn: ‘Use of alumina alone or with silica as sintering aid for 263. G. Petzow, H. Hofmann and K. Weiss: ‘Process for the
boron carbide’, US patent no. 3 632 710, 1972. preparation of carbide-boride products’, US patent no. 4 670
237. B. Y. Yin and L. S. Wang: ‘Study on physical properties of hot- 408, 1987.
pressing sintered B4C ceramic’, Atom. Energy Sci. Technol., 2004, 264. K. F. Cai, C. W. Nan, M. Schumecker and E. Mueller:
38, (5), 429–431. ‘Microstructure of hot pressed B4C–TiB2 thermoelectric compo-
238. M. S. Koval’chenko, Yu. G. Tkachenko, L. F. Ochkas, D. Z. sites’, J Alloys Compd, 2003, 350, 313–318.
Yurchenko and V. B. Vinokurov: ‘Densification kinetics of boron 265. A. Li, Y. Zhen, Q. Yin, L. Ma and Y. Yin: ‘Microstructure and
carbide in hot pressing’, Sov. Powder Metall. Met. Ceram., 1987, properties of (SiC,TiB2)/B4C composites by reaction hot pressing’,
26, (11), 881–884. Ceram. Int., 2006, 32, 849–856.
239. I. T. Ostapenko, V. V. Slezov, R. V. Tarasov, N. F. Kartsev and
266. J. H. Han, S. W. Park and Y. D. Kim: ‘Reaction synthesis and
V. P. Podtykan: ‘Densification of boron carbide powder during
mechanical properties of B4C-based composites’, Mater. Sci.
hot pressing’, Sov. Powder Metall. Met. Ceram., 1979, 18, (5),
Forum, 2007, 534–536, 917–920.
312–316.
267. M. Yokouchi: ‘Effect of Mo content on mechanical properties of
240. R. Angers and M. Beauvy: ‘Hot-pressing of boron carbide’,
B4C(W,Mo)B2 hard material’, J. Jpn Soc. Powder Powder Metall.,
Ceram. Int., 1983, 10, (2), 49–55.
1999, 47, (1), 23–29.
241. G. I. Kalandadze, S. O. Shalamberidze and A. B. Peikrishvili:
268. M. Yokouchi: ‘Effect of B content on mechanical properties of
‘Sintering of boron and boron carbide’, J. Solid State Chem.,
B4C(W,Mo)B2 hard material’, J. Jpn Soc. Powder Powder Metall.,
2000, 154, 194–198.
2001, 48, (7), 660–664.
242. B. Champagne and R. Angers: ‘Mechanical properties of hot-
269. O. N. Grigor’ev, V. V. Kovalchuk, O. I. Zaporozhets, N. D. Bega,
pressed B-B4C materials’, J. Am. Ceram. Soc., 1979, 62, (3–4),
B. A. Galanov, E. V. Prilutskii, V. A. Kotenko, T. N. Kutran and
149–153.
N. A. Dordienko: ‘Synthesis and physicomechanical properties of
243. K. Hirao, S. Sakaguchi, Y. Yamauchi, S. Kanzaki and S. Yamada:
B4C–VB2 composites’, Powder Metall. Met. Ceram., 2006, 45, (1–
‘Boron carbide based sintered compact and method for prepara-
2), 47–58.
tion thereof’, US patent no. 0 059 541 A1, 2005.
270. P. A. D. S. L. Cosention, C. A. Costa, J. B. De Campos and R. R.
244. V. Skorokhod, Jr and V. D. Krstic: ‘High strength-high toughness
De Avillez: ‘Hot pressing of boron carbide using metallic carbides
B4C–TiB2 composites’, J. Mater. Sci. Lett., 2000, 19, 237–239.
as additives’, Ceram. Eng. Sci. Proc., 2008, 28, (5), 135–141.
245. H. Hofmann and G. Petzow: ‘Structure and properties of reaction
hot-pressed B4C–TiB2–W2B5 materials’, J. Less Comm. Met., 271. D. Jianxin and S. Junlong: ‘Sand erosion performance of B4C
1986, 117, 121–127. based ceramic nozzles’, Int. J. Refract. Met. Hard Mater., 2008,
246. J. Deng, J. Zhou, Y. Feng and Z. Ding: ‘Microstructure and 26, 128–134.
mechanical properties of hot-pressed B4C/(W,Ti)C ceramic 272. T. Jiang, Z. Jin, J. Yang and G. Qiao: ‘Property and
composites’, Ceram. Int., 2002, 28, 425–430. microstructure of machinable B4C/BN nanocomposites’, Key
247. D. Jianxin and S. Junlong: ‘Microstructure and mechanical Eng. Mater., 2008, 368–372, (1), 936–939.
properties of hot-pressed B4C/TiC/Mo ceramic composites’, 273. Z. Panek: ‘The synthesis of SiC-B4C ceramics by combustion
Ceram. Int., 2009, 35, 771–778. during hot-pressing’, J. Eur. Ceram. Soc., 1993, 11, 231–236.
248. S. Yamada, K. Hirao, Y. Yamauchi and S. Kanzaki: ‘B4C–CrB2 274. J. J. Petrovic, K. J. McClellan, C. D. Kise, R. C. Hoover and
composites with improved mechanical properties’, J. Eur. Ceram. W. K. Scarborough: ‘Functionally graded boron carbide’, Ceram.
Soc., 2003, 23, 561–565. Eng. Sci. Proc., 1998, 19, (4), 387–393.
249. T. Vasilos and S. K. Dutta: ‘Low temperature hot pressing of 275. K. S. Singhal and B. P. Singh: ‘Sintering of boron carbide under
boron carbide and its properties’, Am. Ceram. Soc. Bull., 1974, 53, high pressures and temperatures’, Ind. J. Eng. Mater. Sci., 2006,
(5), 453–454. 13, (2), 129–134.
250. D. Jianxin: ‘Erosion wear of boron carbide ceramic nozzles by 276. T. L. Hans: ‘Hot isostatic pressing of ceramic powders to dense
abrasive air-jets’, Mater. Sci. Eng. A, 2005, A408, 227–233. ceramic parts’, Ind. Heat., 1984, 51, (1), 39–40, 42.
251. B. Mu, L. Tang, H. Zhang, W. Yan, T. Yin and T. Zhang: 277. T. L. Hans: ‘Dense ceramic parts hot pressed to shape by HIP’,
‘Influence of the rare-earth oxide on the properties of boron Mater. Sci. Res., 1984, 17, 571–582.
carbide ceramics’, Powder Metall. Technol., 2008, 26, (3), 187–191, 278. P. Larsson, N. Axen and S. Hogmark: ‘Improvements of the
195. microstructure and erosion resistance of boron carbide with
252. B. Mikijelj, G. Victor and K. A. Schwetz: ‘Lightweight boron additives’, J. Mater. Sci., 2000, 35, 3433–3440.
carbide materials with improved mechanical properties and 279. N. Cho, Z. Bao and R. F. Speyer: ‘Density-and hardness-
process for their manufacture’, US patent no. 0 010 391 A, 2007. optimized pressureless sintered and pot-hot isostatic pressed B4C’,
253. T. Maruyama and S. Onose: ‘Fabrication and thermal conductiv- J. Mater. Res., 2005, 20, (8), 2110–2116.
ity of boron carbide/copper cermet’, J. Nucl. Sci. Technol., 1999, 280. N. Cho: ‘processing of boron carbide’, PhD thesis, School of
36, (4), 380–385. Materials Science and Engineering, Georgia Institute of
254. T. Jiang, Z. Jin, J. Yang and G. Qiao: ‘Investigation on the Technology, Atlanta, GA, USA, 2006.
preparation and machinability of the B4C/BN nanocomposites by 281. R. F. Speyer and E. A. Judson: ‘New process makes complex-
hot-pressing process’, J. Mater. Proc. Technol., 2009, 209, 561– shaped armor a reality’, Am. Ceram. Soc. Bull., 2006, 85, (3), 21–
571. 23.
282. K. A. Schwetz, W. Grellner and A. Lipp: ‘Mechanical properties sintered, functionally graded boron carbide-aluminum compo-
of HIP treated sintered boron carbide’, Inst. Phys. Conf. Ser., sites’, Mater. Sci. Eng. A, 2008, A488, 333–338.
1986, 75, 413–426. 295. Y. Ling, C. Ge, J. Li and X. Bai: ‘Processing and characterization
283. K. A. Schwetz, L. S. Sigl and L. Pfau: ‘Mechanical properties of of B4C/Cu graded composite as plasma facing component for
injection molded B4C-C ceramics’, J. Solid State Chem., 1997, fusion reactors’, J. Univ. Sci. Technol. Beijing, 2003, 10, (1), 39–43.
133, 68–76. 296. D. Agrawal: ‘Microwave sintering of metals’, Mater. World, 1999,
284. M. H. Bocanegra-Bernal: ‘Hot isostatic pressing (HIP) technology 7, (11), 672–673.
and its applications to metals and ceramics’, J. Mater. Sci., 2004, 297. A. Goldstein, R. Ruginets and L. Geifman: ‘Carbide matrix
39, (21), 6399–6420. composites by fast MW reaction-sintering in air of B4C–SiC–Al
285. F. Zimmerman and J. Toops: ‘Hot isostatic pressing (HIP) mixtures’, Ceram. Int., 2008, 35, (3), 1297–1300.
technology’, Ind. Heat., 2006, 73, (8), 71–74. 298. I. Bogomol, T. Nishimura, O. Vasylikiv, Y. Sakka and P. Loboda:
286. T. Fujikawa, Y. Manabe, M. Yoneda, S. Kofune and T. Nakai: ‘Microstructure and high-temperature strength of B4C–TiB2
‘Recent trends of HIP equipment technology in Japan’, ASME composite prepared by a crucibleless zone melting method’,
Publ. PVP, 2004, 473, 27–31. J. Alloys Compd, 2009, 458, (1-2), 677–681.
287. S. H. Yoo, K. M. Sethuram and T. S. Sudarshan: ‘Apparatus for 299. C. Zhang, X. Huang, Y. Yin, F. Xia, J. Dai and Z. Zhu:
bonding a particle material to near theoretical density’, US patent ‘Preparation of boron carbide-aluminum composites by non-
no. 5 989 487, 1999. aqueous gelcasting’, Ceram. Int., 2009, 35, 2255–2259.
300. W. M. Goldberger, A. K. Reed and R. Morse: ‘Synthesis and
288. B. Klotz, K. Cho, R. J. Dowding and S. D. Sisson:
characterization of HSC silicon carbide’, Proc. Conf. Silicon
‘Characterization of boron carbide consolidated by the plasma
Carbide ’87, (ed. J. D. Cawley), 93–104; 1987, Westerville, OH,
pressure compaction (P2C) method in air’, Ceram. Eng. Sci. Proc.,
The American Ceramic Society.
2001, 22, (4), 27–34.
301. M. Steinbruck, A. Meier, E. Nold and U. Stegmaier:
289. B. R. Klotz, K. C. Cho and R. J. Dowding: ‘Sintering aids in the
‘Degradation and oxidation of B4C control rod segments at high
consolidation of boron carbide (B4C) by the plasma pressure
temperatures’, Institut fur Materialforschung, Programm
compaction (P2C) method’, Mater. Manuf. Process., 2004, 19, (4),
Nukleare Sicherheitsforschung, Forschungszentrum Karlsruhe
631–639. GmbH, Karlsruhe, Germay, 2004.
290. N. Frage, S. Hayun, S. Kalabkhov and M. P. Dariel: ‘The effect 302. M. Steinbruck: ‘Oxidation of boron carbide at high temperatures’,
of Fe addition on the densification of B4C powder by spark J. Nucl. Mater., 2005, 336, 185–193
plasma sintering’, Powder Metall. Met. Ceram., 2007, 46, (11–12), 303. H. Steiner: ‘Modelling of boron carbide oxidation in steam’,
533–538. J. Nucl. Mater., 2005, 345, 75–83.
291. Y. Kodera, N. Isibashi, T. Imai, T. Yamamoto, M. Ohyanagi, 304. R. Zehringer, H. Kunzli and P. Oelhafen: ‘Oxidation behaviour of
U. Anselmi-Tamburini and Z. A. Munir: ‘Spark plasma sintering boron carbide’, J. Nucl. Mater., 1990, 176/177, 370–374.
of less-crystallized boron carbide with defects’, Ceram. Trans., 305. D. Radev and Z. Zahariev: ‘Oxidation stability of B4C–MexBy
2006, 194, 101–111. composite materials’, J. Alloys Compd, 1993, 197, 87–90.
292. C. B. Wang, S. Zhang, Q. Shen and L. M. Zhang: ‘Investigation 306. O. N. Grigorev, T. V. Dubovik, N. D Bega, V. A. Kotenko, V. M.
on reactive sintering process of boron carbide ceramics by XRD’, Panashenko, V. I. Lyashenko, A. A. Rogozinskaya and L. I.
Mater. Sci. Technol., 2009, 25, (6), 809–812. Chernenko: ‘Sintered ceramics based on boron nitride and
293. S. Zhang, R. Yang, Q. Shen, C. B. Wang and L. M. Zhang: carbide’, Powder Metall. Met. Ceram., 2007, 46, (1–2), 46–50.
‘Synthesis and densification of B-C ceramics by spark plasma 307. J. Rodel, A. B. N. Kounga, M. Weissenberger-Eibl, D. Koch,
sintering’, J. Syn. Cryst., 2007, 36, (3), 672–674. A. Bierwisch, W. Rossner, M. J. Hoffmann, R. Danzer and
294. D. M. Hulbert, D. Jiang, U. Anselmi-Tamburini, C. Unuvar and G. Schneider: ‘Development of a roadmap for advanced ceramics:
A. K. Mukherjee: ‘Experiments and modeling of spark plasma 2010–2025’, J. Eur. Ceram. Soc., 2009, 29, 1549–1560.