Boron and Boron Alloys 1
Boron and Boron Alloys
Ulrich Baudis, Degussa, Hanau, Federal Republic of Germany (Chap. 1)
Rudolf Fichte, Nürnberg, Federal Republic of Germany (Chap. 2)
1. Boron . . . . . . . . . . . . . . . . . . . .
1.1. Structure and Polymorphism . . . .
1.2. Physical Properties . . . . . . . . . . .
1.3. Chemical Properties . . . . . . . . . .
1.4. Production . . . . . . . . . . . . . . . .
1.5. Chemical Analysis, Storage, Safety
1.6. Uses, Economic Aspects . . . . . . . .
2. Ferroboron and Other Boron Mas-
ter Alloys . . . . . . . . . . . . . . . . .
2.1. Physical Properties . . . . . . . . . . .
2.2. Chemical Properties . . . . . . . . . .
2.3. Raw Materials . . . . . . . . . . . . . .
1. Boron
The nonmetallic element boron [7440-42-8] is
situated in the top position of the third main
group in the periodic table. Boron is not found
free in nature but is always bound to oxygen. It
occurs as orthoboric acid and as alkali-metal and
alkaline earth metal borates. The most important
sources of boron are the minerals rasorite and
kernite, which are found in extensive deposits in
California in the Mojave desert. There are also
large ore deposits in Turkey and the USSR. Al-
though widespread in nature, boron constitutes
only about 3 ppm of the earth’s crust [9].
Boron was discovered concurrently by the
French chemist Gay-Lussac and the English
chemist Sir Humphry Davy in 1808. Henri
Moissan [10] first obtained considerable quanti-
ties of boron (of 86 % purity) by reduction of bo-
ric oxide with magnesium in 1895. The Moissan
process is still the basis for commercial produc-
tion of amorphous low-purity boron.
In 1909 Weintraub [11] succeeded in
preparing 99 % pure boron by decomposition
of BCl3 in an electric arc. Since then numerous
methods have been developed (see Section 1.4),
but still research continues to find methods for
producing commercial quantities of pure boron.

c 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
10.1002/14356007.a04 281
1 2.4. Production . . . . . . . . . . . . . . . . 7
1 2.4.1. Carbothermic Production . . . . . . . . 7
2 2.4.2. Aluminothermic Production . . . . . . 8
2 2.5. Quality Specifications for Commer-
3 cial Grades . . . . . . . . . . . . . . . . 8
4 2.6. Storage and Shipment . . . . . . . . . 10
5 2.7. Chemical Analysis . . . . . . . . . . . 11
2.8. Pollution Control . . . . . . . . . . . . 11
5 2.9. Uses . . . . . . . . . . . . . . . . . . . . . 11
5 2.10. Economic Aspects . . . . . . . . . . . . 12
6 2.11. Toxicology and Industrial Hygiene . 12
6 3. References . . . . . . . . . . . . . . . . . 12
1.1. Structure and Polymorphism
There are several allotropic forms of boron.
Well established are amorphous boron, α-
rhombohedral boron, and β-rhombohedral bo-
ron. In addition, four tetragonal forms have been
described. However, these are probably stabi-
lized by small amounts of nitrogen or carbon
[4].
The β-rhombohedral form is the thermody-
namically stable modification at all tempera-
tures. Amorphous boron slowly converts to the
β-rhombohedral form at ≈ 1200 ◦ C and to α-
rhombohedral boron above 1500 ◦ C. Any type
of boron recrystallizes in β-rhombohedral struc-
ture when heated above the melting point and
cooled.
The unit cell of β-rhombohedral bo-
ron contains 105 boron atoms grouped
84 B + 2×10 B + 1 B in a complex arrangement.
The structure of α-rhombohedral boron can
be described as a slightly deformed cubic close
packing of B12 icosahedra. The unit cell contains
12 B atoms at the vertices of the icosahedron.
Amorphous boron exhibits broad reflections
in the x-ray diffraction pattern. It is believed
to be a frozen-in intermediate between the α-
and β-modifications or a microcrystalline de-
posit of β-rhombohedral boron [4]. Amorphiza-
tion can be achieved by intensive milling of β-
2 Boron and Boron Alloys

rhombohedral samples [12]. Structures of the
other polymorphs are too complex to be de-
scribed in a few words; however, all boron struc-
tures have been discussed thoroughly elsewhere
[4].
1.2. Physical Properties
Determination of precise physical properties of
boron is made more complicated by the struc-
tural polymorphism and purification problems.
Some values, rather arbitrarily collected from
the literature, are listed below.
the various boron polymorphs are given in the
literature [4], [5].
Boron is composed of two stable isotopes,
10
B [14798-12-0] and 11 B [14798-13-1]. Their
nuclear properties are summarized in Table 1.
The nuclear spin permits NMR spectroscopy.
The high value of thermal neutron cross sec-
tion of the isotope 10 B makes boron useful as
a neutron absorber in nuclear power plants.
Table 1. Nuclear properties of boron
Property Nuclide
10 11
B B

Atomic Relative atomic mass 10.0129

11.0093
number 5
Natural abundance, % 19.8
Relative 80.2
atomic mass 10.811 Nuclear spin +3 − 3/2
Melting point 2050 ± 50 ◦ C Magnetic moment,
Sublimation nuclear magnetons∗ + 1.80063 + 2.68857
point 2550 ◦ C Quadrupole
Density 2.3 g/cm3 amorphous moment, barn∗∗ + 0.074 + 0.036
(20 ◦ C) 2.35 β-rhombohedral Cross section for
2.46 α-rhombohedral (n, α), barn∗∗ 3837 0.005
2.99 liquid at mp
2.13 solid at mp −27 2
∗ 1 nuclear magneton = 5.0508×10 Am .
Crystal amorphous, α-rhombohedral,
∗∗ 1 barn = 10−28 m2 .
structure β-rhombohedral, four tetragonal
Hardness 2390 kg/mm2 crystallized from
(Knoop) melt
2690 vapor deposited
Electrical 7.5×102 Ω cm amorphous
resistivity 7×105 β-rhomb., single 1.3. Chemical Properties
(300 K) crystal
6 7
10 – 10 β-rhomb., poly-
crystalline The chemical properties of boron are determined
−1 −1
Heat 12.054 J K mol amorphous at 300 K to a large extent by its small atomic radius
capacity Cp 11.166 β-rhomb. 300 K
33.955 solid at mp (0.25 nm) and high ionization potentials.
39.063 liquid at mp
−1 −1 Ionization energy
Entropy S 6.548 J K mol amorphous
(298 K) 5.875 β-rhomb. B −→ B+ 798 kJ/mol (8.27 eV)
Enthalpy of B+ −→ B2+ 2426 (25.15)
fusion ∆H f 50.2 kJ/mol B2+ −→ B3+ 3658 (37.92)
Enthalpy of Standard electrode potential
sublima- B + 3 H2
OH3 BO3
tion ∆H s 572.7 kJ/mol + 3 H + + 3 e− − 0.73 V
Electron affinity 32 kJ/mol (0.332 eV)
Electronegativity 2.04 (Pauling)
Boron is the second hardest element, the 2.01 (Mulliken)
diamond allotrope of carbon being the hard- Ionic radius 0.25 nm
Atomic radius 0.80 – 0.95 nm (depending
est. α-Rhombohedral boron is red to brown; β- on type of bonding)
rhombohedral boron lustrous gray black; and Standard enthalpy of formation
amorphous material is brown to gray. The elec- BF3 − 1136 kJ/mol
BCl3 − 402
trical resistivity changes drastically with tem- BBr3 − 239
perature, varying from 1011 Ω cm at − 160 ◦ C B2 O3 − 1269
− 256
to 106 Ω cm at 20 ◦ C and to 0.1 Ω cm at 700 ◦ C
BN

[4] for polycrystalline β-rhombohedral boron,

be havior characteristic of a semiconductor. De- The electronic configuration 2s2 2p1 dictates
tailed information about optical, magnetic, elec- predominant trivalency. However, simple B3+
trical, thermodynamic, and other properties of ions do not exist.

Because boron has more orbitals available for
bonding than electrons (4 orbitals, 3 electrons),
it is an electron-pair acceptor, a Lewis acid, and it
has a tendency to form multi-center bonds. Other
dominant characteristics are the high affinity
for oxygen and the tendency to combine with
most metals to give refractory alloy-like metal
borides.
The chemical behavior of elemental boron
depends upon the morphology and particle size.
Generally speaking, crystalline boron is rather
unreactive, whereas amorphous boron does react
more readily. At room temperature all modifica-
tions of boron are relatively resistant to chemical
attack.
No direct reaction occurs with hydrogen, but
indirect synthesis leads to a variety of boron hy-
drides (→ Boron Compounds).
The halogens react to form the trihalides:
2 B + 3 X2 −→ 2 BX3
Fluorine reacts spontaneously at room tem-
perature; chlorine, at 500 ◦ C; and bromine, at
600 ◦ C [13].
Reaction with oxygen starts at ≈ 600 ◦ C but
is restrained by the formation of a glassy liquid
B2 O3 film on the boron particles [14]. Boron re-
acts with sulfur to form glassy B2 S3 and with
Se to form B2 Se3 , both at ≈ 600 ◦ C. There is
no reaction with Te. With nitrogen, boron ni-
tride, BN, is formed at 1100 ◦ C. Phosphorus re-
acts completely at 1000 ◦ C to give BP. Arsenic
forms BAs at 800 ◦ C under pressure.
Boron and carbon react to give B12 C3 above
2000 ◦ C; with silicon, B4 Si and B6 Si are formed.
Heterocyclic compounds containing C, N, S, O,
and boron have interesting structures and prop-
erties (see Carboranes, Borazine, Borthiine, and
Boroxine under → Boron Compounds). There is
also a large variety of organoboron compounds
[15].
When it does react, elemental boron is an ef-
fective reducing agent. Water vapor is reduced
at 800 ◦ C to give H2 and B2 O3 . Carbon monox-
ide is reduced at 1200 ◦ C; boron burns in car-
bon dioxide at red heat. Nitrogen oxides are re-
duced to give BN and B2 O3 . Sulfur dioxide is
also reduced. When transition metal oxides like
Fe2 O3 , TiO2 , and Cr2 O3 are reacted with ele-
mental boron, B2 O3 and metal borides form. Up
to 1400 ◦ C alkaline-earth oxides and aluminum
oxide do not react with boron.
Boron and Boron Alloys 3
Boron is not attacked by aqueous NaOH
but reacts completely with molten Na2 CO3
or molten mixtures of sodium carbonate and
sodium nitrate.
Boiling nonoxidizing acids, such as HF, HCl,
HBr, or dilute sulfuric or phosphoric acid, do not
attack boron. However, vigorous reaction occurs
with concentrated HNO3 or with HNO3 – H2 O2
mixtures.
The chemical properties of boron are sum-
marized in [17].
1.4. Production
A variety of preparative methods have been de-
scribed. The following are the most important
methods [6]:
1) Reduction of boric oxide with magnesium
2) Reduction of boron halides or fluoroborates
with sodium or another metal
3) Reduction of boron halides with hydrogen
4) Thermal decomposition of boron com-
pounds, especially boron halides and hy-
drides
5) Electrolysis of molten borates or fluorobo-
rates
The modification of boron formed depends
primarily on temperature and reaction time, only
secondarily on the method [18]. As a rule of
thumb, temperature below 900 ◦ C and short re-
action time produce amorphous boron; temper-
ature above 1400 ◦ C and long reaction time pro-
duce β-rhombohedral or the tetragonal modifi-
cations. The optimum conditions for formation
of α-rhombohedral boron are in between.
The usual method for commercial production
of large quantities of amorphous boron is the
reduction of boron trioxide with magnesium in
a thermite-like reaction [19–21]. The principles
of this method date back to the work of Henri
Moissan [10].
B2 O3 + 3 Mg −→ 2 B + 3 MgO
Simultaneously MgO reacts with excess
B2 O 3 :
MgO + B2 O3 −→ Mg(BO2 )2
MgO + 2 B2 O3 −→ MgB4 O7
4 Boron and Boron Alloys
The reduction is very quick and highly
exothermic; finely divided material may react
explosively [7].
Reaction is smoother if there is an excess of
B2 O3 [7], [22]:
2 B2 O3 + 3 Mg −→ 2 B + Mg3 (BO3 )2
4 B2 O3 + 3 Mg −→ 2 B + 3 Mg(BO2 )2
The optimum ratio B2 O3 : Mg is about 1.8 : 3
[7]. Reaction is carried out in vertical steel re-
torts shielded from oxygen by a flow of argon. It
is initiated by electric spark and igniter mixture
or by external heating.
After cooling, the reaction mass is crushed
to 1-mm particles and leached twice with hy-
drochloric acid. Crude amorphous boron of
86 – 88 % purity is obtained [21]. This mate-
rial can be upgraded by treatment with B2 O3
[22] or KHF2 and KBF4 [23], [24], subsequent
leaching with acid, and final heating in a vac-
uum to remove boron suboxide and metals [25].
The boron content is then 90 – 92 or 95 – 97 %,
adequate for use in pyrotechnics and fluxes.
Reduction of KBF4 by sodium
KBF4 +3 Na−→3 NaF+KF+B
was used for the commercial production of
boron in Germany until the end of the 1950s
[26].
A common problem of metallothermic reduc-
tion is incomplete reaction and formation of non-
removable metal borides.
Samples of very pure boron, > 99 % B, can
be obtained by reduction of boron halides with
hydrogen, especially BBr3 [27], [28] and BCl3
[29–32]. This is also the method of choice for
laboratory synthesis [27], [29]. The halides can
be purified by distillation prior to reduction [4],
[27]. However, the efficiency of the hydrogen
reduction process is rather low [19], yields of
5 – 25 % being the usual. Unreacted boron halide
must be recycled [30], washed out, or removed
by other methods [33]. This complicates the pro-
cess and makes it expensive.
Very pure boron is also obtained by thermal
decomposition of BI3 [34], [35], BBr3 [36], or
boron hydrides [37], [38] on tungsten wires or
another type of incandescent filament. Boron of
99.9999 % (six nines) purity was obtained by
decomposition of diborane and subsequent zone
melting [39].
Electrolysis of molten borates or KBF4 [40]
is not an important method for commercial or
laboratory preparation although it has been men-
tioned in numerous articles.
Boron can be refined either by zone melting
[6], [35], [39], [41], [42] or volatilization of im-
purities in high vacuum or hydrogen at 2000◦ C
[25], [35].
1.5. Chemical Analysis, Storage, Safety
Analysis. Boron content in elemental bo-
ron is generally determined quantitatively by
decomposition to borate with fused carbonate in
a platinum crucible, subsequent acid leaching,
neutralization, addition of mannitol, and titra-
tion of boric acid. The mixture HNO3 – H2 O2
also decomposes boron samples. Metal impuri-
ties in boron, such as Mg, Na, and Fe, are de-
termined by atomic absorption or emission spec-
trometry after decomposition of the sample [43].
Chlorine and fluorine are determined by titra-
tion [44]. The elements O, N, H, P, Si, and C
are difficult to determine. However, vacuum hot
extraction and combustion methods [42], [43] or
spark source mass spectrography [35], [45] can
be used.
A sensitive qualitative test for boron is the
green flame test. The sample is usually decom-
posed to methyl borate by heating a mixture of
the sample, sulfuric acid, and methanol to igni-
tion.
Storage. Dry boron is not very sensitive to
oxidation. It is packaged in airtight metal drums,
cardboard or plywood containers, or glass bot-
tles [46]. Boron powder, like other combustible
material, presents a dust explosion hazard. The
lower explosive limit was determined to be
125 g/m3 in air [47].
Boron ignites in air at 600 – 800 ◦ C but does
not burn violently because of the formation of a
glassy boric oxide film that prevents the mate-
rial from oxidizing rapidly [14]. Burning boron
should be covered with sand, aluminum oxide,
sodium chloride, or the like. Water must not be
used, because of the formation of inflammable
hydrogen. Boron is an explosion hazard when

mixed with strong oxidizing agents, such as ni-
trites, chlorates, lead dioxide, and silver fluoride.
Such mixtures can react violently and even ex-
plode [13], [14], [16].
Safety. Elemental boron is considered to be
nontoxic because of its chemical inertness and
insolubility. In contrast, most boron compounds,
especially the hydrides, are extremely toxic [48]
(see Toxicology under → Boron Compounds).
During the production process leading to boron
the possible formation of any toxic boron hy-
drides must be either avoided or controlled.
1.6. Uses, Economic Aspects
Relatively large quantities of amorphous boron
(90 and 95 % B) are used as additives in py-
rotechnic mixtures, especially in flares, igniters,
and delay compositions (→ Pyrotechnics); solid
rocket propellant fuels [49]; and explosives [50].
Some boron is needed for the preparation of re-
fractory metal boride additives for cemented car-
bides. Boron is also a useful reducing additive
in fluxes for soldering stainless steel.
Use of boron in electronics is limited to high-
purity boron (> 99.99 %). It is used as a ppm
additive for germanium and silicon to make
p-type semiconductors [51]. Crystalline high-
purity boron is used in thermistors [52], [53] and
delay lines [54]. Boron filaments have been de-
veloped as reinforcing material for light-weight,
stiff composites for use in commercial and mili-
tary aircraft [55]. Epoxy resins [56], polyamides,
aluminum, magnesium, and other materials are
the matrix [57], [58]. However, graphite fila-
ments have replaced boron filaments in many
applications.
In nuclear technology thin films of boron are
used in neutron counters [52]. Boron powder
dispersed in polyethylene castings is used for
shielding against thermal neutrons [59]. In ad-
dition, composites of boron with Al or Fe, espe-
cially when enriched in 10 B, are used as neutron
shields and absorbers in nuclear reactors [59].
Boron is an effective deoxidizing agent, e.g.,
for production of pure copper [60]. It also is im-
portant in the preparation of amorphous mag-
netic metals and alloys [61]. Boron, as fer-
roboron, is used in microalloyed steel (0.001 %
B). This steel exhibits excellent resistance to
Boron and Boron Alloys 5
stress cracks as well as improved tensile strength
and hardness.
Amorphous boron of 90 – 92 % purity costs
about DM 250 – 300 (≈ $ 100) per kg (1984).
Material of higher purity is much higher in price:
very pure boron (> 99.99 %, four nines) may
cost up to DM 10000 (≈ $ 3500) per kg and
more. Boron enriched in 10 B costs $ 9 – 10 per
gram [59].
The leading producers are H. C. Stark,
Goslar, Federal Republic of Germany, and Kerr
McGee Chemical Corp., Oklahoma, United
States. There are further production facilities
at Degussa AG, Frankfurt am Main; Elek-
troschmelzwerk Kempten, München; Union
Carbide Chemical Corp., New York; NL In-
dustrial Corp., Wilmington, Delaware, United
States; Murex Ltd., Rainham, United King-
dom; and Kawecki-Billiton Corp., Arnhem, the
Netherlands [62]. Boron is also produced in the
Soviet Union.
Total production is estimated to be 30 –50 t/a.
2. Ferroboron and Other Boron
Master Alloys
Ferroboron is basically an iron – boron alloy
containing 10 – 20 wt% B. It is used mainly in
the steel industry. Ferroboron was first produced
in 1893, by Henri Moissan [63], from boric
acid, iron, and carbon in a single-phase electric-
arc furnace lined with carbon. Ferroboron pro-
duced in this way contains carbon. The introduc-
tion of the thermite reaction by Goldschmidt
in 1898 led to the aluminothermic reduction of
boric oxide to ferroboron, for years the main
commercial method for producing ferroboron.
The carbothermic process has again found use
for the production of ferroboron, now as a
raw material for the manufacture of amorphous
metals (→ Metallic Glasses). Aluminothermic
ferroboron contains residual aluminum, which
causes severe casting problems.
2.1. Physical Properties
In the system iron – boron, shown in Figure 1
[64], there are two intermetallic compounds,
FeB [12006-84-7] and Fe2 B [12006-86-9] (
6 Boron and Boron Alloys

6.3 and 7.3 g/cm3 , respectively). The crystal and brittle with a fine or coarse crystalline frac-
structure of FeB is orthorombic (a = 0.5502, ture. The density depends mainly on the boron
b = 0.2948, c = 0.4057 nm), whereas that of Fe2 B content:
is tetragonal (a = 0.5109, c = 0.4249 nm). Addi-
boron, wt % 20.2 17.9
tional physical properties of the two iron borides aluminum, wt % 2.7 0.8
are summarized in Table 2. Also see [68]. density, g/cm3 6.02 6.41

2.2. Chemical Properties

Commercial ferroboron changes in appearance

over prolonged exposure to humid air; its bright
silver disappears, the surface turning dull gray,
with almost red “rusty” stains. Ferroboron dis-
solves in mineral acids (Section 2.7). Distilled
hot water may react slightly with ferroboron
[70]. Some contradictory statements about the
chemical behavior of ferroboron in the litera-
ture are probably due to other elements in the
alloy. Fe2 B dissolves in HCl (1 : 2), hydrogen
and boranes evolving, the latter hydrolyzing into
suboxides [71], [72]. FeB is resistant to HCl
( = 1.19 g/cm3 ) and H2 SO4 ( = 1.84 g/cm3 ),
both at room temperature and at their boiling
point. FeB dissolves completely in HNO3 . Both
FeB and Fe2 B react with nitrogen at tempera-
tures above 350 ◦ C to give boron nitride [65].
The behavior of boronized steels, i.e., steel
with thin layers of FeB on the surfaces, was
Figure 1. Phase diagram iron – boron [64] discussed by A. Matuschka [66]. Such steels
are oxidation resistant up to 700 – 900 ◦ C. The
boronized steel CK45 (AISI 1042) is resistant
Table 2. Properties of Fe2 B and FeB [65–67]
to 20 % HCl, 10 % H3 PO4 , and 10 % H2 SO4
Property Fe2 B FeB at 56 ◦ C. Stainless steels, such as X10CrNiTi 18
9 (Werkstoff Nr. 1.4541, AISI 321, SAE 30321)
Microhardness, Vickers, 100 g,
kN/mm2 13.24 16.19 can be made more resistant to attack by 20 %
Thermal conductivity, W cm−1 K−1 0.2 – 0.3 0.1 – 0.2 HCl or 10 % H2 SO4 at 56 ◦ C by boronizing the
Electrical resistivity, at room surface.
temperature, µΩ cm ≈ 10 ≈ 20
Temperature coefficient of resistance,
µΩ/K 0.18 0.4
Curie temperature, K 1015 598
Coefficient of linear expansion 2.3. Raw Materials
(300 – 1000 K), K−1 8×10−6 10 –
16×10−6
The following boron minerals can be used for the
manufacture of ferroboron: colemanite (51 %
The enthalpies of formation at 1385 K have B2 O3 ), pandermite (48 % B2 O3 ), priceite (51 %
been determined by high-temperature solu- B2 O3 ), and boracite (62 % B2 O3 ). However, the
tion calorimetry [69]: − 67.87 ± 8.05 kJ/mol for raw materials most commonly used are boric
Fe2 B and − 64.63 ± 4.34 kJ/mol for FeB. oxide (≈ 99 % B2 O3 ) and boric acid (≈ 57 %
Commercial ferroboron alloys, either alu- B2 O3 ).
minothermic or carbothermic, are bright silver

2.4. Production
Boric oxide can be reduced by carbon, alu-
minum, or magnesium. Reduction by silicon
is incomplete. Figure 2 shows the calculated
free energies of the corresponding reactions as
a function of temperature [67]. For commer-
cial production, either reduction by carbon (car-
bothermic or endothermic) or reduction by alu-
minum, sometimes with some magnesium (alu-
minothermic or exothermic) is usual. The core-
duction of iron and boric oxide proceeds more
readily than the reduction of either alone because
of the formation of the borides Fe2 B and FeB.
Iron can be replaced by other boride-forming
metals, manganese, nickel, or cobalt. In carboth-
ermic reduction there is a tendency to form bo-
ron carbide, thus leading to a carbon-containing
ferroboron.
Figure 2. Free energies ∆G0 of reactions reducing boric
oxide as a function of temperature
I 2/3 B2 O3 + 2 C −→ 4/3 B + 2 CO
II 2/3 B2 O3 + 7/3 C −→ 1/3 B4 C + 2 CO
III 2/3 B2 O3 + 4/3 Fe + 2 C −→ 4/3 FeB + 2 CO
IV 2/3 B2 O3 + Si −→ 4/3 B + SiO2
V 2/3 B2 O3 + 4/3 Al −→ 4/3 B + 2/3 Al2 O3
VI 2/3 B2 O3 + 2 Mg −→ 4/3 B + 2 MgO
Aluminum and boron also form borides (see
Metal Borides under → Boron Carbide, Boron
Nitride, and Metal Borides), and this results
in residual aluminum in aluminothermic fer-
roboron.
2.4.1. Carbothermic Production
In order to produce a carbothermic ferroboron
with a low carbon content the boron content
Boron and Boron Alloys 7
must be high, i.e., the higher the boron content
the lower the carbon solubility and thus carbon
pick-up.
The reduction of boric oxide by carbon re-
quires high temperature; therefore, the process
is carried out in an electric-arc furnace (single-
or three-phase type) of capacities up to 1500 kV
A. These are relatively small production units,
for the worldwide demand for ferroboron is
low compared with that for other electrothermic
ferro alloys.
The London & Scandinavian Metallurgical
Co., United Kingdom, produces a ferroboron
with 16 – 18 % B, 0.5 % C, and < 0.15 % Al
by carbothermic reduction of boric oxide.
In a Japanese patent [73] the carbothermic
production of ferroboron from boric acid, iron
powder, and charcoal in a Héroult-type electric-
arc furnace with carbon lining is claimed. One
example describes the production of an alloy
with 10.3 % B, 2 % Si, and 0.98 % C in a 350-
kW three-phase electric-arc furnace. The mix is
100 parts boric acid, 135.8 parts iron powder
(92.9 % Fe), and 57 parts charcoal powder. The
boron recovery is 81.7 %, and the power con-
sumption 4550 kWh per tonne of alloy. Another
example describes the small-scale production of
an alloy containing 15.3 % B. Another Japanese
patent [74] claims the carbothermic production
of a B- and Si-containing alloy, e.g., 3.3 wt% B,
2.9 wt% Si, and 3.0 wt% C, in a special vertical
blast furnace. The ferroboron is intended for use
in the manufacture of amorphous alloys.
The production of ferroboron from pig iron
swarf and boric acid in an electric-arc furnace
with a final oxygen blow leads to an alloy with
16.3 % B, 0.03 – 0.06 % Al, and 0.03 – 0.06 %
C. The boron recovery in small-scale runs is
said to be 60 – 65 %; the power consumption,
≈ 16500 kWh per tonne of alloy [75]. Silicon-
containing boron alloy can be produced by car-
bothermic reduction. The process is described
by K. D. Frank in [76]. A mixture of 100 parts
colemanite, 100 parts quartzite, 40 parts iron
turnings, and 60 parts low-temperature coke is
charged to a 1000-kW electric-arc furnace. A
metal containing 5.35 % B, 37.2 % Si, and
0.21 % C is tapped. Boron recovery is 70 %, and
the power consumption is 6000 kWh per tonne
of alloy.
Gesellschaft fuer Elektrometallurgie mbH,
Duesseldorf, Federal Republic of Germany, has
8 Boron and Boron Alloys
developed a process for the carbothermic pro-
duction of ferroboron containing 15 – 20 % B
and < 0.1 % Al in a three-phase submerged
arc furnace, whereby boric oxide and iron ox-
ide are simultaneously reduced by charcoal and
other low-density carbonaceous materials, e.g.,
wood chips [77]. Nickel boron can also be pro-
duced carbothermically. Boric oxide and/or bo-
ric acid and nickel are the raw materials. Lon-
don and Scandinavian Metallurgical Co., Lon-
don, United Kingdom, produces a nickel boron
containing 15 – 18 % B; 0.5 and 0.15 % C (max.);
and 0.20 % Al (max.) in the electric-arc furnace
by carbon reduction.
2.4.2. Aluminothermic Production
Ferroboron can be made batchwise in a conve-
nient way by the reduction of boric oxide and
iron oxide with aluminum powder. Some mag-
nesium in the aluminothermic mix is beneficial:
Magnesium is the stronger reducing agent at
temperatures below its boiling point, whereas
aluminum is more effective above the boiling
point of magnesium, where such metallothermic
reactions generally take place.
The aluminothermic coreduction of bo-
ric oxide and iron oxide (Fe2 O3 ) is highly
exothermic, and only a little additional en-
ergy is necessary for a self-propagating reaction
(→ Aluminothermic Processes). The thoroughly
mixed compounds are charged into a refractory-
lined pot and ignited, either the whole mix (top
firing) or by igniting a starting mix, the rest then
charged as the reaction proceeds over a few min-
utes. The liquid metal and slag separate on ac-
count of differing densities, and after cooling the
metal button, up to 1500 kg, is removed. After
mechanical cleaning, the metal button is bro-
ken and crushed to the desired size. The com-
panies of the Metallurg Group [78], who pro-
duce ferroboron from boric oxide, iron oxide,
and aluminum powder, obtain boron recover-
ies of 70 – 75 % for the 18 – 20 % B grade and
80 – 85 % for the 15 – 18 % B grade by opti-
mizing process parameters. The aluminum con-
sumption can be as low as 4.8 – 5 kg Al per kg
of B.
N. A. Chirkov et al. [79] investigated heat
balances for an electro-aluminothermic fer-
roboron process using either 1) boric oxide or
2) boric acid as the raw material. Three dif-
ferent mixes – igniting, main, and precipitation
– are charged consecutively into a three-phase
electric-arc furnace and reacted to produce a fer-
roboron melt with ≈ 20 % B. The composition
of the charges and the results are summarized in
Table 3. The heat balances for these two cases
are shown in Table 4. The investigators are con-
vinced that the process can be optimized to im-
prove the boron recovery and the consumption
figures.
When borate ores such as boracite or cole-
manite are used as raw materials, instead of boric
oxide, the aluminothermic process gives boron
recoveries as low as 40 – 50 % [80–82]. The spe-
cific aluminum consumption is normally higher
because the process needs additional energy, in
form of either a booster (peroxides or chlorates
plus aluminum powder) or in the form of elec-
tricity by smelting the mix in the electric-arc
furnace (electro-aluminothermic process).
Complex boron additives for steel, which
contain boron in a dilute alloy together with pro-
tective elements, are produced from ferroboron
and other alloying elements by a melting pro-
cess (see Section 2.5, Table 7, and [83]). Other
boron master alloys such as nickel boron and
cobalt boron with ≈ 15 % B and 0.1 % or 1.0 %
Al (max.) can be produced aluminothermically
using boric oxide and nickel or cobalt (as metal
and/or oxide) [84]. Copper boron with ca. 2 %
B is commercially produced by Gesellschaft
fuer Elektrometallurgie [85], using an electro-
magnesiothermic process with copper and boric
oxide as raw materials. Aluminum master alloys
with 2.5 – 4.5 % B and ≈ 5 % Ti + 1 % B are pro-
duced in an induction furnace by adding potas-
sium boron fluoride and potassium titanium flu-
oride to an aluminum bath [86].
2.5. Quality Specifications for
Commercial Grades
Quality standards are specified in Germany by
DIN 17567 [87], which also describes sizing,
sampling, analytical methods, shipment, and
storage. Analyses of the standard grades are
summarized in Table 5. The American ASTM
recognizes six grades of ferroboron; analyses
are given in Table 6. Ferroboron is shipped in
various sizes. In Europe pieces of fist size and
 Boron and Boron Alloys 9
Table 3. Charge composition during electro-aluminothermic production of ferroboron using boric oxide and boric acid raw materials [79]

Mix 1: Mix 2:

Igniting Main Precipitation Igniting Main Precipitation

Raw materials
Boric oxide, kg – 1200 – – – –
Boric acid, kg – – – – 1800 –
Iron ore, kg 200 200 1000 200 180 950
Al powder, kg 65 820 282 65 820 262
Lime, kg 70 100 170 70 450 170

Total, kg 335 2320 1452 335 3250 1382

Time, min 30 98 32 3 114 23
Power consumption, kWh 1130 1980
Products
Ferroboron, kg 1200 ∗ 1100 ∗
%B 20 18
% Al 3 3.9
% Si 1.13 1.7
Slag, kg 2900∗ 3080∗
% B2 O3 14 – 15∗ 10 – 12∗
Boron recovery, % 64 63
Aluminum consumption,
kg Al per tonne of ferroboron 973 1043
Energy consumption,
kWh per tonne of ferroboron 940 1800

∗ Estimated.

Table 4. Heat balances for the electro-aluminothermic production of ferroboron using boric oxide and boric acid as raw materials [79]

Input and consumption From B2 O3 From H3 BO3

6 6
∆H, 10 J ,% ∆H, 10 J ,%

1. Chemical reactions 13182 69.0 12345 58.3

2. Electric power 4072 21.3 7143 33.7
3. Side reactions 1833 9.7 1699 8.0
Total input 19087 21186
1. Heat content of slag 9515 49.3 9237 42.9
2. Heat content of metal 3235 16.7 2907 13.5
3. Heat content of dust 63 0.3 125 0.6
4. Dehydration of acid 48 0.2 1084 5.0
5. Decomposition of carbonates 60 0.3 98 0.5
6. Heat content of gases 141 0.7 2805 13.1
7. Accumulation of heat by furnace
brickwork 4678 24.2 4212 19.6
8. Radiation 1581 8.3 1045 4.8
Total consumption∗ 19319 21514

∗ The discrepancies between input and consumption are 232×106 J (1.2 %) and 328×106 J (1.5 %).

Table 5. German Standards DIN 17567 [87]

Designation Composition

B Al Si C Mn P S Co
wt % max. wt %

FeB16 15 – 18 4.0 1.0

}0.10 }0.50 }0.005 }0.001 }0.005
FeB18 18 – 20 2.0 2.0
FeB12C 10 – 14
}0.50 }4.0 }2.0 }0.50 }0.005 }0.1 }0.005
FeB17C 14 – 19
10 Boron and Boron Alloys
Table 6. United States standards [88]

Grade Composition, wt%

Boron Carbon, Silicon, Aluminum,

min. max. max. max. max.

A1 12.0 14.0 1.5 4.0 0.5

A2 12.0 14.0 1.5 4.0 8.0
B1 17.5 19.0 1.5 4.0 0.5
B2 17.5 19.0 1.5 4.0 8.0
C1 19.0 24.0 1.5 4.0 0.5
C2 19.0 24.0 1.5 4.0 8.0

in the United States sizes such as 2 in or 1 in x
Down are commercial. Ferroboron can also be
ground to powder of desired size (e.g., 20 mesh x
D, i.e., less than 0.84 mm). In the United States,
where the use of boron in steel is fast growing,
and also in the United Kingdom, special boron
alloys have been developed as hardenability in-
tensifiers (Table 7). These complex alloys con-
tain elements to protect boron against oxidation
(Al, Si) and boron nitride formation (Ti, Zr) [89].
Boron-containing aluminum master alloys (Ta-
ble 8) are standardized in Germany [90]. Nickel
boron, cobalt boron, and copper boron are not
standardized. Typical analyses for commercial
alloys are given in Table 8.
In the United States and the United King-
dom special boron additives for the steel in-
dustry have been developed. The trade names,
e.g., BATS (abbreviation for boron-aluminum-
titanium-silicon), are shown in Table 7.
2.6. Storage and Shipment
Ferroboron and other boron master alloys are
generally not toxic, and there is no special legis-
lation on use and handling. Ferroboron is gener-

Table 7. Complex boron alloy “hardenability intensifiers” [83], [89]

Designation Composition a , wt%

B Al Ti Si Zr Mn C

BATS 50 b 0.50 13 20 7 5 8 –
BATS TT b 1.60 11 58 – 3.5 5 –
BATS 2Z b 2.50 11 36 8 6 – –
BATS Wire 2.3 89.7 8 – – – –
CARBOTAM b 2.0 3.0 15 – 20 4 – – 0.50
BALCORE 101 c 2.5 25 – – – – –
BALCORE 102 c 3.4 34 – – – – –
a
The remainder is iron.
b
BATS 50, BATS TT, BATS 2Z, and CARBOTAM are registered trademarks of the Shieldalloy Corp., Newfield, N.J.
c
BALCORE is a registered trademark of the LSM Co., London. The size of BALCORE 101 wire is 3.2 mm (34 g/m). The size of
BALCORE 102 wire is 5 mm (75 g/m).

Table 8. Composition of boron master alloys [83–85]

Alloy Analysis, wt%

B Ti Al Si C Others

Aluminum boron V-Al B 3 2.5 – 3.4 – rest max. 0.2 – ∗

V-Al B 4 3.5 – 4.5 – rest max. 0.2 – ∗
Aluminum-titanium-boron V-Al Ti 5 B 1 0.9 – 1.4 5.0 – 6.2 rest max. 0.2 – ∗
Nickel boron 15 – 18 – 0.1 – 1.0 max. 0.8 0.1 – 0.5 rest Ni
Cobalt boron 15 – 18 max. 1.0 – – rest Co
Copper boron ≈2 – – – – rest Cu

∗ See DIN 1725 [90].


ally packed in steel drums marked with material
grade, size, lot number, and producer. The ship-
ment is accompanied by a data sheet on safe
handling including physical and chemical prop-
erties, safe storage, and handling directions, e.g.,
use of protective gloves or dust respirators. Fer-
roboron and other boron master alloys and ad-
ditives should be stored in a dry area in their
original containers.
2.7. Chemical Analysis
For the determination of boron in ferroboron
the sample is dissolved in HCl (1 : 1) or H2 SO4
(1 : 1) containing a few drops of HNO3 and re-
fluxed. Residues rich in boron are fused with
sodium peroxide. The solution is passed through
an ion-exchange column, neutralized, diluted
with polyalcohol, and titrated with sodium hy-
droxide [91–93]. Small amounts of boron in steel
are determined by special methods [89]. One
photometric determination of boron in steel is
the curcumin method. A fully automated deter-
mination of boron in ferroboron, aluminum, and
complex ferro alloys by neutron transmission is
a convenient method for routine analyses [94].
Standard analytical methods in the United States
and the United Kingdom [95], [96] have been
described.
2.8. Pollution Control
During production the usual proscriptions on
pollution have to be obeyed.
In both the carbothermic and the exothermic
reduction processes the dust off-gases have to be
cleaned, either dry in bag filters or electrostatic
dust precipitators or wet in disintegrators or Ven-
turi scrubbers (O. Renz in [76]). A special com-
bined dry – wet cleaning plant for the off-gases
of an aluminothermic plant is described by Sey-
bold [97].
2.9. Uses
The main use of ferroboron is in steel (→ Steel)
[89], [98]. Very small amounts of boron improve
Boron and Boron Alloys 11
the hardenability of both plain carbon and al-
loyed steels. Boron acts as a hardenability inten-
sifier of other hardening elements, such as car-
bon, manganese, chromium, molybdenum, etc.
The boron should be present in the concentra-
tion range of 5 – 15 ppm (max., 30 ppm). Thus
the use of boron saves the expense of more
costly alloying elements. Because of the high
affinity of boron for oxygen and nitrogen, also
that dissolved in steel, boron has to be protected
from these two elements. Therefore, good pre-
deoxidation by calcium, aluminum, or silicon
and denitrification by titanium or zirconium are
necessary. In the United States and the United
Kingdom complex boron master alloys that con-
tain these protective elements have been devel-
oped and have proved very effective for con-
trolled boron addition to steels. In case-hardened
steels, boron exhibits better hardenability and
strength; in nonaging steels, especially for the
automotive industry, the sheet-forming proper-
ties are improved. Boron also offers benefits in
high-strength low-alloy (HSLA) steels, and it
improves the cutting properties in high-speed
steels.
In stainless steels of the chrome – nickel
type (ASTM 316), 0.004 – 0.009 % B signifi-
cantly improves the ductility in the hot form-
ing range (950 – 1250 ◦ C). In very low con-
centration (0.002 – 0.005 %) boron is beneficial
to creep properties in austenitic heat-resistant
stainless steels, as well as in ferritic steels, then
in combination with titanium, molybdenum, or
niobium. Steels with boron contents up to 2.5 %
are used for control rods in nuclear reactors be-
cause the thermal neutron cross section of boron
is so high. Boron is also used in hardfacing and
abrasion-resistant alloys; e.g., Colmonoy, a Ni-
Cr-Si-B alloy containing up to 3 % B, and Stel-
lite, an abrasion-resistant Co-Cr-W alloy con-
taining up to 2.5 % B.
The copper – boron master alloy is the best
agent for deoxidizing copper for the produc-
tion of a highly conducting metal. Aluminum
is treated with aluminum – boron master alloy
to increase the electrical conductivity and with
aluminum – titanium – boron master alloy to re-
fine the grain [86].
A new field of boron usage is the produc-
tion of amorphous alloys or metallic glasses
(→ Metallic Glasses). Intensive development
has been carried out by Allied Chemical Corp.
12 Boron and Boron Alloys
[99]. These alloys consist of a transition metal
(Fe, Ni, or Co) and about 20 mol % of a met-
alloid (B, C, Si, or P). They exhibit extraordi-
nary physical properties, especially the magnetic
properties, and may be used for low-hysteresis-
loss transformer cores [100].
2.10. Economic Aspects
The consumption of ferroboron is relatively low
due to the small concentrations necessary in
steel. In the Western World and Japan, fer-
roboron production was ≈ 1400 t/a in 1982 and
≈ 2000 t/a in 1983, showing an increasing ten-
dency. In 1981 only 2 % of the total boron con-
sumption in the United States was for the metal-
lurgy and nuclear fields [101] (→ Boron Com-
pounds). According to American Metal Market
(28 Dec. 83), ferroboron costs $ 3.89 per pound
(one pound = 454 g); nickel boron, $ 5.57 per
pound of the regular grade, $ 5.67 per pound for
the low-aluminum grade, and $ 6.30 per pound
for the low-carbon grade.
2.11. Toxicology and Industrial Hygiene
Ferroboron and boron master alloys are gener-
ally not toxic, but in the handling of raw materi-
als for their production protective measures must
be taken, e.g., the use of protective gloves and
glasses as well as dust respirators when handling
boric acid. In the production facilities the usual
protective measures (clothing, glasses, dust res-
pirators) must also be taken.
3. References
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14 Boron and Boron Alloys
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