ll.

Methods of Preparation of Amorphous Boron

A. F. ZHIGACH and D. C. STASINEVICH

1. Introduction

Preparation of pure elemental boron presents certain difficulties.

The conditions necessary for its preparation must be carefully main-
tained because boron reacts strongly with many substances at high
temperatures required for reduction of its compounds. Any by-products
formed during the reduction are difficult to separate.

Properties of elemental boron depend to a large extent upon the method

of its preparation. The first of these conditions is temperature. At
comparatively low temperatures, about 600-800 D C, boron is usually
obtained in the form of amorphous powder. At temperatures above 1000 D C
crystalline boron is produced, in many cases, as a mixture of various
modifications. Crystalline modifications of elemental boron are often
produced by special thermal treatment of amorphous boron obtained at
lower temperatures. It is difficult to draw a clear distinction between
methods of preparing amorphous and crystalline boron because they are
based on the same reaction. In aarly works the structure of boron was
not usually investigated. The reactions resulting in a mixture of
amorphous and crystalline boron without distinctly marked structure
will be discussed in this Chapter. Naturally, the main attention will
be focused on the processes of current practical application, and
processes capable of development. Information about investigations
on boron preparation, which generally did not lead to high purity can
be found in MELLOR (1924), LAUBENGAYER et al. (1943), GMELIN'S Hand-
book (1954), SAMSONOV et al. (1960b), NEWKIRK (1961), OLEMPSKA (1967)
and BOWER (1970).

The known methods of boron preparation may be divided into four groups.
Three of them are based on reduction of boron compounds by metals,
hydrogen and other agents, or by electrolysis. The fourth method
consists of thermal decomposition of boron compounds.

2. Reduction of Boron Compounds by Metals

Boron oxide, borax, metal borates, the halogenides (chloride; less

frequently bromide, fluoride and iodide) and metal tetrafluorborates
are types of boron compounds which can be used for the practical
production of elemental boron.

As was shown by thermodynamic calculation (EFREMKIN, 1957) isobaric

potentials of boron oxide reduction by magnesium, calcium, and aluminum
are negative in a temperature range of 298 to 2000 D K, and therefore,
these metals can readily reduce B 2 0 3 to boron. Silicon reduces weakly
at temperatures up to 1900 DK, but does not reduce at higher temper-
atures. Sodium cannot reduce boron oxide to elemental boron in stoichio-
metric proportions of reagents in the above range of temperatures.
From the metals listed above only magnesium has found practical appli-
cation in boron production. Powdered magnesium is readily available
and is inexpensive in comparison with such reducers as alkaline metals
and calcium.

The thermomagesium method of boron production developed by MOISSAN

(1892) is based on a reaction which is usually written as:

B 20 3 + 3Mg = 2B + 3MgO (1 )

Successful reaction depends on the use of an excess of boron oxide

which binds the formed magnesium oxide in the form of borates. Thus,
the following reactions take place:

2B203 + 3Mg 2B + 3MgO • B203 (2)

4B203 + 3Mg 2B + 3 (MgO • B203) (3 )

Boron Nitride can used as a crucible for Boron production.

The reduction process of boron oxide by magnesium metal is strongly

exothermal. The thermal effect of reaction (1) is equal to 136 Kcal.,
and is estimated that temperatures as high as 2540 0 C can be developed
in the reactive mixture, if there is no heat loss (EFREMKIN and
MIKULINSKII, 1957).

Energetic interaction, characterized by a fast temperature increase

and blaze appearance, takes place when the finely-divided reagents
are heated to the reaction temperature. Reduction occurs within
several seconds. Thermographical studies have shown (MIKHEEVA and
MARKINA, 1957) that exothermal reaction begins at 700-880 o C, i.e.,
above the melting points of boron oxide and magnesium metal. At the
initial stage, the reaction takes place between two liquid phases.
At higher temperatures the evaporation of magnesium begins promoting
the loosening of a film of reaction products at the interface of
boron oxide with magnesium. When this occurs, the speed of reaction
is sharply increased. Probably the boron oxide reduction (EFREMKIN
and MIKULINSKII, 1957) occurs by stages. The first stage is apparently
the formation of boron suboxide:

2BO + MgO (4)

2BO + 2Mg 2B + 2MgO (5)

RAY (1914) gives other formulas for boron suboxides present in boron
obtained by the thermomagnesium method. Investigations show that a
reaction with magnesium oxide forms other subborates, such as MgB30010.
Their presence in thermomagesium boron was proved experimentally
(MARKOVSKII and BELOV, 1967; MARKOVSKII, 1970). The interaction of
magnesium metal with boron results in the simultaneous formation of
borides MgB 2 , MgB4 and MgB12. These borides are thermally unstable
and dissociate into boron and magnesium at the high temperatures
developed during the reduction (MARKOVSKII et al., 1955; MARKOVSKII
and KAPUTOVSKAYA, 1962). This last fact is extremely important because
it explains why preparations with a high percentage of boron cannot
be obtained by using other metals as reducers. Calcium and aluminum,
for example, form stable borides.
216

If the boron reduction is carried out in air, the formation of BO and

boron nitride is possible due to interaction of boron with oxygen and
nitrogen. In this case, excessive boron anhydride and magnesium borates,
produced during the reaction, form a film on the surface of boron
particles. This film prevents further oxidation and nitridation of
boron. KROLL (1918) and MIKULINSKII et al. (1957a) proposed adding
sulfur to the reaction charge. It was believed that a film of melted
magnesium sulfide would then prevent boron interaction with air.

Investigations showed that the effect of the cooling rate on the

oxidation of boron products results in decreased oxygen content in
boron. Sulfur usage was rejected by MIKULINSKII et al. (1957a). Its
use does not considerably improve the quality of the product, and it
requires and additional comsumption of magnesium. Besides, the product
contains an impurity of sulfur up to 0.3% which forms hydrogen sulfide
during the acid treatment.

The substitution of boric acid for boron anhydride has also been at-
tempted (MIKULINSKII et al., 1957a). In this process water is formed
during the dehydration of boric acid. This water reacts with magnesium
at higher temperatures, consuming additional magnesium and evolving
hydrogen. Because presence of hydrogen may lead to formation of an
explosive mixture, the use of boric acid was abandoned when a con-
venient method of preparing boron anhydride was developed (MARON and
VAL'SHCHIKOV, 19621 MIL'MAN and BOBKOV, 1962).

For preparation of pure boron, use of raw materials in as pure a form

as possible is recommended, since all the impurities tend to gather
in the end product. Aluminum, which forms stable borides, is especially
undesirable. Fine crushing of reagents is not necessary. Magnesium
with particle size of 0.3-0.8 mm is recommended (MIKULINSKII, et al.,
1957a) .

Use of borax as a raw material for boron production (MARCHESINI, 1968)

has been found acceptable. Small amounts of boron were produced in
crusibles of chamotte or stainless steel (MOISSAN, 1892, MIKULINSKII
et al., 1957a), using powdered or briquetted charge (MIKULINSKII et
al., 1957a). For reductions carried out on a production scale, vacuum
retort or tunnel ovens are used (MARON and VAL'SHCHIKOV, 19621 MIL'MAN
and BOBKOV, 1962).

There are some indications that the quality of the product is higher
when the charge is spread in a thin layer as reduction then takes
place at a lower temperature (MARCHESINI, 1968). Under laboratory
conditions this reaction can be carried out in an argon atmosphere
without external heating. Potassium chlorate is added to the charge
as an oxidizer (PERMINOV and NERONOV, 1969).

The cake thus produced is rapidly cooled in air, crushed and treated
with acid for dissolution and decomposition of impurities, such as
magnesium oxide, magnesium borates, and magnesium borides. Early
workers used prolonged boiling with hydrochloric acid for the decom-
position of magnesium borides (MOISSAN, 1892). (It should be noted
that during the acid decomposion of magnesium borides, formation of
small amounts of highly toxic boron hydrides may occur.) Acid treatment
was followed by alkaline treatment and finally by boiling with hydro-
fluoric acid and drying in vacuum. After such treatment, the product
contained 94-95% of boron, 2-4% magnesium and 1.2-1.5% undissolved
residue.
 217

Later, the treatment of the product was simplified (MIKULINSKII et

al., 1957a). After 2-4 h of treatment with 12-15% hydrochloric or
20-25% sulfuric acid (POLYAK et al., 1957), washing and drying, the
product is subjected to oxidative roasting in air at temperatures of
540-560 o C for ten minutes. During this treatment, magnesium borides
are oxidized, but boron remains unchanged (MIKULINSKII et al., 1957b;
SEREBRENNIKOVA, 1962). Treatment of the boron cake with superheated
steam at 500°C produces the same effect.

After roasting, the product is treated with an acid for the second
time, washed with water, dried at 80-90 o C, and packed into tightly
sealed packages (EFREMKIN and SHEVELEVA, 1957). It will gradually
oxidize if stored in air. The product obtained by this method is a
brown powder with 94.5-95.5% boron (MIKULINSKII et al., 1957a). The
yield of boric acid is 40% and that of magnesium is 57%. Some of the
boric acid may be regenerated from the wash liquid (MIKULINSKII et
al., 1957a).

An X-ray study of thermomagesium boron shows that it is amorphous.

The only lines seen on the film are those given by the impurities of
magesium boride MgB 1Z (MARKOVSKII et al., 1955).

Magnesium boride impurities may be separated from boron by fusing the

mixture with a large amount of boron oxide (MOISSAN, 1892; MAZZA et
al., 1958). After acid treatment the product contained 98.3% of base
substance, 0.4% magnesium and 1,2% of a residue undissolved in nitric
acid (apparently boron nitride). It is possible to obtain preparations
containing 99.2-99.6% B, when the reaction is carried out in an inert
atmosphere. Boron is also fused with a KBFq + KHFz mixture at 950 to
1000 0 C for purification from magnesium (YANNACAKIS and NIES, 1960).
Impurities of metals contained boron, are turned into volatile chlo-
rides during treatment by boron chloride at 1200-1350 o C (CUEILLERON
and PICHAT, 1965a)
Cold crucible vaccum melting will lead to even higher purity.
Magnesium removal and an increase of boron content is accomplished by
annealing the product in a vacuum (5.10- z -5.10- 1 0mm Hg). However, for
complete removal of magnesium, temperatures of 1400-1800 o C are in-
sufficient (SHAMRAI, MIKHEEVA, 1957). Only at 1900-2000 o C is it possible
to achieve a product containing 99.5-99.8% boron. That is comparable
to the degree of purification obtained in the best samples using other
methods (ZINTL et al., 1940; MARKOVSKII et al., 1955; HAAG, 1957;
SWIFT and WHITE, 1957). Floating with oleic acid in a water medium may
be used to remove some impurities such as boron carbide, iron, etc.,
from boron (SCHAEFFER and SCHMIDT 1964; 1965; 1967).

If it were possible to produce pure boron by reduction of the boron

oxide with metallic aluminum, this would be the most economical proc-
ess. However, the primary product of the interaction of these sub-
stances is aluminum boride (WOHLER and St. CLAIR DEVILLE, 1857). There
is evidence that boron can be produced by metallic aluminum reduction
of melted borax when the metallic aluminum is in such a ratio as to
produce a low-melting Bz03'Alz03 slag. However, such product is of low
quality (89% B, 7% AI, 0.8% Fe and 2.3% of an undissolved residue).

Boron oxide reduction by alkaline metals, lithium, sodium and potassium

(ANDRIEUX, 1929; MARKOVSKII, KONDRASHEV, 1957), as well as their hy-
drides, results in products with low boron content. Calcium boride
(CaB 6) is usually produced by reduction of boron oxide by calcium,
calcium hydride and calcium carbide (HAGENMULLER and DE PAPE, 1959).
218

Thermodynamic calculations have shown that boron can be produced by

reduction of its halogenides (BC13' BF3) by different metals (EFREMKIN,
1957). These processes, however, have no practical application since
halogenides are very expensive, and the equipment needed is very com-
plicated.
Laboratory experiments were carried out to investigate reduction of
boron halogenides by sodium (KAMENAR, 1962; PICHAT and FOREST, 1967;
HOBBS et al., 1964; SCHOTT and HANSLEY, 1964), potassium and potassium-
sodium alloy (PICHAT and FOREST, 1967), magnesium (HOBBS et al., 1964),
zinc (FEDOROV et al., 1960; HIGASHI, 1961; ITO et al., 1962, 1963a,b,c:
HOBBS et al., 1964; CUEILLERON and PICHAT, 1965; NISEL'SON et al.,
1965; PICHAT and FOREST, 1967), aluminum and tin as well as by lithium
hydride and calcium hydride (HAGENMULLER and DE PAPE, 1959).

The reaction of boron chloride with a liquid alloy of K-Na is inter-

esting, because it permits the production of elemental boron at very
low temperatures (about 50°C) (PICHAT and FOREST, 1967). The reaction
with molten sodium and its vapors is carried out at 440-460 o C.

Boron chloride reduction by zinc vapors at 850-950 o C attracted atten-

tion because zinc is one of the few metals which does not form borides
(FEDOROV et al., 1960; NISEL'SON et al., 1965).

3. Electrolytic Method of Boron Production

Boron is produced by electrolysis of melts, containing metal borates

or metal fluoroborates (KAHLENBERG, 1925; ANDRIEUX, 1927, 1929, 1948;
ANDRIEUX and DEISS, 1965). The majority of workers believe that boron
formation is the result of a secondary chemical reaction between alka-
line metals, initially evolved on a cathode, and boron compounds con-
tained in the melts. There are indications, however, that boron is
produced in the primary electrode process (MEERSON and SMIRNOV, 1955).
Boron is formed as loose powder on a cathode. This layer is impregnated
with melt and can be isolated after cooling and treatment with hot
water.

A high quality product was obtained by use of an electrolyte containing

potassium fluoroborate mixed with potassium cloride and potassium fluo-
ride (COOPER, 1945, 1951a,b; COOPER and SCHAEFER, 1959; SAMSONOV et al.,
1959, 1960a). The approximate composition of the electrolyte is as
follows:

KBFq - 17.8%, KCl - 70%, KF - 12%, H20 - 0.2%

Electrolysis was carried out at 750-800 o C (ANDRIEUX 1927, 1948; DEISS

and ANDRIEUX, 1959; PICHAT, 1967). The walls of the elctrolysis vessel
were made of fine-grained graphite which was used as an anode. The
metal cathode was made of Monel metal. Current density was 80 A/dm 2 ,
6 adn the voltage of electrolysis was 5-6 volts. Yield of current was
74% and electric energy consumption was 55 kw/h/kg. The product con-
taining 94-95% boron was obtained after washing and drying. This proc-
ess permitted the production of several kilograms of boron per month
(COOPER and SCHAEFER, 1959).

Other compositions of electrolytes may be used for electrolytic produc-

tion of boron, for example: B203 + KBF~ + KC1; B203 + KF + KC1; B203 +
K2 0 + KF; MgO'B 20 3 + MgF2 (KAHLENBERG, 1925; ANDRIEUX, 1927, 1948;
ANDRIEUX and DEISS, 1955; NIES et al., 1958; MILLER, 1959, 1960)
B 20 3 + Na3A1Fs (MONIER et al., 1965).
 219

X-ray studies of electrolytic boron do not give simple results. Some

samples appeared to be amorphous (MILLER, 1959, 1960). However, the
films of other samples, showed lines, not always distinct, that in-
dicated a crystalline structure (COOPER, 1945, 1951a,b; COOPER and
SCHAEFER, 1959).

Another electrolytic method for preparation of pure boron is based on

the dissolution of a low purity boron or boron carbide at the anode
and the deposition of pure boron on the cathode. Electrolysis is car-
ried out at 800°C. The electrolyte consists of KBF4 (20%), NaCl (40%)
and KCl (40%). After acid treatment, washed and dryed, the product
contained 99.8% boron (STERN and LYNDS, 1958; STERN, 1960a,b).

The electrolytic boron isolated on a cathode can be subjected to refin-

ing. In primary electrolysis where the graphite walls of the vessel are
used as a cathode, the anode is also made of graphite. After deposition
of boron sediment on the walls of the vessel, a rod of low-carbon steel
is introduced. As this rod becomes a cathode, and the walls of the
vessels become an anode, the electrolysis can be repeated (YANO et al.,
1961,1962).

4. The Preparation of Amorphous Boron by Reduction of Boron Compounds

by Hydrogen

Thermometal and electro-chemical methods of boron preparation have

many disadvantages. Among others, they produce a low yield and a low-
quality product. The complicated procedures are difficult to control.
There are difficulties in material selection for large installations,
use of non-standard reactors, complicated purification of the end-
product, etc. For these reasons, boron production by hydrogen reduction
of boron compounds is preferred (SAMSONOV et al., 1960a).

Among the investigated boron compounds only boron halogenides are

suitable for boron production. Hydrogen reduction of copper borate (DEB
and KHUNDAR, 1958), nickel borate (HUG et al., 1958) and cobalt borate
(JAHAN and KHUNDAR, 1961) results only in formation of metals and boron
oxides.

Comparative thermodynamic calculations of the reduction of boron halo-

genides (BF 3 , BC1 3 , BBr3) by hydrogen have shown (CUEILLERON, 1944;
EFREMKIN, 1957; STERN and LYNDS, 1958) that boron fluoride may be re-
duced only at very high temperatures (2000 0 C), thus excluding the pos-
sibility of its practical application. Hydrogen reduction of boron
chloride to elementary boron takes place at temperatures above 1000 o C,
according to the following reaction:

2BC13 + 3H z = 2B + 6HCl (6)

An increase of ratio of BC13 to Hz in the reactice mixture and a de-
crease of pressure increases the yield of boron (CUEILLERON, 1944;
EFREMKIN et al., 1957; STERN and LYNDS, 1958; NISEL'SON et al., 1965;
KRENEV et al., 1972). At lower temperatures (700-900 0 C) interaction
of boron chloride with hydrogen leads more readily to formation of di-
chlorborane (ZHIGACH and STASINEVICH, 1968) according to equation:

BC13 + Hz = BHClz + HCl (7)

Boron bromide is reduced by hydrogen more easily than boron chloride.

The reaction occurs at 750-850 o C.
220

Bromide and iodide of boron are inaccessible and expensive products

and can be used only under laboratory conditions. For these reasons
only boron trichloride has practical significance for boron production
from boron haligenides.

Hydrogen reduction of boron halogenides is endothermic, in constrast

to reduction by metals and the reaction must be carried out by use of
an external heat supply.

There are three means for heating reactive gases: the plasma of elec-
tric arc, discharge in tubular electric ovens, or incandescent heated
filaments or rods.

Because the quality of the product is strongly dependent upon the purity
of the initial materials (FETTERLY, 1960), the available grades of
boron halogenides and hydrogen are sUbjected to thorough purification.

Boron halogenides are easily boiled and readily separated during rec-
tification from metal and nonmetal impurities including boron suboxides.
Consequently, a product of any required degree of purification can be
obtained.

a) Reduction in a Plasma Reactor

With the plasma method of heating, boron formation takes place in plasma
volume or in heated parts of the reactor. By feeding the mixture of
boron trichloride and an excess of hydrogen into a powerful high-vol-
tage arc of alternating current, boron of 99.8-100% purity was obtained
in the form of layers between the 900ling copper electrodes. Highly
dispersed powder, containing up to 99% boron after washing by water
was also found on the walls of the reactor (WEINTRAUB, 1907, 1913). In
these experiments, however, the yield of boron was low, and the coeffi-
cient of energy consumption and productivity of the equipment was also
small.

A better yield from boron trichloride conversion (up to 50%) results

when the process is carried out in a glow discharge at pressures of
up to 150 mm Hg (at about 4000 volts) and a frequency of 1000 Hz on
the cooling copper electrodes. The gas mixture, containing a large ex-
cess of hydrogen, is fed into a discharge through the channel inside
the electrode (HOBBS et al., 1964). Boron is deposited on the walls of
the discharge tube as a black, dispersed powder (containing traces of
Si, Fe, and Al) .

It was recommended by CUEILLERON and CRUIZAT (1973, 1974) that reduction

of boron trichloride by hydrogen be carried out in argon plasma, created
in a cooling quartz tube. They use alternating current of a 12 KW gen-
erator with a frequency of 5-10 Mhz. Gas was supplied in the following
quantities: 15 l/min of argon, 1.0-1,5 l/min of hydrogen, and 0.11-0.22
l/min of boron trichloride.

The axis of the plasma reactor registered 16000 0 K and on periphery,

8000 o K. A thin coating of elemental boron, forming at a rate of 4 g/h
was observed on the walls of the tube. This coating was found to consist
of a-rhombohedral boron structure.

The boron yield, on the basis of consumed boron trichloride, was 70-75%.
Emission spectroscopy analYSis of the product has shown the presence
of silicon, carbon, aluminum, oxygen and other impurities. The total
of the impurities amounted to less than 0.4%. Si (from the tube walls)
was 0.09% and C (formed from phosgene impurities in boron trichloride)
was also 0.09%.
 221

The use of a plasma reactor for chemical reactions at high temperatures

has been proposed by ITO et al. (1964). Hydrogen reduction of boron
trichloride in a plasma burner, capable of producing 250 g/h with 25-
30 KW., has been described also (HAMBLYN et al., 1973). A product has
been obtained with a particle size of 0.5 >J and 99% of boron content.
Pure elemental boron in the form of rods was obtained on electrodes
when a mixture of boron tribromide and hydrogen was heated in plasma
(CUEILLERON, 1944). In this case, black highly dispersed "colloidal"
boron was deposited on the walls of the reactor.

Boron of 98.6-99.5% purity was also obtained by passing the mixture

of boron tribromide and hydrogen through a high frequency arc, formed
between tungsten electrodes (HACKSPILL et al., 1931). X-ray studies
have shown that boron produced in the arc, has a structure ranging
from amorphous to crystalline (CUEILLERON, 1944). The latter was re-
ported to be of rhombohedral form.

b) Reduction in Tubular Electric Ovens

To obtain elemental boron, a mixture of boron halogenides with hydrogen
is passed through a quartz tube inside an electric oven.

Initially, this process produced a low yield of elemental boron con-

taminated by silicon and other impurities from the reactor walls.
Later, boron of 98.9% purity was obtained by a more thorough purifica-
tion of the initial products and hydrogen reduction of boron trichlor-
ide in a tube of high-quality quartz (KIESSLING, 1948).

It has been reported (EPELBAUM and STAROSTINA, 1958) that a product con-
taining 98.9% boron and the following impurities: Al - 0.4%; Si - 0.1%;
Mg - 0.2%; O2 - 0.1% and H - 0.1% was obtained during the hydrogen
reduction of boron tribromide in a quartz tube at 800°C. The same
results were obtained on reduction of boron trichloride in a quartz
tube at 1200 0 C (ITO et al., 1964). A 63% yield of high purity boron
can be produced when the molecular ratio of hydrogen to boron trichlor-
ide equals 60.

A still higher degree of purity in boron was reported by NIEMYSKI and

OLEMPSKA (1963a, b). They passed the pure boron trichloride mixture
with purified hydrogen through a quartz tube heated externally up to
1000-1250 o C. Amorphous boron with 99.9999% B purity and a polycrystalline
product with 99.99% B content was deposited on the walls of the tube.
The amor~hous boron contained the following impurities: Si - 10- 4 % and
Mg - 10- %. The impurities in the crystalline product were: Si - 10- 2 %
and Mg - 10- 5 %.

c) Reduction of Boron Halogenides in the Reactor with Incandescent

Filament or Rods
This method was proposed for the first time in 1922 (KOREF, 1922) and
described in detail by BELYAEV et al. (1969) and POWELL et al. (1960).

In this process, the reduction of boron halogenides occurs on the sur-

face of a heated filament or rod. Simultaneous intermediate hydrogen-
ation reactions of boron halogenides are possible since chloroborane
and diborane are found in the condensed boron trichloride which did
not participate in the reaction.

Amorphous boron produced by this method is the result of the reduction

of boron trichloride at 600-1000 o C (LAUBENGAYER et al., 1943; TALLEY
et al., 1960). Reduction of boron trichloride and boron tribromide on
a heated filament at higher temperatures (1075-1475 0 C), leads to various
222

crystalline modifications of boron. In comparison, by reduction in a

heated tube, crystalline boron can be prepared at lower temperatures
(750-800 0 C). This may be related to lower concentrations of boron com-
pounds in the reaction zone and, consequently, lower velocities of the
atoms forming elemental boron. Consequently, the atoms have time to
take their places in a crystalline lattice. Such slow crystal growth
may not occur in reactions where the boron deposition is rapid.

Kinetic process data on reduction of boron tribromide by hydrogen on

tungsten filament were reported by LAUBENGAYER et al. (1943).

The conditions of preparation of amorphous boron include a rate of

hydrogen flow of 500 cc/min at 1 atm and 25°C. Boron tribromide con-
tent in the reactive mixture is 8-10 mol %. Samples of tungsten wire
of 25 rom in diameter and 5 cm in length are heated to 1130 o C. Under
these conditions the rate of deposition is 4.5 mg B/cm 2 /min. The
diameter of the wire is increased by 1 rom in 25 min. Before deposition
the wire is conditioned in hydrogen at 1430 0 C for 5-10 min. The sample
temperature during deposition must not exceed 1230 o C. At higher temper-
atures boron is deposited in a polycrystalline form. The rate of deposi-
tion is relatively low at temperatures below 830°C.

A horizontal position for the sample is preferred to the vertical one,

since is decreases temperature differences along the length of the
sample, and simplifies the process control. The rate of deposition is
increased as the consumption of gas mixture increases, and as the
ratio of boron tribromide to hydrogen approaches the stoichiometric
proportions. Boron is obtained in the form of small cylinders, approxi-
mately 2 rom in diameter and 5-10 cm in length, as well as in the form
of spheres and cones. The samples contain 98.8% (wt) boron. The major
part of the impurities comes from the tungsten core and consists of
0.5% on the average.

The type of boron obtained in this manner is referred to as amorphous,

because X-ray studies show the presence of two diffuse haloes, typical
for glassy materials. Heating at 1260 0 C and above can convert "amor-
phous" boron into another modification.

5. Production of Amorphous Boron by Thermal Decomposition of Boron

Compounds

In practical applications, preparation of boron by the thermal decom-

position method utilizes only boron halogenides and hydrides. Borides,
such as nitrides, sulphides, phosphides and metal boron hydrides form
products of unknown composition when heated to 1200-1500 o C (l'lEINTRAUB,
1909; TALLEY et al., 1960).

a) Decomposition of Boron Halogenides

Fine crystalline boron (ARMINGTON et al., 1964; WIEBERG et al., 1966)
or red a-rhombohedral boron (McCARTY and CARPENTER, 1960; AMBERGER and
DIETZE, 1964) can be formed by thermal decomposition of boron tri-
iodide. In this case amorphous boron may be formed only as an inter-
mediate phase, which quickly turns crystalline at temperatures of
about 1000 o C. Other crystalline boron modifications can also be formed
during thermal decomposition in the arc discharge (MEYER and ZAPPNER,
1921) or on the incandescent tungsten wires (ARKEL 1934; UNO, 1958).

A mixture of polycrystalline and amorphous boron is deposited when

tungsten filament is at about 1200 0 C (McCARTY and CARPENTER, 1960).
 223

b) Decomposition of Boron Hydrides

Amorphous boron of a varying degree of purity can be formed by decom-
position of diborane, pentaborane and decaborane in a temperature range
from 300 to 900°C (TODD and MILLER, 1946; APKER et al., 1948; SCHLESIN-
GER and SCHAEFFER, 1950; JOHNSTON et al., 1951; LAGRENAUDIE, 1953;
DEVYATYKH, 1966). Decomposition is carried out by passing a gaseous
hydride, usually diluted with hydrogen, through the heated quartz tube.
Similar results were also obtained by heating solid boron hydrides at
800-900 o C in a small boat (made of boron nitride) •

Pyrolysis on an incandescent tungsten and tantalum (WIRTH and DIETZE,

1964; HINZ and WIRTH, 1965) filament results in formation of boron rods
or films (SCHRANGLE and DIETZE, 1972) with crystalline structure.

References

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