Synthesis and characterization of boron

nitride powder
Cite as: AIP Conference Proceedings 1971, 020007 (2018); https://doi.org/10.1063/1.5041102
Published Online: 07 June 2018

Ying Li, Yong Shen, Chen Gong, et al.

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AIP Conference Proceedings 1971, 020007 (2018); https://doi.org/10.1063/1.5041102 1971, 020007

© 2018 Author(s).
 Synthesis and Characterization of Boron Nitride Powder
Ying Li 1, a), Yong Shen 2, b), Chen Gong 1, Bentao Li 1, Hui Huang 1, Kejian Ji 1
1
CNGC Institute 53, Jinan 250031, China
2
Shandong Quality Inspection Center for Medical Devices, Jinan250101, China
a)
Corresponding author: liying-0427@163.com
b)
shen1208@126.com

Abstract. The boron nitride powder is prepared from precursor sintering process and the boracic acid and melamine as
raw materials. The effect of raw material ratio, reaction temperature, charging sequences in the synthesis process of
precursor on total carbon content and boron-nitrogen mole ratio in precursors is studied. The synthesis condition with
2:1 raw material ratio and 90ćsynthesis temperature is determined, and determine to synthesize a precursor with a new
structure by XRD, IR spectrogram characterization. The effect of sintering temperature and sintering atmosphere on the
each component content in the high-heat treatment process is further studied; the technological conditions of preparation
process are optimized, the heat treatment temperature is screened as the main factor to control the content of boron
trioxide, thus, boron nitride powders with different purity are manufactured.

Key words: boron nitride; boron trioxide; precursor; synthesis.

INTRODUCTION
The boron nitride has excellent thermal stability, low dielectric constant, low dielectric losses and good
mechanical properties, ceramic materials made by boron nitride has high temperature resistance, wear resistance,
corrosion resistance and other special properties, and it occupies the absolute advantage position in the supersonic
and hypersonic missile radome. The properties of boron nitride and its components are closely related, for example,
excessive boron trioxide in boron nitride will cause permanent expansion of ceramics, reduce the ceramic strength;
free boron volatilize in the sintering process, cause the ceramic density to be greatly reduced; trace impurities such
as iron, calcium will reduce the thermal shock strength of ceramics, make its brittleness change, the dielectric
properties of boron nitride will be reduced simultaneously. Therefore, we need to control the impurity elements such
as boron trioxide in the synthesis process of boron nitride, in order to make boron nitride powder with different
purities, and provide guarantees for the development work of boron nitride ceramic materials.

PREPARATION METHOD OF BORON NITRIDE

The preparation of uniform and stable boron nitride powder and the commonly used methods are solid-state
reaction route, hydrothermal synthesis, chemical vapor deposition, and the precursor sintering method.

Solid-state Reaction Route

Solid-state reaction route usually takes borax, boron trioxide and ammonium chloride and so on as raw materials,
and carried out in agitated reactor at 500ć~600ć, but there may be side reactions in the reaction process, affect the
purity of the product [1, 2]. The occurrence of solid-state reaction starts from the contact of two reactant molecules,
and then goes through diffusion-reaction-nucleation-growth four stages, chemical reaction is the main step to control

Materials Science, Energy Technology and Power Engineering II (MEP2018)

AIP Conf. Proc. 1971, 020007-1–020007-7; https://doi.org/10.1063/1.5041102
Published by AIP Publishing. 978-0-7354-1678-9/$30.00

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the reaction rate. Only a lower reaction temperature greatly affects the purity of boron nitride, it is necessary to be
ammoniated and other subsequent treatment [3], otherwise the agglomeration phenomenon of final product is
serious. Although the production efficiency is high, the post-processing is tedious and the purity of the product is
low.

Chemical Vapor Deposition

Chemical vapor deposition generally uses the hot wall reactor, the gaseous material with boron and nitrogen is
introduced into the reaction chamber through carrier gas, the chemical reaction among gaseous materials occurs at
high temperature to produce boron nitride powder [4]. The powder made by this method has uniform particle, high
purity, small particle size and good depressiveness [5]. R. Gao[6] made ball-milling for raw materials with 1:1 B/N,
heated to 900ć~1000ć, the white boron nitride product can be obtained. Other researchers [7] also uses boron
powder and magnesium oxide as raw material to heat up to 1300ć under ammonia atmosphere, and boron nitride
with high purity is prepared. The metal institute of Chinese Academy of Sciences has been innovating for many
years, the BCl3 as boron source, NH3 as nitrogen source, under the 1900ć, boron nitride with high purity was
prepared by induction furnace [8].

Precursor Sintering Method

Precursor sintering method is to synthesize the compound containing boron and nitrogen after chemical reaction,
and then the final product is produced by sintering at high temperature. The precursor usually contains B, N, O, C
and other elements, the materials which are used for the synthesis of precursor are: boric acid, boracic acid,
melamine, ammonium chloride, etc. Paine [9, 10] use a precursor method to synthesize compound sol containing
boron oxazine ring, then boron nitride is produced by pyrolysis under the protection of 1200ć inert gas. C.
Deng[11,12] takes BCl3 and NH4Cl as raw material, synthesize boron three chlorine borazine, the and methylamine,
dimethyl amine, n-propyl amine or its system constituent system to carry out aminolysis substitution reaction, get
the polymer precursor, after decarburization, and get boron nitride pyrolysis after process. The productivity of this
method is high, but the product contains boron oxide, free boron and other impurities.
In order to study the technological conditions to control boron oxide, this paper adopts precursor sintering
method to synthesize boron nitride, select the proper raw material ratio, synthesized temperature, sintering
atmosphere, sintering temperature and other influencing factors.

RESEARCH ON THE INFLUENCING FACTORS OF PRECURSOR SYNTHESIS

PROCESS

Raw Material Ratio

The boric acid and melamine as raw materials, the effects of raw material ratio on the total carbon content and
the boron and nitrogen ratio in the precursor is studied, as shown in Figure 1-2.

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 FIGURE 1. Effect of raw material ratio on the boron and FIGURE 2. Effect of raw material ratio on total carbon content
nitrogen ratio in precursor in precursor

It can be seen from Figure.1 that the boron-nitrogen ratio of product increases with the increase of boric
acid/melamine ratio, when the mole ratio of boric acid/melamine exceeds 2:1, the boron-nitrogen ratio reaches the
maximum and remains the unchanged. This shows that excessive boric acid does not react with melamine to
produce the precursor, but dissolves in water, and it has little effect on the composition precursor.
As can be seen from the Figure.2, with the increase of proportion of boric acid/melamine, total carbon content in
the product gradually reduced, when the mole ratio of boric acid and melamine is more than 2:1, total carbon content
in the precursor reaches minimum. Too much carbon content in high temperature sintering will react with boron to
produce boron carbide, and affect the purity, therefore, the mole ratio of boric acid and melamine is 2:1, which is the
optimal raw material ratio of the precursor.

Reaction Temperature
Reaction temperature has direct effect on the synthesis of precursor, the boric acid and melamine as raw
materials, mole ratio is 2:1, the effect of reaction temperature on the total carbon content and boron and nitrogen
ratio in the precursor is studied, the results is listed in Table.1.

TABLE 1. Effect of reaction temperature on the total carbon and boron nitrogen ratio in the precursor
Order number Reaction temperature /ć Total carbon content % B/N Productivity /%
1 60 13.9 0.35 65
2 70 14.1 0.36 70
3 80 14.0 0.33 72
4 90 13.8 0.34 78
5 100 13.6 0.34 70

It is known from Table.1 that when the temperature is higher than 60ć, the reactants gradually dissolve in the
water, as the temperature rises, the solution system gradually becomes clear. The results show that the total carbon
content and boron nitrogen ratio in the precursor synthesized at different temperatures do not change much, the
productivity increases with the increase of the reaction temperature, it shows that reaction temperature has no effect
for the structure composition of the synthesized precursor, high temperature can improve the solubility of the
reactants, and it can accelerate the reaction. Therefore, the optimum reaction temperature for the synthesized
precursor is 90ć.

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 Structure Characterization of Precursor

The boric acid and melamine as raw materials, the mole ratio is 2:1, reaction temperature is 90ć, heated for 6h,
filtration and drying after natural cooling, and obtain the precursor product, and make structure characterization for
it, and the XRD and IR spectrogram of boric acid and melamine are compared, the results as shown in Figure.3-
Figure.4.

FIGURE 3. XRD diagram of precursor and raw material FIGURE 4. IR diagram of precursor and raw material

As can be seen from Figure.3, when the melamine in the 19°, 24°and 29° 2ș angle, it has obvious diffraction
peaks, when boric acid in 16°, 30°2ș angle, it has have obvious diffraction peaks, and the synthesized precursor is
the powder with good crystallization, the diffraction peak position is obviously different from melamine and boric
acid. When 2ș=14°, characteristic peaks appear, it shows that the reaction produces new material, and not a simple
mixture of boric acid and melamine, and under the condition of synthesis, raw materials boric acid and melamine are
not separated out.
As can be seen from Figure.4, we can see that melamine has obvious absorption peaks in 3300cm-1, 1551cm-1,
1022cm-1 and 814cm-1, which correspond to N-H stretching vibration, bending vibration, torsional vibration and B-
N stretching vibration, respectively, 1551cm-1 and 814cm-1 correspond to the structure of carbon-nitrogen triazine
ring. The boric acid has obvious absorption peaks near 3210cm-1, 1500cm-1 and 1200cm-1, which correspond to
the O-H stretching vibration of boric acid, and the stretching vibration of B=O, B-N. As can be seen from the IR
spectrogram of precursor, 3520cm-1 is stretching vibration of O-H bond, 3415cm-1 is anti-symmetric stretching
vibration peak of NH2, compared with NH2 corresponding absorption peak of melamine, low wavenumber direction
move, it shows that hydrogen bond exist in molecules; 1551cm-1 and 1438cm-1 absorptions peak are caused by
three triazine ring characteristic peak and B-O bond stretching vibration; 1236cm-1 and 802cm-1 belong to
stretching vibration peak of B2O3.
It can be seen that the precursor contains the structure of triazine ring, amidogen, B-OH bond and so on, which is
a new substance produced by boric acid and melamine reaction, the possible reaction formula is as follows:

H3BO3+C3N6H6ĺ(H3BO3)2C3N6H6 (1)

RESEARCH ON HEAT TREATMENT TECHNOLOGY OF PRECURSOR

The heat treatment technology of the precursor can be divided into two parts: pre-sintering and high temperature
sintering of carbon tube furnace. The purpose of pre-sintering is to remove carbon from precursors and prevent
subsequent reactions from forming boron carbide, at the same time, pre-sintering can improve boron nitrogen ratio
in precursors, and this reaction needs to be carried out under the condition of air circulation. High temperature
sintering of carbon tube furnace is an important step to obtain boron nitride, reasonable sintering temperature is not

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only conducive to the growth of boron nitride crystals, but also plays an important role in controlling boron oxide
content in the components.

Pre-sintering Temperature
The precursor is put into corundum crucible, under the condition of air circulation, it is heated to a certain
temperature heat in muffle furnace and for 5h, the effect of pre-sintering temperature on total carbon content in the
pre-sintering product and boron and nitrogen ratio is studied, and the result is shown in Figure.5-6.

FIGURE 5. Effect of pre-sintering temperature on total carbon FIGURE 6. Effect of pre-sintering temperature on the boron-
content in pre-sintering product nitrogen ratio in pre-sintering product

As can be seen in Figure.5, when the temperature is below 400ć, the total carbon content of the pre-sintering
product is 14%, with the increase of temperature, the total carbon content will decrease significantly, and the total
carbon content will decrease to 0.2% at 600ć. Hereafter, the temperature will continue to rise and the total carbon
content will remain unchanged. The reason for this phenomenon is the oxidation temperature of carbon in the air is
500ć~600ć, when the temperature exceeds 500ć, the carbon-nitrogen of triazine ring structure is resolved in the
precursor, carbon in triazine ring combines with oxygen in the air to produce carbon dioxide to escape, resulting in a
decline in the total carbon content, carbon in the pre-sintering product are basically removed carbon to 700ć,.
It can be seen in Figure 6, between 400 ć~700ć, boron nitrogen ratio of pre-sintering product enlarges with the
increase of temperature, it shows that the precursor starts to decompose, carbon and nitrogen in triazine ring escape
in the form of carbon dioxide and nitrogen, respectively, when the temperature reaches 700ć, boron nitrogen ratio
tends to be stable, produce the pre-sintering product with 4:3 boron-nitrogen ratio, the optimum pre-sintering
temperature of the precursor is 700ć.

High Temperature Sintering Temperature

The above pre-sintering products together with corundum crucible are put into graphite carbon tube furnace, high
purity nitrogen is bubbled, flow is 2L/min, pressure is 0.1MPa, first heated to 800ćat 10ć/min, then the heated to
1100v at 5 ć/min or higher, preserve heat for 2h, get boron nitride powder. The effects of sintering temperature on
the total nitrogen, total boron, boron oxide and free boron in boron nitride are investigated and so on. The results are
shown in Table 2.

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 TABLE 2. Effect of high-temperature sintering temperature on the content of boron nitride
Measured value /%
Sintering temperature /ć
Total nitrogen Total boron Boric oxide Free boron
1100 42.0 35.7 5.01 0.061
1200 46.8 41.0 4.16 0.058
1300 54.6 42.5 1.08 0.051
1400 54.8 42.4 0.96 0.049
1500 54.9 42.6 0.96 0.052

It can be known from table 2 that the content of total nitrogen and total boron increase with the increase of
sintering temperature, and the content of boron oxide shows the opposite trend, and the temperature affect free boron
little. The precursor is resolved in the carbon tube furnace, and form part of boron oxide and free boron, when a
certain temperature reaches a certain level, boron oxide or free boron can react with nitrogen and transform into
boron nitride. The reaction formula is as follows:

2B2O3+5N2ĺ4BN+6NO (2)

2B+N2ĺ2BN (3)

Therefore, the high-temperature sintering temperature is the main condition for controlling the content of boron
oxide in boron nitride.

Sintering Atmosphere at High Temperature

High temperature sintering can be carried out under the conditions of nitrogen protection and in the vacuum
environment. The pre-sintering of precursors is divided into two with equal weights. Under the conditions of
nitrogen and vacuum, respectively, they are heated to 1300ć, and preserve heat for 2h, the contents of each
component in two boron nitride are measured, and the results are listed in Table 3.

TABLE 3. Effect of high temperature sintering atmosphere on the content of boron nitride
Measured value /%
Sintering atmosphere
Total nitrogen Total boron Boric oxide Free boron
vacuum 49.5 46.5 1.17 0.055
nitrogen 54.6 42.5 1.08 0.051

As can be seen from Table 3, under the same conditions, the total nitrogen content of boron nitride produced by
the vacuum atmosphere is significantly lower than nitrogen atmosphere sintering product, the reason is that nitrogen
not only plays a role in protecting gas., at the same time also participate in part of reaction, and provide nitrogen
source for the synthesis of boron nitride.

Structure Characterization of Boron Nitride

The XRD and IR spectrogram of the boron nitride products made from different sintering temperatures and
sintering atmospheres are shown in Figure.7-8.
As can be seen from Figure.7, under 1200ć~1500ć nitrogen sintering conditions, a few obvious sharp
diffraction peaks appear near 2ș=26° and 2ș=40°, by consulting and contrast JCPDS card, it is found that it matches
with in BN 34-0421; at the same time, the obvious diffraction peaks occur near 2ș=43°, 2ș=55°, 2ș=76° as well, by
consulting and contrast JCPDS card, it is consistent with the boron nitride in 45-1171. Under the conditions of

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vacuum sintering at 1300ć, the characteristic peaks of the products also conform to the standard spectrogram of
boron nitride, but there are more obvious impure peaks.

FIGURE 7. XRD diagram of products under different FIGURE 8. IR diagram of products under different sintering
sintering temperatures and atmospheres temperatures and atmospheres

As can be seen from Figure.8, when the temperature is higher than 1300ć, obvious absorption peaks occur in
1383cm-1 and 813cm-1, here is the stretching vibrations and flexural vibrations of B-N bond, when the temperature
is 1200ć, you can see an obvious absorption peak in the vicinity of 3200cm-1, it is caused by the B-O bond
vibration, there is some boron oxide in the product.

CONCLUSION
Through the research on the raw material ratio, reaction temperature and charging sequence in the synthesis
process of the precursor, a kind of new material which is different from boric acid and melamine is synthesized, the
total carbon content of this material is about 13%, mole ratio of boron nitrogen is 1:3, XRD, IR spectrogram show
that the precursor has triazine ring structure.
The effects of pre-sintering temperature, high temperature sintering atmosphere and sintering temperature on the
content of each component in the product are studied in the sintering process of precursor, and boron nitride powder
with controllable boron oxide content is prepared.

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