Boron Carbide, Boron Nitride, and Metal Borides : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScie...

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Boron Carbide, Boron Nitride, and Metal Borides Email this page
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Jochen Greim1 and Karl A. Schwetz1
1ESK Ceramics GmbH & Co. KG, A Ceradyne Company, Kempten, Germany
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Copyright © 2006 by Wiley-VCH Verlag GmbH & Co. KGaA. All rights reserved.
DOI: 10.1002/14356007.a04_295.pub2
Article Online Posting Date: December 15, 2006 Advanced Product Search
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Abstract
The article contains sections titled:

1. Boron Carbide
1.1. Crystal Structure
1.2. The Boron - Carbon System
1.3. Physical Properties
1.4. Chemical Properties
1.5. Production
1.6. Uses
1.7. Economic Aspects
2. Boron Nitride
2.1. Properties
2.2. Production
2.3. Uses
3. Metal Borides
3.1. Properties
3.2. Production
3.3. Uses

[Top of Page]

1. Boron Carbide
Boron carbide [12069-32-8] belongs to the important group of nonmetallic hard materials, which includes alumina, silicon carbide, and diamond [1].
Although it was first prepared over a century ago, in 1883, by JOLY [2], the formula B4C was assigned only in 1934 [3]. Today a homogeneity range
from B4.3C to B10.4C has been established. The composition of commercial boron carbide is usually close to a boron : carbon stoichiometry of 4 : 1,
the stoichiometric limit on the high-carbon side.

Boron carbide is an exceedingly hard material, inferior in hardness only to diamond and cubic boron nitride. In addition, it has a high melting point, high
mechanical strength combined with low density, and high neutron cross section, and is a semiconductor. General information about boron carbide is
available in the reviews of LIPP [4], THEVENOT et al. [5], [6] and TELLE et al. [7].

1.1. Crystal Structure

Structurally, boron carbide can be considered a prototype of the so-called interstitial compounds of -rhombohedral boron [8], which include B12C3 [
12075-36-4] (= B4C), B12C2Al [9], B12S, B12O2, B12As2, B12P2, and B3 – 4Si [10]. The crystal structure for these materials consists of icosahedra that
occupy the points of a rhombohedron, plus a chain of atoms that runs along the c axis of the rhombohedron. For the most part, boron atoms occupy
the points of the icosahedra. The second constituent — C, Al, O — in general occurs on the chain (Fig. 1). (There is no chain at all in -rhombohedral
boron.) The rigid framework of polyatomic units of closely bonded atoms is reflected in the refractory nature and great hardness.

Figure 1. The structure of boron carbide for the stoichiometry B13C2.

For compositions close to B12C3, the lattice parameters are aH = 0.55980 nm and cH = 1.20707 nm [11]. However, the details of the boron carbide
structure [12], [13] are not firmly established. According to investigations [14] the sequence C–B–C can be assumed for the chain. In addition to these
two carbon atoms per unit cell, carbon likely replaces boron at the boron sites in the icosahedra. With 15 atoms per unit cell (B12C3) and 20 mol % C,
boron carbide can be reformulated as (B11C)CBC to show this effect. However, SCHWETZ and KARDUCK [15] reported B4.3C as the carbon-rich limit of
the homogeneity range of boron carbide. Optical absorption and reflectivity measurements on B4.3C indicated a structure with 81 % C – B – C chains,
19 % C – B – B chains, and exactly one carbon atom located in the B11C icosahedral site [16].

On the boron-rich side the extension of the homogeneity range to 8.7 mol % C, the ratio B : C = 10.4, has been reported by BOUCHACOURT, THEVENOT
[17], who propose the structural formula B12 –xCx (C/BxC1 –x /C) and n = 15.33 atoms per unit cell for B10.4C. The density of boron carbide at the

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Boron Carbide, Boron Nitride, and Metal Borides : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScie...
boron-rich end is 2.465 g/cm3; the volume of the unit cell, only 2.5 % larger than B4C, corresponding to the lattice parameters aH = 0.5651 nm and c
H = 1.2196 nm.

1.2. The Boron – Carbon System

Although numerous studies are available, not all parts of the B – C system have yet been fully elucidated.

SAMSONOV, SHURAVLOV, et al. [18], [19] reported the compounds B13C2 and B12C3, both with a large homogeneity range, in addition to the carbon-rich
BC2 and the boron-rich B12C phases. In the diagram of DOLLOFF [20], rhombohedral B13C2 and B12C3 phases are combined with a wide range of solid
solubility of only one carbide phase, B4+xC, which is stable only below 1800 °C. ELLIOT [21] reported the solid solubility of boron carbide from ca. 8 to
20 mol % C over the temperature range from room temperature to the melting point of 2450 °C. The B4C – C eutectic temperature was reported to be
2375 °C at 29.0 mol % carbon. Investigations by KIEFFER et al. [22] support this broad range of solid solubility. In addition to the compounds given in
these publications, B25C [23], B8C [24], and B13C3 [25] have been reported. These are likely low-temperature phases, which are often observed in
chemical vapor deposition. THEVENOT and BOUCHACOURT [5], [17] postulated a peritectic transformation of the -rhombohedral boron – carbon mixed
crystal, giving homogeneity range limits of B10.4C (8.8 mol % C) and B4.0C (20.0 mol % C). Their X-ray diffraction studies indicated a discontinuity in
the lattice parameters at the composition B6.5C. According to the phase diagram reported in 1983 by BEAUVY [26], the carbon-rich limiting composition
corresponds to B3.63C, i.e., “B11C3” with 21.6 mol % C. Investigations of the B – C system indicated [15], however, that the carbon content of fused
boron carbide in equilibrium with graphite is only 19.2 mol%, corresponding to the formula B4.3C. The phase diagram is presented in Figure 2. Recent
careful measurements of the lattice constants on high-purity boron carbide showed the boundaries of the single-phase region to be at about 9 atom %
C and near to, but likely some what less than, 20 atom % C [11]. Information on phase equilibria in the quaternary system B C Si N is
available in [27].

Figure 2. The B – C phase diagram [15]

The degenerated reaction at the B-rich corner is most probably an eutectic.

1.3. Physical Properties

The purest B4C crystals yet obtained by the electrothermic production process are deep black and shiny, a contrast to SiC crystals, which in their
purest form are transparent and colorless. The crystals melt congruently at ≈ 2450 °C; the liquid boils above 3500 °C. The density of B4C having the
natural isotopic composition is 2.52 g/cm3; 10B4C is less dense, 2.37 g/cm3.

The Knoop microhardness number HK-0.1, i.e., the hardness measured with a load of 0.1 kp ( 0.98 N), is ≈ 3000 [28] (2000 for -Al2O3, 2600 for
SiC and elemental boron, 4700 for cubic BN, and 7000 – 8000 for diamond). Therefore, except for diamond, the hardest known materials all contain
boron. Table 1 presents some mechanical properties of hot-pressed B4C and B4C-based composites manufactured by ESK. The fracture mode of
these materials is almost 100 % transgranular [29]. Boron carbide must be considered to be a refractory material, since hardness and strength do not
degrade up to 1500 °C in an inert atmosphere [4].

Table 1. Mechanical properties of various B4C ceramics

Property Materials

HP B4Ca B4C (5 % C)b BT 60/40c

Bulk density, g/cm3 2.51 2.51 3.30

Flexural strength (4-point, 20 °C), MPa 480 560 730
Knoop hardness 2910 2860 2900
Fracture toughness KIc, MPa · m1/2 2.2 2.1 6.5

Young's modulus, GPa 441 450 480

Mean grain size, µm 5 2 5

a Axially hot pressed B C with 1.7 wt % free carbon (C

4 total = 21.7 wt % C).
b HIP treated sintered B C with 4 wt % free carbon.
4
c HIP treated sintered B C – TiB composite with 40 vol % TiB .
4 2 2

The average coefficient of thermal expansion is 4.6 × 10–6K–1 over the range 25 – 800 °C, i.e., almost identical with that for pure SiC ceramic. The
coefficient of thermal expansion as a function of temperature (t in °C) is

Thermal conductivity decreases with temperature:

t, °C 25 200 400 600 800

, W m–1 K–1 35 28 23 19 16

However, B4C has low resistance to thermal shock [30].

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Boron Carbide, Boron Nitride, and Metal Borides : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScie...
Boron carbide is a high-temperature p-type semiconductor. The width of the forbidden band is 0.8 eV. The electrical conductivity depends on the B : C
ratio and impurity content. The specific electrical resistance of B4C is 0.1 – 10 Ω · cm, i.e., of the same magnitude as that of SiC and graphite [4], [31].
Boron carbide has a negative temperature coefficient of resistivity, similar to other ceramic materials. Boron carbide is notable for its high
thermoelectric power, which increases with temperature [5]. Electronic properties, i.e., electric conductivity, thermoelectric power, and the Hall effect,
were measured as a function of B : C ratio by WERHEIT et al. [14]. A metal – insulator transition occurs at the composition B4C.

The nuclear properties of boron carbide are such that it is a very effective neutron absorber in most types of reactors [4]. The effectiveness of boron as
a neutron absorber is due to the large cross section of the 10B isotope (≈ 4000 b). The natural abundance of 10B is 19.9 ± 0.3 mol %. The (n, )
reaction

produces helium plus lithium — and no radioactive nuclei. (In contrast, cadmium or the lanthanides do produce radioisotopes.) In addition, the
secondary gamma radiation is so small that it can be ignored. The cross section is a linear function of the neutron energy and follows a 1/v relation.
The cross sections of boron over the entire neutron energy spectrum, 0.01 – 1000 eV, are sufficiently large to make boron effective in thermal,
intermediate, and fast reactors.

1.4. Chemical Properties

Boron carbide is one of the most stable compounds. It is not dissolved by mineral acids or aqueous alkali; however, it is decomposed slowly by mixed
hydrofluoric – sulfuric acid or hydrofluoric – nitric acid. One technique of refining B4C from free carbon and boron is based on the differing oxidation
rates of the parent elements and boron carbide. The boron carbide powder is heated in a mixture of H2SO4, HNO3, HClO4, and K2Cr2O7 [32].

Molten alkali decomposes boron carbide to give borates. Boron carbide reacts with many metal oxides at elevated temperature to give carbon
monoxide and metal borides. Boron carbide reacts with many metals that form carbides or borides at 1000 °C, i.e., iron, nickel, titanium, and zirconium.
Aluminum [9] and silicon [33] form substitutional compounds with boron carbide. Boron carbide withstands metallic sodium fairly well at 500 °C [34] but
is slowly etched by hydrogen at 1200 °C. At that temperature it does not interact with sulfur, phosphorus, or nitrogen. Above 1800 °C it reacts with
nitrogen to give boron nitride. Elemental carbon can be dissolved in B4C at the B4C – C eutectic temperature of about 2400 °C, precipitating again on
cooling [20].

Chlorine attacks B4C at about 600 °C and bromine attacks it at 800 °C and above. These reactions can be used to prepare boron halides. Boron
carbide can be melted without decomposition in an atmosphere of carbon monoxide, but it reacts in the temperature range 600 – 750 °C with CO2 to
form B2O3 and CO. Oxidation in air starts at 500 °C and is severe at 800 – 1000 °C. However, the oxidative damage depends to a great extent on the
surface area of the object, powder being attacked more severely than bulk samples.

Detailed descriptions of chemical, mass spectrometric, and spectrochemical analysis of boron carbide have been issued by the American Society for
Testing and Materials (ASTM) [35].

Etching methods for polished sections for microstructural inspections of dense boron carbide materials are described thoroughly by PREDEL et al. [36].

1.5. Production
Powder. The most common method for large-scale production of boron carbide is carbothermic reduction of boric oxide:

The process is so strongly endothermic, 1812 kJ/mol or 9.1 kWh/kg, that it is usually carried out at 1500 – 2500 °C in an electric furnace. Either arc
furnaces or resistance furnaces, analogous to Acheson furnaces for SiC, are used [4]. The starting material is an intimate mixture of boric oxide and
carbon, e.g., petroleum coke or graphite. Large quantities of carbon monoxide, 2.3 m3/kg, are generated, and boron can be lost by evaporation of B
2O3 at the high temperatures. In the electrothermic process used by ESK, a subsidiary of Wacker Chemie, the product is cooled, and the unconverted
outer-zone material is removed to leave a fused coarse-grained boron carbide of high purity: B plus C ≥ 99 wt %, total metal impurity ≤ 0.2 wt %, N
plus O ≤ 0.3 wt %, B : C mole ratio of 4.0 – 4.3. This boron carbide is obtained in the form of regular blocks, which are broken up and milled to produce
the B4C grain size appropriate for final use.

If the carbothermic reduction is carried out below the melting point of B4C, e.g., at 1600 – 1800 °C, in a vented graphite tube furnace starting from a
dehydrated mixture of H3BO3, acetylene black or sugar, and ethylene glycol, very fine-grained (0.5 – 5 µm), stoichiometric B4C powders are produced
[37], although productivity is low.

Uniformly sized submicrometer powders of boron carbide (specific surface area 20–35 m2/g) can be synthesized continuously by rapid carbothermic
reduction (RCR) of boron oxide in a graphite transport reactor at ca. 2000°C [38], [39].

Boron carbide powders are produced directly (no need for the expensive comminution) by magnesiothermic reduction of boric oxide in the presence of
carbon at 1000 – 1800 °C:

This reaction is strongly exothermic. It is carried out either directly by point ignition (thermite process) or in a carbon tube furnace under hydrogen [40].
The product is washed free of magnesium oxide and unconsumed magnesium metal with hydrochloric or sulfuric acid and can be further purified by
heating under vacuum at 1800 °C. Since the MgO acts as a grain growth inhibitor, ultrafine boron carbide particles on the order of 0.1 – 1.5 µm are
obtained.

There are other methods of powder preparation:

1. synthesis from the elements

2. reduction of boron trichloride by hydrogen in the presence of carbon

3. chemical vapor deposition [41]

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However, these methods are generally used only on the laboratory scale for preparing high-purity boron carbide crystals or coatings [4].

Dense Shapes. Self-bonded [42] boron carbide shapes having 100 % theoretical density, small final grain size, and high mechanical strength can be
produced by hot pressing [43]. This is accomplished by placing a loose powder or a compact preform in a graphite die and applying uniaxial pressure
of 10 – 30 MPa at a temperature exceeding 2000 °C for 5 – 10 min. Inert or reducing atmospheres are necessary to protect B4C and the graphite from
oxidation. Increasing the boron content to the composition B13C2 has been found to facilitate sintering by reducing the necessary temperatures and to
almost double the strength [44]. However, for boron-rich B4+xC compositions, expensive boron nitride-lined graphite molds must be used, to avoid
carburization resulting in formation of carbon-rich B4C [45].

In 1977, ESK developed a process for pressureless sintering of boron carbide, a process now used in everyday production [46]. The key observation,
that carbon additives are extremely effective in inducing densification of B4C, was also made by HENNEY, JONES [47] and SUZUKI et al. [48] almost
simultaneously. There are two necessary conditions for obtaining a high sintered density:

1. The use of submicrometer B4C powders, i.e., powders with a mean particle size below 1 µm
2. The use of small amounts of elemental carbon-containing additive (novolac resin), which pyrolyes to amorphous carbon during the heating cycle
[29]

Up to the early 1990s, the carbon was added almost exclusively as novolac resin. However, after an improved method of dispersing carbon black
(particle size 20 nm) was developed, the resin route was replaced by the carbon black method [49]. Using nanosized carbon black as sintering aid
gives a better sintering behavior with very fine grained materials (mean grain size of B4C = 1 – 4 µm) having an approximate composition of 96 wt %
B4C and 4 wt % C. The properties of sintered B4C can be improved further by near net shape injection molding [50] and post-HIPing (HIP, hot isostatic
pressing) after pressureless sintering [50], [51]. In this post-HIP stage, the sintered shapes are densified to > 99.5 % TD at 1950 – 2050 °C in a high-
pressure autoclave (≥ 10 MPa).

The pressureless sintering/HIP route has also been used to prepare B4C – SiC composites [52], [53] and B4C – TiB2 composites [54], [55]. The B4C –
SiC composites combine the good thermal shock and oxidation resistance of silicon carbide with the hardness and low density of boron carbide. In
this way, a maximum strength of 550 MPa (four-point bend) was achieved for a composite of 59 wt % SiC, 37 wt % B4C and 4 wt % C. This composite
can be used in oxidizing atmospheres up to 1200 °C [52]. Excellent tribological and wear properties were obtained by KEVORKIJAN et al. [53] for B4C –
SiC composite materials, which suggest their use for heavily loaded mechanical seals and bearings.

The newly developed B4C – TiB2 composite materials [54], [55] are electroconductive and combine excellent fracture toughness (see Figure 3), with
the high hardness of boron carbide (Table 2). They are used as nozzle materials for hard alumina grits in abrasive air-jet cleaning in dental
laboratories. While the above-mentioned composite materials are formed by mixing the desired metal boride phases and subsequent sintering,
processes have also been described in which the desired metal boride composition is only formed after a suitable reaction of the starting materials
during the sintering step. SKOROKHOD and KRSTIC [56] fabricated a 85 vol % B4C – 15 vol % TiB2 composite with a flexural strength of 621 MPa and a
fracture toughness of 6.1 MPa · m1/2 (measured by the SENB method with 100 m notch width) by reaction hot pressing of a boron carbide powder
with submicrometer particle size using additions of submicrometer-sized TiO2 and carbon at 2000°C. The formation of uniformly distributed TiB2
particles (< 5 m grain size) was in accordance with the reaction.

Another approach to produce tough and high-strength B4C ceramics is liquid-phase sintering. LEE and KIM [57] showed that addition of alumina (Al2O
3) promotes densification of boron carbide, and a maximum density of 96% of theoretical can be obtained with 3 wt % alumina-doped B4C sintered at
2150°C, i.e., above the melting point of Al2O3. The microstructure showed equiaxial B4C grains with a mean grain size of about 7 m. However, when
the addition of Al2O3 exceeded 3 wt %, exaggerated grain growth occurred, which was attributed to the liquid phase. It has been reported [58] that by
hot pressing of B4C with alumina additions of up to 5 vol % at 2000 °C the mechanical properties can be remarkably increased as compared to
undoped, hot-pressed B4C of 88 % relative density. Fracture toughness increased steadily with the addition of Al2O3 from ca. 3 MPa · m1/2 (2.5 vol %
Al2O3) up to 3.8 MPa · m1/2 (10 vol % Al2O3). However, the achieved flexural strength was below 560 MPa.

The fracture toughness of boron carbide can be improved by addition of yttria [59] or of yttria in combination with other oxides [60]. The fracture
toughness of B4C can be increased to 3.9 MPa·m1/2 by vacuum sintering at 1900 – 1975°C of powder compacts of composition 97.5 wt % B4C and
2.5 wt % carbon packed in a yttria grit of 0.15 – 1.4 mm grain size [59]. The vacuum allows yttria vapor to penetrate the powder compact and promote
reaction sintering of carbon-doped B4C to full density (2.62 g/cm3). X-ray diffraction showed that yttrium boride and yttrium borocarbide were
coexistent with B4C. The method disclosed in [60] uses liquid-phase sintering under vacuum or streaming argon of powder compacts comprising B4C
powder (average particle size 0.6 – 3.5 m) and 1 – 28 wt % additions of Y2O3 in combination with Al2O3 or aluminum nitride (AlN) and La2O3 or
CeO2.

Figure 3. Fracture toughness of B4C – TiB2 composites and self-bonded B4C as a function of free carbon content

60/40 and 80/20 indicate B4C/TiB2 vol % in the starting mixture [54].

1.6. Uses
The uses of boron carbide are described in [4-6], [30], [31], [61].

Uses Based on Hardness. The major industrial use of boron carbide is as abrasive grit or powder. Commercial grits are available in particle sizes
from 1 µm to 10000 µm and predominantly used as polishing, lapping, and grinding media for hard materials, especially cemented tungsten carbide
and fine ceramics. Water and commercial oils serve as lubricant and coolant. Available as a substitute for loose powders is B4C paste, which can
withstand temperatures up to 350 °C.

The second category is wear-resistant engineering components made of dense, sintered shapes. Boron carbide sand-blasting nozzles are now the
most common form of such a component. These nozzles are characterized by minimum wear, even with corundum or silicon carbide grit. Sintered-B4C

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wheel dressing sticks are used to produce new cutting edges on surface grains of grinding wheels with minimum wear. So-called hand laps are used to
render the cutting edges of cemented carbide tools keen and smooth. Mortars and pestles of boron carbide are suitable for grinding hard materials
without contamination from the grinding equipment.

Ultrahard substances are nonductile. This factor, together with a density of only 2.5 g/cm3, is fully exploited in the use of dense B4C as ceramic plates
against armor-piercing bullets of caliber up to the thickness of the plates [61]. Lightweight ceramic tiles have been used extensively for the protection of
helicopters; monolithic breastplates, for the protection of personnel [62], [63]. Hot pressings made from a finer grade of boron carbide are used in air
bearings of inertial navigation equipment.

Uses in Nuclear Technology [30], [64]. Boron carbide is both cheaper and easier to fabricate than the element boron itself. As a result it has found
almost exclusive usage as a control rod material, neutron poison, and a neutron shielding material. The bulk density of vibro-packed B4C powder,
better the sintered density of self-bonded boron carbide pellets, or the 10B : 11B ratio can be varied to adapt absorber efficiency to the specific
conditions in thermal (BWR, PWR), high-temperature (HTR), and fast breeder reactors (FBR).

A 10B-enriched boron carbide, e.g., corresponding to ≤ 92 mol % 10B, is commercially available; thus, the nuclear worth of an absorbing element can
be increased nearly 4.5-fold by substituting enriched for natural material, without a change in dimensions. The helium formed during reactor exposure
is partially retained within the solid B4C as micropores, but the fraction released ( 50 %) must be accommodated by some aspect of control
assembly design, such as a plenum within an individual pin or a reliable pressure relief vent. The He and Li atoms, because of their relatively large
size, cause some radial swelling ( 10 %) of the B4C pellets.

In a typical thermal reactor the operating temperature of the absorber is below 500 °C, and low-density (ca. 75 % of theoretical density) B4C pellet
columns clad in metal sheets have proved adequate for large-scale commercial use. In gas-cooled reactors, boronated graphite containing about
40 wt % B meets the high-worth control rod requirements. Ceramic-based dispersions, i.e., combinations of relatively small amounts of B4C in an inert
matrix, exhibit smaller macroscopic neutron absorption cross sections but swell less and release less gas. So-called burnable poison rods, which are
consumed at the same rate as the fuel, are commonly designed in this fashion. Examples are Al2O3 – 3 vol % B4C for water-cooled reactors and
boronated graphite (ca. 6 wt % B4C) for gas-cooled reactors.

10B-enriched B4C has been chosen as the absorber for fast-breeder reactor control material. A potential alternative for future fast breeder generations
is10B-enriched europium hexaboride, which has better engineering properties and which loses its absorption reactivity because of 10B burnup about

40 % slower than B4C [65]. Carbon-bonded boron carbide plates (TETRABOR®) [66] provide for the closest possible arrangement of spent fuel
elements in high density intermediate storage pools. Sizes range up to 500 mm in length and down to 2 mm in thickness. These shield plates with
> 50 vol % B4C usually contain more absorber material than aluminum-bonded B4C (Boral) and silicone-bonded B4C plates (ESK-Elastosorb). Doors,
windows, or walls in laboratories where radioactive matter is investigated are screened with B4C plates. Their low density of ca. 1.6 g/cm3 makes them
excellent for lining containers for nuclear fuel or any matter radiating neutrons.

Chemical Uses. Boron carbide powder is used to introduce boron into the surface layer of steels and other ferrous materials [31], [67]. This takes
place by diffusion of boron into the surface layer, resulting in the formation of a thin (10 – 1000 µm) but hard, wear-resistant layer of iron boride, Fe2B.
Vickers hardness numbers of 2400 HV-0.1, corresponding to tungsten carbide or -Al2O3, were measured on the surface of high-alloyed tool steels.
The surfaces of cemented carbides (WC–Co, WC–TiC–TaC– Co/Ni/Fe, and Ferrotic) and stellite alloys can even be hardened further by boron [68].
According to the EKabor powder packing method B4C – SiC powder mixtures with added sodium tetrafluoroborate activator are used.

Its high boron content makes B4C useful as a raw material for the production of other boron compounds, including the boron halides and metal borides
[4]. Much of the BCl3 made commercially is used in the production of boron filament for reinforcement of metals and plastics. The exceptionally high
heat of combustion of B4C makes powders with a mean particle size of 2 µm useful energy carriers in solid rocket propellants [4].

Uses in Refractories. In carbon-bonded refractories, B4C powder is used as an antioxidant. Small additions of B4C to the refractory material reduce
the burn out of the carbon and improve the corrosion resistance against slags and steel melts. A simultaneous addition of B4C and a metallic
antioxidant results in better oxidation resistance of the refractories than the addition of B4C or the metallic antioxidant alone [69], [70]. The effect
depends on the oxidation of the antioxidants and reaction with the oxides of the refractory material, which creates oxidic phases and gaseous
components. Both prevent the infiltration of molten slag or steel, and the oxide phases protect the carbon against oxidation by forming a protective
oxidic layer at the hot face of the refractory.

Uses in Metal Matrix Composites. Metal matrix composites (MMCs) made of B4C and Al or Al-alloy have a higher stiffness, strength and hardness
and lower weight than the metal itself. The content of B4C in the MMCs is up to 50 wt %. This material could be used to produce magnetic disks for
hard disk drives, automotive components, sports goods, etc. [71-73].

Other Uses. The thermoelectric properties of B13C2 [74] are such that B13C2 could be an interesting material for high-temperature thermoelectric
conversion. Thermoelements made of the couple B4C – C can be used for temperature measurements up to 2300 °C [75].

1.7. Economic Aspects

ESK is the world's largest producer of boron carbide. The granular and sintered B4C products of this company are sold commercially under the
trademark TETRABOR®. The price of B4C is 10 – 150 $/kg, depending on grit size. Annual world production is about 3500 t.

[Top of Page]

2. Boron Nitride
The elements boron and nitrogen, both neighboring carbon in the periodic table, form the 1 : 1 compound BN [10043-11-5], which has allotropes
isostructural to the allotropes of carbon:

1. Alpha-BN, hexagonal modification with a layered structure similar to graphite, sometimes called white graphite
2. Beta-BN, high-pressure diamond-like modification, cubic zinc blende structure
3. Gamma-BN, dense hexagonal modification, wurtzite structure

More detailed reviews of the properties, preparation, and uses of the various BN modifications are given in [76-78], [63].

2.1. Properties

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-BN. The most common form of boron nitride is the graphitelike hexagonal, used increasingly because of its unique combination of properties: low
density, 2.27 g/cm3; high-temperature stability, mp near 3000 °C; chemical inertness, especially its resistance to acids and molten metals and its
stability in air up to 1000 °C and in inert gases like N2, CO, and Ar up to 2700 °C; stability to thermal shock; workability of hot-pressed shapes;
extremely low electrical conductivity, which makes it an excellent insulator; and high thermal conductivity.

In thermal conductivity BN ranks with stainless steel at cryogenic temperatures and with beryllium oxide, BeO, at higher temperature. Above 700 °C
the thermal conductivity of -BN exceeds that of BeO. Boron nitride has a dielectric constant of 4, one half that of -Al2O3, which also has high
dielectric strength. It is a lubricant over a wide range of temperatures; its low coefficient of friction is retained up to 900 °C, whereas other solid high-
temperature lubricants, e.g., graphite and molybdenum disulfide, burn away well below 900 °C [80].

Because of its stability at high temperature and inertness towards carbon and carbon monoxide up to 1800 °C, it is used as a refractory ceramic. In this
function it is superior to the nitride ceramics Si3N4 and AlN and the oxide ceramics MgO, CaO, and ZrO2. It is not wet by and thus is stable against
attack by molten glass, molten silicon, boron, nonoxidizing slags, molten salts such as borax and cryolite, and reactive molten metals, including
aluminum, iron, copper, and zinc. Because it sinters poorly, dense shapes of -BN are produced exclusively by hot pressing. Two material types are
important for practical applications

1. Shaped bodies of pure hexagonal BN

2. Shaped bodies of hexagonal BN with addition of refractory oxides, carbides and nitrides with BN contents ≥ 20 wt % (composite ceramics)

Typical properties of hot-pressed BN and BN – ZrO2 composite ceramics are summarized in Table 2.

Table 2. Property data on boron nitride ceramics

Hot-pressed Hot isostatically Hot-pressed composite

BN pressed BN ceramics BN/ZrO2

Bulk density, g/cm3 2.0 2.2 2.8 – 3.6b

Porosity, vol % <7 <1 <7
Modulus of rupture (4-point), a MPa 100/80 50 130/70
Young's modulus, a GPa 70/35 30 80/35
Thermal conductivity, c Wm–1K–1
20 °C 65/45 50 35 – 25/20 – 18 b
400 °C 50/30 40 31 – 21/17 – 15
700 °C 30/20 30 28 – 18/15 – 13
1000 °C 15/10 20 25 – 15/13 – 18
Thermal expansion coefficient, a 10–6 K–1 1.2/8.0 4.0 4.5 – 9.0/8.5 – 11.0 b
(at 20 – 1000 °C)
Specific heat, J/gK (at 20 °C) 0.8 0.8 0.7
Electrical resistivity, Ωcm (at 20 °C) > 1012 > 1012 > 1012
Dielectric strength, kV/mm (at 20 °C) >6 >6 >6

a Test orientation vertical/parallel to pressing direction.

b Dependent on BN/ZrO ratio.
2

Most chemical and physical properties of axial hot-pressed BN shapes depend on the nature and amount of densification additives (≤ 5 wt % B2O3 or
metal borates) [77]. In addition, the coefficient of expansion and thermal conductivity as well as the flexural strength and Young's modulus are
anisotropic; they vary with the direction of hot-pressing. In this respect, BN is similar to graphite. However, isostatic hot-pressing (HIP) of canned BN
powder, produces pure isotropic -BN shapes of theoretical density. Such shapes possess superior thermal and mechanical properties (see Table 2)
[81].

-BN. The cubic form of boron nitride, -BN, the commercial Borazon, resembles diamond in crystal structure and other properties. Pure -BN is
colorless and a good electrical insulator. Doping with Li3N or the elements Be, Si, C, or P turns -BN yellow to black and changes other properties,
such as conductivity or toughness.

The theoretical density of -BN is 3.48 g/cm3. The Knoop hardness number HK-0.1 is ca. 4700, somewhat less than the > 7000 for diamond. Because
-BN is stable in air up to 1400 °C — diamond burns away at only 800 °C — it is an effective high-temperature abrasive.

-BN. Wurtzite boron nitride, -BN, which is metastable at the pressures and temperatures where -BN is fabricated, has a density close to cubic -
BN. Above 5.5 GPa and 1300 °C -BN transforms to cubic -BN [82].

2.2. Production
Hexagonal -BN was prepared for the first time by BALMAIN [83] in the middle of the nineteenth century. It remained a laboratory curiosity until the mid-
1900s, when hot-pressed -BN shapes were made for the first time [84]. Although there are a number of general methods of producing powder [76],
principally two reactions are used on an industrial scale:

1. Reaction of boric oxide or boric acid with ammonia in the presence of a carrier, often tricalcium orthophosphate:

A second heat treatment for purification and stabilization is carried out > 1500 °C under N2.
2. Reaction of boric acid or borax with organic nitrogen compounds, e.g., urea or melamine:

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Method 1 usually gives crystalline -BN in the form of thin hexagonal platelets with a thickness of about 0.1 – 0.5 µm and a diameter of up to 5 µm.
Method 2 can give a “turbostratic” boron nitride, a hexagonal structure characterized by partial or complete absence of three-dimensional order among
its lamellae [85], [86].

Dense -BN is produced in two ways:

1. Axial hot-pressing [84] or hot isostatic pressing [81] of fine powders to give billets that can be easily machined
2. Pyrolysis of a boron trichloride – ammonia mixture,

on a graphite substrate on which the -BN is deposited.

Pyrolytic BN, though pore-free and impervious to helium, is anisotropic because the -direction layer planes of the hexagonal structure deposit parallel
to the substrate surface [87]. -BN is also available in the form of fibers [88], thin films [89], and multidimensional fiber infiltrated BN – BN composites
[90].

The cubic zinc blende form of boron nitride was first prepared from the graphitic form by applying pressures of 4 – 6 GPa (40 – 60 kbar) at 1400 –
1700 °C in the presence of a lithium or magnesium nitride catalyst [91]. Later, the use of the ternary compound Ca3B2N4 as the catalyst has been
proposed to produce -BN crystals of outstanding purity, quality, and size (0.1 – 0.3 mm) [92]. Details of the various high-pressure, high-temperature
(HP-HT) syntheses and low-pressure syntheses for -BN can be found in [63]. Deposition of -BN coatings, mainly produced by PVD and plasma CVD
methods, has been investigated. Due to the difficulties of growing large -BN crystals and depositing thick layers, the low-pressure sintering method is
not commercially used today.

Cubic BN particles can be sintered into strong masses at the high temperatures and high pressures at which this diamond-like form is stable [93]. Also
starting from shock-synthesized -BN of 0.1 – 0.5 µm particle size and hot pressing at 6.7 GPa and 1600 °C produces self-bonded compacts of
theoretical density and predominantly cubic structure, 80 % – 20 % -BN [82].

Wurtzite-type boron nitride, -BN, can be obtained by static compression above 6.0 GPa or by dynamic compression at 12 – 13 GPa below 1700 °C
[94], [95].

2.3. Uses
The many uses for -BN powder and hot-pressed shapes are summarized in Table 3, which classifies specific properties. As can be seen from this
table, -BN has established itself in the various fields of chemistry, metallurgy, high-temperature technology, electrotechnics, and electronics. -Boron
nitride powder is also available in the form of coating suspensions and as a convenient aerosol spray. Annual world production of -BN powder is
ca. 1000 t (ca. 2005); the price of -BN is 30 – 100 $/kg.

Table 3. Uses and potential uses for -boron nitride

Use Property desired

R T E I L M

-BN powder
Solid lubricant for high-temperature bearings + +

Mold release for die casting of glass and metals + + +

Active filler for rubber, resins, and plastics + + + + +

Additive to oils and high-temperature greases + +

Ultrahigh-pressure transmitting agent + + +

Coatings for evaporation plants, as parting agent for deposited metal films + +

Raw material for -BN +

Component for cosmetic applications + +

Coatings of tundishes for nonferrous metals + +

Mold release for injection molding of plastics +

Coating for graphite hot-pressing molds + + +

Embedding medium for heating wires + + +

Boron source for preparation of other boron compounds +

-BN hot-pressed shapes

Crucibles for melting glass and metals + + + +

Break rings for horizontal continuous casting of high-alloy steels + + + +

Break rings for low-alloy steels + + + +

Spanker plates used in the production of TV tubes + + +

End-dam material for thin-strip casting + + + +

Seal rings for gas sensors (lambda sensor) + + + +

Components for high-temperature electric furnaces + + + + +

Structural parts for magnetohydrodynamic devices (MHD) + + + +

Dielectric for radar antennas and windows + +

+ + +

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Insulators for low- and high-frequency equipment
Insulators for plasma-jet furnace, arc pulse generators, and ion engines + + +

Holders, mounting plates, substrates, and heat sinks in valve and transistor circuits + + +

Pump components, pipes, and nozzles for handling liquid metals + + +

Protective tubes and insulating sleeves for thermocouples + + + + +

Protective sleeves for electrodes in automatic welding + + + +

Wafers for boron doping of semiconductors + +

Molds for hot-pressing of ceramics like B6O or B6.5C + + + + +

Neutron absorbers and shields for nuclear reactors + + + +

R high-temperature refractoriness; T thermal conductivity; E electrical insulator; I chemical inertness, nonwetting; L lubricity; M machining
ease.

Since cubic boron nitride is the second hardest material after diamond, its uses are similar to those of diamond — machining and drilling. Grinding
wheels made from resin- or metal-bonded -BN grits in many cases are superior and more economical than diamond wheels because of their better
chemical resistance and greater toughness. Sintered dense compacts of -BN are being used increasingly as cutting tools for hard steels and tough
nickel-based superalloys, as wire drawing dies, and as cutting heads in rock drills [63]. The longer life of cutting tools containing wurtzite-type -BN in
addition can be related to the lubrication provided by the -BN that forms from the less stable -BN during cutting [96].

[Top of Page]

3. Metal Borides
Boron combines with a large number of metals and semimetals to form binary or higher solid compounds, the so-called borides. Most binary borides,
especially those formed from transition metals having high melting points, are metallic high-temperature materials that can be grouped with the
carbides, nitrides, and silicides as refractory hard materials [1], [97]. Although boride cermets [98], [99] that combine the extreme hardness of
refractory borides with the high toughness and ductility of a metallic binder have been recently developed, they are far from attaining large-scale
application.

Nevertheless, metal borides have some unique properties and are used in some specialized fields of modern industry, especially when the
requirements cannot be met by other materials. More information about metal borides is available in [31], [61], [100-108], [109]], [7].

3.1. Properties
Metal borides are unique in the number of stoichiometries; compositions corresponding to at least 24 M : B ratios between 5 : 1 and 1 : 66 are known.
However, the most common are the monoborides, MB; diborides, MB2; tetraborides, MB4; hexaborides, MB6; dodecaborides, MB12; and hectoborides,
MB66. The binary compounds of boron are given in the form of a periodic table in Table 4. As can be seen, many metal – boron systems contain three
or more intermediate phases.

Table 4. Binary compounds of boron

Main group elements

H3B a

Li5B4 Be4B (B (B BO BF3

b
12C) 12N2)
Li6B19 Be2B (B13C BN B 2 O2
2)
Li3B14 BeB2 B4.3C B 2 O3
LiB6 BeB6 BO2
(LiB (BeB12) BO3
10)
B12O2

NaB6 MgB2 AlB2 (B14Si) B12P2 B12S2 B2Cl4

NaB15 MgB4 AlB12 B12Si2 B13P2 BS BCl3
(MgB6) B3Si BP B2S2
MgB7 B2S3
(MgB12) BS2
B2S5
KB6 CaB4 B B BBr3
12As2 12Se2
CaB6 B BSe
13As2
BAs B2Se3
BSe2
(RbB SrB6 BI3
6)
(CsB

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Boron Carbide, Boron Nitride, and Metal Borides : Ullmann's Encyclopedia of Industrial Chemistry : Wiley InterScie...
6) BaB6

Transition elements
ScB2 TiB V3B2 Cr2B Mn2B Fe2B Co3B Ni3B
ScB12 TiB2 VB Cr5B3 MnB FeB Co2B Ni2B
V5B6 CrB Mn CoB Ni4B3
3B4
V3B4 Cr3B4 MnB2 NiB
Cr2B3
V2B3 CrB2 MnB4
VB2 CrB4

YB2 ZrB2 Nb Mo2B Tc3B Ru7B3 Rh7B3 Pd4B (AgB2)

3B2
YB4 ZrB12 NbB MoB Tc7B3 Ru Rh5B4 Pd3B
11B8
YB6 Nb MoB2 TcB2 RuB RhB Pd5B2
5B6
YB12 Nb MoB2.3 Ru2B3 Pd2B
3B4
YB66 Nb Mo RuB2
2B3 1–xB3
YB66 NbB2

* HfB Ta2B W2B Re3B OsB IrB0.9 Pt4B (AuB2)

HfB2 Ta3B2 WB Re7B3 Os2B3 IrB1.1 Pt2B
TaB WB2 ReB2 OsB2 IrB1.3 PtB0.7
Ta5B6
Ta3B4 W2B5
TaB2 W
1–xB3
**

* LaB4 CeB4 Pr2B5 Nd2B5 PmB4 Sm2B5 EuB6 Gd2B5 TbB2 DyB2 HoB2 ErB2 TmB2 YbB2 LuB2
LaB6 CeB6 PrB4 NdB4 PmB6 SmB4 GdB2 TbB4 DyB4 HoB4 ErB4 TmB4 YbB4 LuB4
LaB9 PrB6 NdB6 SmB6 GdB4 TbB6 DyB6 HoB6 ErB12 TmB12 YbB6 LuB12
NdB66 SmB66 GdB6 TbB12 DyB12 HoB12 ErB66 TmB66 YbB12 LuB66
GdB66 TbB66 DyB66 HoB66 YbB66

** ThB4 UB2 NpB2 PuB2 AmB4 CmB4

ThB6 UB4 NpB4 PuB4 AmB6 CmB6
ThB66 UB12 NpB6 PuB6 (AmB
12) (CmB12)
NpB12 PuB12 AmB66 CmB66
NpB66 PuB66

a And higher boranes.

b Parentheses around a compound indicate that its existence has not been confirmed. Note: high pressure phases are not listed.

A classification of borides was first given by KIESSLING [110] on the basis of boron structural elements typical for various M : B ratios. With increasing
M : B ratio the tendency to form boron – boron bonds increases, and pairs (M3B2 ), zigzag chains (MB), branched chains (M11B8 ), double chains (M
3B4 ), plane nets (MB2 ), and finally three-dimensional arrays of boron atoms, including cross-linked nets (MB4), interconnected B6 octahedra (MB6),
B12 cubic octahedra (MB12), and interconnected B12 icosahedra (MB66) are all found.

The most characteristic properties of the metal borides are their high melting points, extreme hardness, and in many cases high electrical and thermal
conductivities, fair corrosion resistance, good wear resistance, and thermal shock resistances superior to those of oxide ceramics. Some physical
properties of the most common and typical metal borides are given in Table 5. The most stable binary borides at high temperatures are the diborides of
titanium, zirconium, and hafnium, each melting above 3000 °C. The melting points of the boron-rich borides MBn, n 2, are generally higher than
those of the parent transition metals. On the other hand, melting points of metal-rich borides are often as low as those of their parent metals. Most of
these borides are paramagnetic. Knoop hardness numbers HK-0.1 usually fall in the range of 1100 – 2600 for diborides, 1650 – 2100 for hexaborides,
and 2300 – 2600 for dodeca- and hectoborides; therefore, many borides are harder than WC or -Al2O3, two cutting and grinding materials widely
used. Hardness and high melting points reflect the properties of the rigid, three-dimensional boron frameworks.

Table 5. Physical properties of some refractory borides [61]

Boride CAS Registry Density, Melting Electrical Knoop

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no. point resistivity, hardness,
103 kg/m3 K 10–8 Ω · m 0.1 kp load

TiB2 [12045-63-5] 4.52 3470 9 – 15 2600

ZrB2 [12045-64-6] 6.09 3520 7 – 10 1830
ZrB12 [12046-91-2] 3.61 2520 60 – 80 2580
HfB2 [12007-23-7] 11.2 3650 10 – 12 2160
VB2 [12007-37-3] 5.10 2670 16 – 38 2110
NbB2 [12007-29-3] 7.21 3270 12 – 65 2130
TaB2 [12007-35-1] 12.60 3370 14 – 68 2500
CrB2 [12007-16-8] 5.20 2170 21 – 56 1100
Mo2B5 [12007-97-5] 7.48 2370 18 – 45 2180
W2B5 [12007-98-6] 13.1 2470 21 – 56 2500
Fe2B [12006-85-8] 7.32 1663 1800
FeB [12006-84-7] 7.15 1820 30 1900
CoB [12006-77-8] 7.32 1535 26 2350
NiB [12007-00-0] 7.39 1325 23
LaB6 [12008-21-8] 5.76 2985 7 – 15 2010
EuB6 [12008-05-8] 4.91 2890 80 – 170 1840
UB4 [12007-84-0] 9.38 2768 30 1850
UB12 [12008-80-9] 5.65 2500 22 2630
CaB6 [12007-99-7] 2.46 2540 160 1650
SiB6 [12008-29-6] 2.43 2140 2×105 2140
B4C 2.52 2720 105 – 107 3000
-B 2.35 2420 1012 2600

The electrical characteristics, however, cover the entire spectrum: semiconductors, the MB66, MB6, and MB12 phases of Be, Mg, Ca, Eu, Al, and Si;
metallic conductors, TiB2, ZrB2, and the majority of transition-metal borides; superconductors, NbB, YB6, and ZrB12.

In addition, LaB6 and other lanthanide and actinide borides (YB6, ThB6, GdB6, etc.) belong to the best-known high-temperature electron emitters. Most
of these borides are intensively colored: for example, ZrB12 is pink, GdB6 is blue, LaB6 is purple, and ThB6 is scarlet [61, 111].

The metal borides display resistance to oxidation in air at elevated temperatures, most of them up to 1000 °C, and to attack by molten metals, basic
slags, and molten salts. Except for alkali metal and alkaline earth metal borides, which are saltlike and ionic, they are not readily attacked by
nonoxidizing acids and aqueous alkalis. Resistance to oxidation is greatest for the transition metal diborides and is lower for greater boron contents.
The controlling factor is the surface layer of parent boron and transition metal oxides, which prevents further oxidation up to temperatures at which
boric oxide has appreciable volatility. Most metal borides are inert in hydrogen, nitrogen, and carbon, even at high temperatures. Chlorine and fluorine
react vigorously with all borides, fluorine even at 400 °C. All types of borides are readily attacked by oxidizing molten salts such as nitrates and
carbonates and hydroxides in the presence of air, and this is a usual method of decomposition for chemical analysis [112].

3.2. Production
Metal borides can be prepared by the following high-temperature reactions [61]:

1. synthesis from the elements by melting, sintering, or hot-pressing

2. borothermic reduction of metal oxides
3. aluminothermic, silicothermic, or magnesiothermic reduction of metal oxide – boric oxide mixture
4. carbothermic reduction of metal oxide – boric oxide mixtures, e.g.,

5. reduction of metal oxide with carbon and/or boron carbide, i.e., the boron carbide method, e.g.,

6. electrolysis of fused salts containing metal oxide and boric oxide

7. auxiliary-metal bath method, M + B being dissolved in molten Al, Cu, Sn, or Pb
8. deposition from the vapor phase involving coreduction of a metal halide – boron halide mixture by hydrogen, optionally as a plasma [113]:

Reactions 1, 2, 6, 7, and 8 give pure products but are almost always restricted to the laboratory. For large-scale production, borides are prepared by
reactions 4 and 5 followed by purification. These reactions are usually carried out in electric furnaces much like those for production of boron carbide.
Molten metal borides often contain up to 3 wt % carbon and boron carbide, although these impurities can be scavenged with additional metal oxide or
boric oxide on reheating the powdered mixture above 1400 °C under a partial vacuum. After cooling, the metal boride is crushed and milled to its final
grain size. Monolithic boride shapes usually are fabricated from commercial boride powders by powder metallurgy techniques ( Powder Metallurgy
and Sintered Materials):

1. cold forming — isopressing, slip casting, etc. — followed by pressureless sintering of the powder compact [113-116], [117]

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2. axial hot-pressing [118-121] and hot isostatic pressing [116], [122] (see Section Production, production of B4C powder)

TiB2 – Fe hard metals have been developed to sintered densities above 99 % TD by using fine-grained raw materials and vacuum sintering [98], [123-
128]. The microstructure contains some Fe2B and Ti2O3, which can be avoided by additions of Ti or TiH2. The interesting strength, toughness and
hardness properties of these materials (see Figure 4) suggest some future applications.

Figure 4. Hardness and fracture toughness of TiB2 – Fe hard metals compared with commercial hard metals [129]

Cemented ternary transition metal borides have also been developed based on, e.g., Mo2(Fe, Ni)B2 as the hard phase sintered with iron metals (Fe,
Ni, Co). Especially the Mo2FeB2-base cermet shows excellent wear behavior [130], [131]. Mo2NiB2 cermets were produced from a Mo2NiB2-type
complex boride as a hard phase and a Ni-base binder by a novel sintering technique, named reaction boronizing sintering. The phase transformation
of the Mo2NiB2-type complex boride from orthorhombic to tetragonal with optimal addition of Cr and V was essential for improvement of the
mechanical properties (flexural strength, 2.5 GPa; Rockwell A hardness, ca. 90) and microstructural refinement of the cermet [99].

3.3. Uses
The principal use for metal diborides is as a crucible material for nonferrous metals, especially for aluminum, copper, magnesium, zinc, tin, and lead.
Monolithic shapes of dense TiB2 [132] are used for the electrolytic production of aluminum with the Hall – Héroult cell [133]. Hot-pressed TiB2 armor
plates are used in the protection of ground-based military vehicles. Their inertness to molten aluminum and cryolite and excellent electrical conductivity
suggest titanium diboride and zirconium diboride as cathode leads, electrodes, and thermocouple sheaths in aluminum metallurgy [134]. Related uses
are TiB2 – BN or TiB2 – BN – AlN hot-pressed composite crucibles, so-called evaporation boats, for the continuous evaporation of aluminum metal for
vacuum metallizing [135]. The composites show high corrosion resistance against molten metals and good electrical conductivity (TiB2 has high
electrical conductivity). The crucibles/boats are heated in direct current, and by varying the BN content the electrical conductivity of the boats can be
controlled. Coatings of BN are used in a wide range of applications due to the extraordinary properties of BN. They are used in the aluminum and steel
industries to enhance corrosion resistance and reduce wear on sliding parts like crankshafts for compressors. Because of the nonwettability of BN
against many metallic and nonmetallic melts various parts are often coated with BN, e.g., silicon in the semiconductor industry, or BN is used for
linings to prevent reactions with Si or Al. Coatings can be produced by CVD techniques to obtain well-crystallized linings with relatively high strength.
Also BN layers can be produced by spraying, brushing, dipping, and pouring. The coatings provide improved high-temperature electrical insulation for
the semiconductor industry. In molding equipment BN coatings reduce sticking and reactions between powder and mold. High-temperature lubrication
properties are important in aluminum and steel manufacturing processes such as casting. On BN-coated preforms, metal layers can be deposited and
easily peeled off to give free-standing metal sheets. BN coatings on SiC or Al2O3 fibers reduce the thermal mismatch between fiber and matrix and
also reduce fiber – matrix interfacial shear strength in ceramic matrix composites to give higher overall strength and toughness [63].

TiB2 – Fe cermets are suitable for machining aluminum alloys [129], whereas ternary boride cermets based on Mo2FeB2, Mo2NiB2 and WCoB are
suitable as machine parts for injection molding, bearings, wire-drawing cones, and cutting tools [99], [131]. The world production of TiB2 is ca. 250 t/a,
much of this for the manufacture of these resistance-heated evaporation boats. The price of TiB2 powder is 30 – 60 $/kg.

Calcium hexaboride, CaB6, is used as a deoxidizer for high-conductivity copper [136-138]. CaB6 and ZrB2 are used as antioxidants in carbon-bonded
refractories (cf. Uses in Refractories.). For ZrO2 – C submerged nozzles used in the continuous casting of aluminum a partially or total change of ZrO2
to ZrB2 at the powder can more than double corrosion resistance [139]. A major use of NiB, CrB, and CrB2 is the production of welding and hard-facing
alloys based on nickel – chromium – boron – silicon, called colmonoy [140]. An iron – boron alloy 85 wt % Fe/15 wt % B is used to introduce boron into
steel (at about 0.002 wt %) in order to improve hardenability [141]. The ternary boride Fe14Nd2B has been developed for use as a magnetic material (
Magnetic Materials) [142].

The hardness and wear properties of borides are utilized economically as thin coatings on metal surfaces, prepared by the so-called boronizing
process (cf. the chemical uses of B4C in Chemical Uses.). Lanthanum hexaboride is useful as a high-current-density electrode for electron
microscopes, electron-beam furnaces, and other devices of highest electronic emissivity. The lifetime of LaB6 electrodes is reported to exceed that of
tungsten cathodes by two orders of magnitude [143, 144].

The refractory hexaboride of europium was suggested as a neutron absorber to control the power of fast breeder reactors. As a neutron absorber
EuB6 is equivalent to 35 mol % 10B-enriched boron carbide, and its nuclear worth is ca. 15 % higher than europium sesquioxide [30], [64], [65].

[Top of Page]

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