CN100402417C - Hexagonal nanometer boron nitride microsphere and its synthesis process and application - Google Patents

Hexagonal nanometer boron nitride microsphere and its synthesis process and application Download PDF

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CN100402417C
CN100402417C CNB2005100199340A CN200510019934A CN100402417C CN 100402417 C CN100402417 C CN 100402417C CN B2005100199340 A CNB2005100199340 A CN B2005100199340A CN 200510019934 A CN200510019934 A CN 200510019934A CN 100402417 C CN100402417 C CN 100402417C
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boron nitride
hexagonal
nanometer
alcohol
monohydroxy
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CN1931719A (en
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唐成春
丁晓夏
高建明
祁守仁
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Huazhong Normal University
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Huazhong Normal University
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Abstract

The present invention is hexagonal nanometer boron nitride microsphere and its synthesis process and application. The hexagonal nanometer boron nitride microsphere is laminated structure of 30-150 nm diameter and with 30-50 nm diameter fraction not less than 60 %. The preparation process includes the esterification between boron oxide and monobasic alcohol to produce the mixture of trihydroxy boric acid ester and boric acid, carrying the mixture into nitriding furnace to react with excessive ammonia at high temperature, and washing the reaction product with methanol to eliminate boron oxide to obtain hexagonal nanometer boron nitride microsphere. The preparation process is simple, reliable, low in cost and suitable for large scale production, and the synthesized hexagonal nanometer boron nitride microsphere has high purity and is used as lubricant.

Description

A kind of hexagonal nanometer boron nitride microsphere and synthetic method and application
Technical field
The present invention relates to the method and the application thereof of a kind of synthetic hexagonal boron nitride (h-BN) nanometer ball.
Background technology
The solid lubricant that often uses mainly contains graphite and molybdenumdisulphide and a spot of organic solid lubricant at present.Usually under the condition of high temperature and high loading, use.But because the restriction of the physicochemical property of this class solid lubricant itself makes their range of application be subjected to certain influence.Can not surpass 450 ℃ as the use temperature of graphite, the use temperature of molybdenumdisulphide can not surpass 400 ℃ or the like.
Hexagonal boron nitride has the laminate structure of class graphite, and its physics is similar with graphite with chemical property, and oilness and thermal conductivity are all good.The title that " white graphite " therefore arranged.The performance of hexagonal boron nitride is: 3000 ℃ of fusing points (decomposition), proportion are 2.27; Mohs' hardness 2.Hexagonal boron nitride is in rare gas element and nitrogen, and use temperature can reach 2800 ℃.Use temperature also can reach 900-1000 ℃ in air or oxidizing atmosphere.Just because of the good performance of hexagonal boron nitride, therefore, the report that has some to use at present about them.But the hexagonal boron nitride of these reports is micro-meter scale, the irregular powder of pattern.The production technique that these powders adopt has following several:
1, borax synthesis method; With borax (Na 2B 4O 710H 2O) and ammonium chloride be raw material, logical ammonia synthesis hexagonal boron nitride powder in 700-1000 ℃ of Reaktionsofen.
2, Wyler's process: with boron oxide (B 2O 3) or boric acid (H 3BO 3) and urea ((NH 2) 2CO) be raw material, 900-1300 ℃ of synthetic boron nitride.But this method synthetic boron nitride is to have hexagonal boron nitride and cubic boron nitride (c-BN) and unformed boron nitride powder simultaneously.
3, halogenide synthesis method: with halogenation boron and ammonia is raw material, 600-1000 ℃ of synthetic boron nitride.Common product is for having hexagonal boron nitride and cubic boron nitride simultaneously.
The boron nitride that above-mentioned synthetic method obtains is random powder body material, and its microscopic appearance is uncontrollable.And some synthesis technique more complicated, productive rate is lower, cost is higher.
Just because of it is BN is high temperature resistant, nontoxic, pollution-free.Be expected to use in occasions such as high temperature, food and weavings.There are some researches show: after having added BN, reduced 50% than the wear intensity of the candidate oil that does not add the BN powder.
Summary of the invention
The purpose of this invention is to provide a kind of hexagonal nanometer boron nitride microsphere and synthetic method and application; this hexagonal nanometer boron nitride microsphere can be used for lubricant additive; simple, reliable, the cheap and suitable large-scale production of its synthetic method, synthetic hexagonal boron nitride purity height.
A kind of hexagonal nanometer boron nitride microsphere of the present invention is laminate structure, and diameter is the 30-150 nanometer.Wherein diameter is hexagonal nanometer boron nitride microsphere amount 〉=60% of 30-50 nanometer.
A kind of preparation method of hexagonal boron nitride microballoon of the present invention, preparation process is followed successively by:
1st, be to take by weighing raw material at 1: 3 by the mol ratio of boron oxide and monohydroxy-alcohol, under the state that stirs, divide several slowly to join in the monohydroxy-alcohol boron oxide, complete and the monohydroxy-alcohol reaction until boron oxide, obtain the settled solution of the mixture of trihydroxy-boric acid fat and boric acid, described monohydroxy-alcohol is methyl alcohol or ethanol
2nd, the trihydroxy-boric acid fat that step 1 is obtained and the mixture solution of boric acid, with nitrogen or rare gas element volatile trihydroxy-boric acid fat is brought in the nitriding furnace, react at high temperature with excess of ammonia gas, enter the material quantity of Reaktionsofen with the flow control of nitrogen or rare gas element, the flow of nitrogen and ammonia is decided on the volume of nitriding furnace, and temperature of reaction is 1000-1400 ℃;
3rd, at the following wind direction of nitriding furnace air-flow, product is collected in the temperature lower, obtains being mainly hexagonal nanometer boron nitride microsphere;
4th, the reaction product that step 3 is obtained is with methyl alcohol or distilled water wash, to remove the boron oxide in the product, centrifugation, oven dry, promptly obtaining diameter is the hexagonal boron nitride microballoon of 30-150 nanometer, wherein diameter is 30-50 nano-hexagonal boron nitride nanometer ball 〉=60%.
The another kind of preparation method of hexagonal boron nitride microballoon of the present invention, preparation process is followed successively by:
1st, be to take by weighing raw material at 1: 3 by the mol ratio of boron oxide and monohydroxy-alcohol, under the state that stirs, divide several slowly to join in the monohydroxy-alcohol boron oxide, complete and the monohydroxy-alcohol reaction until boron oxide, obtain the mixture clear soln of trihydroxy-boric acid fat and boric acid, described monohydroxy-alcohol is methyl alcohol or ethanol;
2nd, the trihydroxy-boric acid fat that step 1 is obtained and the mixture solution of boric acid, behind ultrasonic atomizatio or high-speed gas atomization one-tenth micron droplet, utilize nitrogen or rare gas element to bring in the nitriding furnace again, react at high temperature with excess of ammonia gas, enter the material quantity of Reaktionsofen with the flow control of nitrogen or rare gas element, the flow of nitrogen and ammonia is decided on the volume of nitriding furnace, and temperature of reaction is 1000-1400 ℃;
3rd, at the following wind direction of nitriding furnace air-flow, product is collected in the temperature lower, obtains being mainly hexagonal nanometer boron nitride microsphere;
4th, the reaction product that step 3 is obtained is with methyl alcohol or distilled water wash, to remove the boron oxide in the product, centrifugation, oven dry, promptly obtaining diameter is the hexagonal boron nitride microballoon of 30-150 nanometer, wherein diameter is 30-50 nano-hexagonal boron nitride nanometer ball 〉=60%.
Hexagonal boron nitride microballoon of the present invention is used for lubricant additive.
Boron oxide and monohydroxy-alcohol generation esterification reaction, the mixture of generation trihydroxy-boric acid fat and boric acid, reaction equation is as follows.
B 2O 3+3(ROH)→B(OR) 3+B(OH)
Generally, monohydroxy-alcohol is best with methyl alcohol, ethanol takes second place, and propyl alcohol etc. are too high because of carbon content, easily generates decolorizing carbon and make impurity in products too much in follow-up nitrogenizing reaction, so do not advise adopting, generate the mixture of trihydroxy-boric acid fat and boric acid, wherein trihydroxy-boric acid fat is volatile, can utilize nitrogen to be taken in the nitrogenizing reaction stove, react under 1000-1400 ℃ of high temperature with excessive ammonia, generate hexagonal boron nitride and carbonic acid gas and water.Reaction equation is as follows:
B(OR) 3+NH 3→BN+CO 2+H 2O
Also can be directly boron oxide and monohydroxy-alcohol be carried out the trihydroxy-boric acid fat that generates behind the esterification reaction and the mixture of boric acid, be atomized into the droplet of micron with ultrasonic atomizer after, be brought in the nitrogenizing reaction stove with nitrogen, with excessive ammonia 1000-1400 ℃ of pyroreaction, that is:
B(OR) 3+NH 3→BN+CO 2+H 2O
B(OH)3+NH 3→BN+3H 2O
The methyl alcohol of reacted product after methanol wash still can use as raw material.
High resolution TEM shape appearance figure such as Fig. 3 of synthetic hexagonal nanometer boron nitride microsphere.As can be seen from the picture, this hexagonal nanometer boron nitride microsphere has very perfect laminate structure.Formed complete spheroid.Its diameter is the 30-150 nanometer.Studies show that in 800-900 ℃ air and calcine, the sign of non-oxidation.Under 30 MPa pressure, its structure does not have any variation and destruction.
The advantage of method of the present invention is that what synthesize is hexagonal nanometer boron nitride microsphere, the purity height.And the hexagonal boron nitride that additive method synthesizes is the random powder of micron.Method that has even synthetic BN have two kinds of hexagonal boron nitride and cubic boron nitrides mutually, and purity is lower.Present method is simple, and is reliable, is suitable for large-scale production.
Hexagonal nanometer boron nitride microsphere of the present invention is applied in the lubricant, can reduce friction.And, self-repair function is arranged for the position of having worn and torn because its particle diameter is very little.Nano microsphere is filled in the parts surface of two relative movement, and rolling resistance is changed in sliding friction.The frictional coefficient that reduces greatly.Studies show that last non seizure load has improved 17%.
Description of drawings
Fig. 1 is the device synoptic diagram of the synthetic hexagonal boron nitride of trihydroxy-boric acid fat
Fig. 2 is the device synoptic diagram of the synthetic hexagonal boron nitride of boron oxide
Fig. 3 is the high resolution TEM shape appearance figure of synthetic hexagonal nanometer boron nitride microsphere
The title of sequence number representative among the figure: 1 air valve, 2 under meters, 3 three-way cocks, 4 reaction raw materials, 5 tube furnaces, the outlet of 6 alundum tubes, 7 tail gas, 8 ultrasonic atomizers
Specific embodiments
Embodiment 1
Step 1. is according to reaction equation:
B 2O 3+3(ROH)→B(OR) 3+B(OH) 3
By the mol ratio of boron oxide and monohydroxy-alcohol is to take by weighing raw material at 1: 3, under the state that stirs, (monohydroxy-alcohol is best with methyl alcohol to divide several slowly to join monohydroxy-alcohol boron oxide, ethanol takes second place, propyl alcohol etc. are too high because of carbon content, easily generate decolorizing carbon and make impurity in products too much in follow-up nitrogenizing reaction.Below all do representative with methyl alcohol) in go, after directly causing boron oxide and reacting fully, obtain clear soln with methyl alcohol;
Step 2. is according to the synthesizer that connects shown in Figure 1.Tube furnace uses alundum tube.Under guaranteeing bubble-tight situation switch is screwed to nitrogen and only leads in the material container, with the air emptying in the container, logical nitrogen amount is that 5 times of the interior air holding capacity of container get final product; Then threeway Ji is closed pipe and be screwed to nitrogen only towards Reaktionsofen, emptying air, the volume of logical nitrogen are that 5 times of reaction vessel volume get final product; Continue logical small amount of nitrogen, make tube furnace under nitrogen protection, temperature is risen to 1250 ℃; Close nitrogen, open ammonia, the flow of adjusting ammonia is 2 liters/minute, continues to be warming up to 1350 ℃;
When step 3. reaches 1350 ℃ when temperature, open nitrogen, adjusting flow is 1 liter/minute, simultaneously, the flow of ammonia corresponding whole be 1 liter/minute, (flow changes with reference to the size of reaction vessel) reaction 1 hour; After reaction finishes, close ammonia, threeway Ji is closed be screwed to nitrogen only towards Reaktionsofen; Naturally cool to below 600 ℃; Following wind direction in pipe is collected a large amount of fluffy white granular products;
The product that step 4. is collected step 3 adds methanol wash 2 times, centrifugation, and＜120 ℃ of oven dry, promptly obtaining diameter is the hexagonal boron nitride microballoon of 30-150 nanometer, wherein diameter is 30-50 nano-hexagonal boron nitride nanometer ball 〉=60%.Embodiment 2
Step 1. is according to reaction equation:
B 2O 3+3(ROH)→B(OR) 3+B(OH) 3
By the mol ratio of boron oxide and monohydroxy-alcohol is to take by weighing raw material at 1: 3, under the state that stirs, boron oxide is divided slowly to join in the methyl alcohol for several times go, and after directly causing boron oxide and reacting with methyl alcohol fully, obtains clear soln;
Step 2 is according to the synthesizer that connects shown in Figure 2, tube furnace uses alundum tube, is guaranteeing under the bubble-tight situation, threeway Ji is closed be screwed to nitrogen only in material container, with the air emptying in the container, the volume of logical nitrogen is 5 times of volume of air in the container getting final product; Then the three-way cock pipe is screwed to nitrogen and only leads to Reaktionsofen, emptying air, the volume of logical nitrogen are that 5 times of reaction vessel volume get final product; Continue logical small amount of nitrogen, make tube furnace under nitrogen protection, temperature is risen to 1250 ℃; Close nitrogen, open ammonia, the flow of adjusting ammonia is 2 liters/minute, continues to be warming up to 1350 ℃;
When step 3. reaches 1350 ℃ when temperature, open nitrogen, adjusting flow is 1 liter/minute, and simultaneously, the flow of ammonia is corresponding to be adjusted into 1 liter/minute, and ultrasonic atomizer is opened, and reacts 1 hour; After reaction finishes, close ammonia, three-way cock is screwed to nitrogen only leads to Reaktionsofen, cool to naturally below 600 ℃; Following wind direction in pipe is collected a large amount of fluffy white granular products;
The product that step 4. is collected step 3 adds methanol wash 2 times, centrifugation, and＜120 ℃ of oven dry, promptly obtaining diameter is the hexagonal boron nitride microballoon of 30-150 nanometer, wherein diameter is 30-50 nano-hexagonal boron nitride nanometer ball 〉=60%.
Characterize: the XRD test shows of product, product are hexagonal boron nitride.High resolution TEM image has shown the laminate structure that it is good, sees Fig. 3.

Claims (4)

1. a hexagonal nanometer boron nitride microsphere is characterized in that this microballoon is a laminate structure, and diameter is the 30-150 nanometer, and wherein diameter is hexagonal nanometer boron nitride microsphere amount 〉=60% of 30-50 nanometer.
2. the preparation method of the described hexagonal nanometer boron nitride microsphere of claim 1 is characterized in that preparation process is followed successively by:
1st, be to take by weighing raw material at 1: 3 by the mol ratio of boron oxide and monohydroxy-alcohol, under the state that stirs, divide several slowly to join in the monohydroxy-alcohol boron oxide, complete and the monohydroxy-alcohol reaction until boron oxide, obtain the settled solution of trihydroxy-boric acid fat and mebor, described monohydroxy-alcohol is methyl alcohol or ethanol;
2nd, the settled solution of the mixture that step 1 is obtained, with nitrogen or rare gas element volatile trihydroxy-boric acid fat is brought in the nitriding furnace, at high temperature react with excess of ammonia gas, enter the material quantity of Reaktionsofen with the flow control of nitrogen or rare gas element, the flow of nitrogen and ammonia is decided on the volume of nitriding furnace, and temperature of reaction is 1000-1400 ℃;
3rd, at the following wind direction of nitriding furnace air-flow, product is collected in the temperature lower, obtains being mainly hexagonal nanometer boron nitride microsphere;
4th, the reaction product that step 3 is collected, remove boron oxide in the product with methyl alcohol or distilled water wash, centrifugation then, oven dry, promptly obtaining diameter is the hexagonal boron nitride microballoon of 30-150 nanometer, and wherein diameter is 30-50 nano-hexagonal boron nitride nanometer ball amount 〉=60%.
3. the preparation method of the described hexagonal nanometer boron nitride microsphere of claim 1 is characterized in that preparation process is followed successively by:
1st, be to take by weighing raw material at 1: 3 by the mol ratio of boron oxide and monohydroxy-alcohol, under the state that stirs, divide several slowly to join in the monohydroxy-alcohol boron oxide, complete and the monohydroxy-alcohol reaction until boron oxide, obtain the settled solution of trihydroxy-boric acid fat and mebor, described monohydroxy-alcohol is methyl alcohol or ethanol;
2nd, the settled solution of the mixture that step 1 is obtained, behind ultrasonic atomizatio or high-speed gas atomization one-tenth micron droplet, utilize nitrogen or rare gas element to bring in the nitriding furnace again, at high temperature react with excess of ammonia gas, enter the material quantity of Reaktionsofen with the flow control of nitrogen or rare gas element, the flow of nitrogen and ammonia is decided on the volume of nitriding furnace, and temperature of reaction is 1000-1400 ℃;
3rd, at the following wind direction of nitriding furnace air-flow, product is collected in the temperature lower, obtains being mainly hexagonal nanometer boron nitride microsphere:
4th, the reaction product that step 3 is collected is with methyl alcohol or distilled water wash, to remove the boron oxide in the product, centrifugation, oven dry, promptly obtaining diameter is the hexagonal boron nitride microballoon of 30-150 nanometer, wherein diameter is 30-50 nano-hexagonal boron nitride nanometer ball amount 〉=60%.
4. the application of the described hexagonal nanometer boron nitride microsphere of claim 1 is characterized in that being used for lubricant additive.
CNB2005100199340A 2005-12-01 2005-12-01 Hexagonal nanometer boron nitride microsphere and its synthesis process and application Expired - Fee Related CN100402417C (en)

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CN101318636B (en) * 2008-05-12 2011-04-13 中国科学院上海硅酸盐研究所 Method for in situ preparing hexagonal boron nitride containing composite material with nitridation
CN101698808B (en) * 2009-10-21 2012-06-27 北京科技大学 Plate-strip steel cold-rolling emulsified oil containing nanometer hexagonal boron nitride particles, and preparation method
CN103569976B (en) * 2012-08-03 2016-09-14 燕山大学 Ultrahigh hardness nano twin crystal boron nitride block materials and synthetic method thereof
JP6464461B2 (en) * 2014-02-12 2019-02-06 デンカ株式会社 Boron nitride fine particles and method for producing the same
CN105980298B (en) * 2014-02-12 2018-12-18 电化株式会社 Spherical particulate boron nitride and its manufacturing method
CN107522177A (en) * 2016-06-21 2017-12-29 张家港市山牧新材料技术开发有限公司 A kind of preparation method of boron nitride micron and nanometer composite structure
CN108275662B (en) * 2018-02-02 2021-05-25 吉林大学 Preparation method of oxygen-doped hexagonal boron nitride diluted magnetic semiconductor nano material
WO2021193764A1 (en) * 2020-03-26 2021-09-30 デンカ株式会社 Boron nitride particle and resin composition and container comprising same
CN111483983B (en) * 2020-05-06 2021-08-03 河北工业大学 Preparation method of hexagonal boron nitride nanosphere with layered cavitation structure
CN115448263A (en) * 2022-08-05 2022-12-09 深圳市宝硼新材料科技有限公司 Nano spherical boron nitride and preparation method thereof

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CN1227531A (en) * 1996-08-06 1999-09-01 大塚化学株式会社 Boron nitride and process for preparing the same
JP2000327312A (en) * 1999-05-19 2000-11-28 Advanced Ceramics Corp Production of spherical boron nitride and its precursor substance, production facility and product

Patent Citations (2)

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Publication number Priority date Publication date Assignee Title
CN1227531A (en) * 1996-08-06 1999-09-01 大塚化学株式会社 Boron nitride and process for preparing the same
JP2000327312A (en) * 1999-05-19 2000-11-28 Advanced Ceramics Corp Production of spherical boron nitride and its precursor substance, production facility and product

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