CN100572264C - A kind of preparation method of flying saucer shaped nano-hexagonal boron nitride powder - Google Patents
A kind of preparation method of flying saucer shaped nano-hexagonal boron nitride powder Download PDFInfo
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- CN100572264C CN100572264C CNB2008100469305A CN200810046930A CN100572264C CN 100572264 C CN100572264 C CN 100572264C CN B2008100469305 A CNB2008100469305 A CN B2008100469305A CN 200810046930 A CN200810046930 A CN 200810046930A CN 100572264 C CN100572264 C CN 100572264C
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Abstract
The invention belongs to a kind of preparation method of flying saucer shaped nano-hexagonal boron nitride powder.The present invention is prepared into the boron precursor powder with the boron raw material through after the spraying drying; Ball milling mixing boron precursor powder and nitrogen compound obtain boron nitrogen precursor powder; Then boron nitrogen presoma mixed powder is put into approximate airtight reaction vessel, after the warm processing, obtained unbodied boron nitride powder in the process; With unbodied boron nitride powder ball-milling processing, be placed in the High Temperature Furnaces Heating Apparatus again, under nitrogen atmosphere, carry out pyroprocessing.With the product distilled water wash that obtains after the pyroprocessing, remove the impurity such as boron trioxide that may exist in the product, pass through the washing, drying of dehydrated alcohol again after, obtain flying saucer shaped nano-hexagonal boron nitride powder.The flying saucer shaped nano-hexagonal boron nitride powder of the present invention preparation has that granularity is adjustable, purity is high, the characteristics of good dispersity, and the granularity of powder is controlled at 20nm～500nm.Technology of the present invention is simple and direct, easy to control, do not pollute, cost of investment is low, is suitable for commercial scale production.
Description
Technical field
The invention belongs to the preparation method of boron nitride powder.
Background technology
Hexagonal boron nitride (HBN) has with laminar structured like the graphite-like, and outward appearance is a white, thereby claims also that sometimes this boron nitride is class graphitic nitralloy boron or white graphite.Its lattice parameter a=0.251nm ± 0.002nm, c=0.670nm ± 0.004nm, density p is 2.25g/cm
3Hexagonal boron nitride is highly stable in air, and ability 2270K high temperature distils when 3270K, has excellent electric insulating, thermal conductivity, chemical resistance, oxidation-resistance and oilness; Have very strong neutron receptivity, chemical property is stable, to nearly all molten metal inertia all clear.Can be used as pipeline, the pump component of crucible, boat, liquid metal transfer lime, rocket spout, high power device base, the deposite metal of melting evaporated metal, mould of cast steel etc.; Make high temperature member, rocket chamber liner, the thermoshield of spaceship, the corrosion-resistant piece of magnetic current spare generator etc.; Be applied to the isolator of high voltagehigh frequency electricity and plasma arc and the insulator of various well heaters, heating tube sleeve pipe and high temperature, high frequency, High-Voltage Insulation thermal component, the material of frequency applications electric furnace; When boron nitride was used as lubricant, it can be dispersed in Heat-Resisting Grease, water or the solvent; Be sprayed on the friction surface, treat solvent evaporates and form dried mould; Be filled in resin, pottery, matallic surface layer as high temperature resistant self-lubricating composite; The additive that also can be used as various materials.
The method of synthetic hexagonal boron nitride is a lot:
(1) chemical combination or reduction～chemical combination method
A. borax～ammonium chloride method will be sloughed crystal water borax and ammonium chloride mixing afterwards, and reacting by heating in ammonia flow promptly gets boron nitride with the clean system of reactant;
B. borax～Wyler's process the borax that will slough crystal water mixes with urea, and reacting by heating in nitrogen gas stream promptly gets boron nitride with the clean system of reaction product;
C. boric acid～tricalcium phosphate method tricalcium phosphate mixes with boric acid as weighting material, reacts in ammonia flow and gets.
D. the pure boron nitriding promptly gets boron nitride with pure boron powder reacting by heating in nitrogen or ammonia flow with the clean system of reaction product;
(2) a kind of hexagonal nanometer boron nitride microsphere and synthetic method and application
With boron oxide and monohydroxy-alcohol generation esterification, generate the mixture of trihydroxy-boric acid ester and boric acid, carry it in the nitriding furnace with nitrogen or rare gas element, react at high temperature with excess of ammonia gas; Or after directly reaction mixture being utilized ultrasonic atomizer or high-speed gas atomization to become the micron droplet, carry it in the nitriding furnace with nitrogen or rare gas element, react at high temperature with excess of ammonia gas.The product that obtains of reaction, with methanol wash, remove the boron oxide in the product after, obtain hexagonal nanometer boron nitride microsphere (Tang Chengchun, Ding Xiaoxia, Gao Jianming, Qi Shouren.A kind of hexagonal nanometer boron nitride microsphere and synthetic method and application, publication number: CN1931719, the applying date: on December 1st, 2005);
(3) the fibrous compound that contains boron and nitrogen carries out heat treated and the processing powder of gained is pulverized under 400～800 ℃ temperature in non-oxidized gas atmosphere, crushed material is heat-treated under 1000～1800 ℃ temperature in non-oxidized gas atmosphere then, this hexagonal boron nitride powder be shaped as oval plate-like or discoid, and minor axis L a, longitudinal axis L b and thickness t satisfy following formula: 50nm≤La≤Lb≤400nm, 20nm≤t≤150nm, t≤La, 0.5 (the F FOX is carried Nu Si in≤La/Lb≤1.0, Gu Zhen helps people, bell Jiang Zhengyi.Boron nitride and manufacture method thereof, publication number: CN1227531, the applying date: on September 1st, 1999);
(4) with BBr
3And NaNH
2Under the raw material room temperature condition, synthesized the boron nitride hollow ball.(Luyang?Chen，YunleGu，Liang?Shi，Zeheng?Yang，Jianhua?Ma，Yitai?Qian.A?room-temperature?approach?to?boronnitride?hollow?spheres.Solid?State?Communications，130(2004)537-540)；
(5) preparation method of hexagonal boron nitride and the hexagonal boron nitride polycrystalline body powder that makes thereof
With NaBH
4, KBH
4And NaBF
4Deng alkali metal fluosilicate borate, CaB
6Deng metal boride is the boron source, with NaNH
2Deng being nitrogenous source, control reactant ratio, 500～600 ℃ of reactions down, product promptly obtains nanometer and submicron sheet hexagonal boron nitride polycrystalline body powder by washing, filtration and dry.Can prepare the hexagonal boron nitride polycrystalline body is different-shapes such as trilateral sheet, hexagon sheet, oval sheet, irregular sheet.The size and the pattern of sheet boron nitride are even, and the above particle of 80wt.% is included in (Gu Yunle, Liu Yingliang, Zheng Mingtao in median size ± 20% scope.The preparation method of hexagonal boron nitride and the hexagonal boron nitride polycrystalline body powder that makes thereof, publication number: CN1955109, the applying date: on 09 07th, 2006);
There is part can control the powder particle pattern in the above-mentioned synthetic method.It is all different with the present invention that these are reported in synthetic method, reaction scheme and target product aspect.The UFO-like hexagonal boron nitride uniform particle diameter of the present invention preparation is controlled, technology is simple and direct, easy to control, cost of investment is low, is suitable for commercial scale production.
Summary of the invention
The purpose of this invention is to provide and a kind ofly can control the preparation method that the powder particle pattern is suitable for the hexagonal boron nitride powder of preparation of industrialization.Comprise the boron raw material is prepared into the boron precursor powder through after the spraying drying, the precursor powder granularity is controlled at 10nm～500nm; Ball milling mixing boron-nitrogen compound obtains boron nitrogen precursor powder, and (can bear pressure is 0.5～3MPa), after the warm processing, obtains unbodied boron nitride powder in the process then boron nitrogen mixing precursor powder to be put into approximate airtight reaction vessel; With amorphous boron nitride powder ball-milling processing, be placed in the High Temperature Furnaces Heating Apparatus again, under nitrogen atmosphere, carry out pyroprocessing.The product that obtains after the pyroprocessing with distilled water wash, is removed the impurity such as boron trioxide that may exist, and passes through the washing of dehydrated alcohol again, after the drying, obtains flying saucer shaped nano-hexagonal boron nitride powder.The flying saucer shaped nano-hexagonal boron nitride powder of the present invention preparation has that granularity is adjustable, purity is high, the characteristics of good dispersity, and the controllable granularity of powder is built in 20nm～500nm.The present invention thereby technology is simple and direct, easy to control, do not pollute, cost of investment is low, is suitable for commercial scale production.The flying saucer shaped nano-hexagonal boron nitride powder of preparation can be used for mechanical seal, high temperature solid lubricant, and the filler that also can be used as metal and pottery is made bearing etc.
The present invention will be described in detail below in conjunction with accompanying drawing 1:
1, raw material:
(1) the boron raw material is the compound of boron:
The compound of boron: boric acid (H
3BO
3), boron trioxide (B
2O
3) a kind of and sodium tetraborate (Na among both
2B
4O
710H
2O);
(2) the nitrogen raw material is a nitrogen compound:
Nitrogen compound can be selected a kind of in following for use: urea (CO (NH
2)
2), ammonium chloride (NH
4Cl);
2, drying process with atomizing:
Drying process with atomizing: the concentration of aqueous solution of boron raw material is 30～70wt.%, and the spraying drying temperature is controlled at 150～180 ℃, and ambiance is an air;
3, the mixing of nitrogen boron compound: after spray-dired boron raw material and the mixing of nitrogen compound ball milling, ratio of grinding media to material is 8: 1, and the ball milling time is 12 hours, obtains boron nitrogen mixing precursor powder;
4, nitriding process:
With boron nitrogen mixing precursor powder put into approximate airtight reaction vessel (can bear pressure is 0.5～3MPa), through in warm processing, treatment temp is controlled at 800～900 ℃, in 20 minutes～1 hour treatment time, obtains unbodied boron nitride powder; With unbodied boron nitride powder ball-milling processing, ratio of grinding media to material is 10: 1 again, and the ball milling time is 24 hours; Unbodied boron nitride powder behind the ball milling is placed in the High Temperature Furnaces Heating Apparatus, carries out pyroprocessing under nitrogen atmosphere, treatment temp is controlled at 1200～1400 ℃, and the treatment time was controlled at 2～4 hours;
5, product is handled and collection process
To remove the impurity such as boron trioxide that may exist in the product through the product behind the nitriding treatment with distilled water wash 1～2 time, through 2～3 washings of dehydrated alcohol, after 80 ℃ of dryings, obtain flying saucer shaped nano-hexagonal boron nitride powder again.
The flying saucer shaped nano-hexagonal boron nitride powder of the present invention preparation has that granularity is adjustable, purity is high, the characteristics of good dispersity, and the controllable granularity of powder is built in 20nm～500nm.The present invention thereby technology is simple and direct, easy to control, do not pollute, cost of investment is low, is suitable for commercial scale production.The flying saucer shaped nano-hexagonal boron nitride powder of preparation can be used for mechanical seal, high temperature solid lubricant, and the filler that also can be used as metal and pottery is made bearing etc.
Description of drawings
Fig. 1: preparation technology's schema of flying saucer shaped nano-hexagonal boron nitride powder;
Fig. 2: the X ray diffracting spectrum of flying saucer shaped nano-hexagonal boron nitride powder;
Fig. 3: the sem photograph of flying saucer shaped nano-hexagonal boron nitride powder.
Specific embodiments
Embodiment 1:
With 498 gram boric acid (H
3BO
3) and 98 gram sodium tetraborate (Na
2B
4O
710H
2O) raw material is miscible in 1400 milliliters distilled water, makes the boron precursor powder through 180 ℃ of air atmosphere spraying dryings, again with 700 gram urea (CO (NH
2)
2) the dry grinding ball milling puts into approximate airtight reaction vessel after mixing (can bear pressure is 0.5～3MPa), thermal treatment is 20 minutes in 800 ℃ of silicon-carbon stoves, obtain the amorphous powder of boron nitride, after dry grinding is handled through ball milling, be placed in the High Temperature Furnaces Heating Apparatus, carry out pyroprocessing under nitrogen atmosphere, treatment temp is 1200 ℃, and the treatment time was controlled at 3 hours.With product distilled water wash 1 time that obtains after the pyroprocessing, remove the impurity such as boron trioxide that may exist in the product, through 3 washings of dehydrated alcohol, after 80 ℃ of dryings, obtain flying saucer shaped nano-hexagonal boron nitride powder again.
Embodiment 2:
With 498 gram boric acid (H
3BO
3) and 179 gram sodium tetraborate (Na
2B
4O
710H
2O) raw material is miscible in 290 milliliters distilled water, makes the boron precursor powder through 150 ℃ of air atmosphere spraying dryings, again with 1292 gram ammonium chloride (NH
4Cl) (can bear pressure is 0.5～3MPa) to put into approximate airtight reaction vessel after the dry grinding ball milling mixes, thermal treatment is 40 minutes in 900 ℃ of silicon-carbon stoves, obtain the amorphous powder of boron nitride, after dry grinding is handled through ball milling, be placed in the High Temperature Furnaces Heating Apparatus, carry out pyroprocessing under nitrogen atmosphere, nitriding temperature is 1280 ℃, and nitridation time was controlled at 2 hours.With product distilled water wash 2 times that obtain after the pyroprocessing, remove the impurity such as boron trioxide that may exist in the product, through 2 washings of dehydrated alcohol, after 80 ℃ of dryings, obtain flying saucer shaped nano-hexagonal boron nitride powder again.
Embodiment 3:
With 280 gram boron trioxide (B
2O
3) and 80 gram sodium tetraborate (Na
2B
4O
710H
2O) raw material is miscible in 540 milliliters distilled water, makes the boron precursor powder through 160 ℃ of air atmosphere spraying dryings, again with 724 gram urea (CO (NH
2)
2) the dry grinding ball milling puts into approximate airtight reaction vessel after mixing (can bear pressure is 0.5～3MPa), thermal treatment is 60 minutes in 850 ℃ of silicon-carbon stoves, obtain the amorphous powder of boron nitride, after dry grinding is handled through ball milling, be placed in the High Temperature Furnaces Heating Apparatus, carry out pyroprocessing under nitrogen atmosphere, treatment temp is 1400 ℃, and the treatment time was controlled at 4 hours.With product distilled water wash 1 time that obtains after the pyroprocessing, remove the impurity such as boron trioxide that may exist in the product, through 3 washings of dehydrated alcohol, after 80 ℃ of dryings, obtain flying saucer shaped nano-hexagonal boron nitride powder again.
Embodiment 4:
With 280 gram boron trioxide (B
2O
3) and 157 gram sodium tetraborate (Na
2B
4O
710H
2O) raw material is miscible in 291 milliliters distilled water, makes the boron precursor powder through 180 ℃ of air atmosphere spraying dryings, again with 1290 gram ammonium chloride (NH
4Cl) (can bear pressure is 0.5～3MPa) to put into approximate airtight reaction vessel after the dry grinding ball milling mixes, thermal treatment is 30 minutes in 880 silicon-carbon stoves, obtain the amorphous powder of boron nitride, after dry grinding is handled through ball milling, be placed in the High Temperature Furnaces Heating Apparatus, carry out pyroprocessing under nitrogen atmosphere, treatment temp is 1300 ℃, and the treatment time was controlled at 2.5 hours.With product distilled water wash 2 times that obtain after the pyroprocessing, remove the impurity such as boron trioxide that may exist in the product, through 2 washings of dehydrated alcohol, after 80 ℃ of dryings, obtain flying saucer shaped nano-hexagonal boron nitride powder again.
Claims (1)
1, a kind of preparation method of flying saucer shaped nano-hexagonal boron nitride powder, it is characterized in that be 10nm～500nm boron precursor powder with the boron raw material through being prepared into granularity after the spraying drying, ball milling mixing boron precursor powder and nitrogen compound obtain boron nitrogen precursor powder, then boron nitrogen presoma mixed powder is put into reaction vessel, through in after the warm processing, obtain unbodied boron nitride powder, again with unbodied boron nitride powder ball-milling processing, be placed in the High Temperature Furnaces Heating Apparatus, under nitrogen atmosphere, carry out pyroprocessing.With the product distilled water wash that obtains after the pyroprocessing, remove the impurity such as boron trioxide that may exist in the product, pass through the washing, drying of dehydrated alcohol again after, obtain flying saucer shaped nano-hexagonal boron nitride powder, wherein:
(1) raw material:
The boron raw material is boric acid or the boron trioxide a kind of and sodium tetraborate among both;
The nitrogen raw material is urea or ammonium chloride;
(2) spraying drying:
The concentration of aqueous solution of boron raw material is 30～70wt.%, and the spraying drying temperature is controlled at 150～180 ℃, and ambiance is an air;
(3) mixing of boron-nitrogen compound:
Spray-dired boron raw material and nitrogen compound ball milling are mixed, and ratio of grinding media to material is 8: 1, and the ball milling time is 12 hours, obtains boron nitrogen mixing precursor powder;
(4) nitriding process:
Boron nitrogen mixing precursor powder is put into reaction vessel, and the pressure that reaction vessel bears is 0.5～3MPa, through warm processing in 800～900 ℃, in 20 minutes～1 hour treatment time, obtains unbodied boron nitride powder; With unbodied boron nitride powder ball-milling processing, ratio of grinding media to material is 10: 1 again, and the ball milling time is 24 hours; Unbodied boron nitride powder behind the ball milling is placed in the High Temperature Furnaces Heating Apparatus, carries out pyroprocessing under nitrogen atmosphere, treatment temp is 1200～1400 ℃, and the treatment time was controlled at 2～4 hours;
(5) product is handled and collection process:
To remove the impurity such as boron trioxide that may exist in the product through the product that obtains behind the nitriding treatment with distilled water wash 1～2 time, through 2～3 washings of dehydrated alcohol, after 80 ℃ of dryings, obtain flying saucer shaped nano-hexagonal boron nitride powder again.
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| CN101734680B (en) * | 2009-12-14 | 2011-06-08 | 武汉理工大学 | Method for preparing spherical amorphous boron powder by spray drying method |
| CN102515120A (en) * | 2011-12-05 | 2012-06-27 | 沈阳大学 | Preparation method of hollow hexagonal boron nitride microsphere |
| CN102899659A (en) * | 2012-10-16 | 2013-01-30 | 哈尔滨工业大学 | Preparation method of boron nitride nanotube hydrophobic membrane |
| CN102976295B (en) * | 2012-12-27 | 2014-07-23 | 山东大学 | Method for preparing two-dimensional hexagonal boron nitride nanosheet through molten caustic soda |
| CN103043634A (en) * | 2013-01-16 | 2013-04-17 | 华南农业大学 | Hexagonal boron nitride two-dimensional ultrathin nanometer sheet as well as preparation method and application thereof |
| CN103224224B (en) * | 2013-04-10 | 2014-12-03 | 武汉理工大学 | Super thick wall tadpole-like boron nitride nanometer powder preparation method |
| CN103864029B (en) * | 2014-03-28 | 2016-01-13 | 武汉科技大学 | A kind of hexagonal boron nitride powder preparation method |
| CN104058372B (en) * | 2014-07-09 | 2016-03-30 | 河北工业大学 | A kind of preparation method of hexagonal boron nitride nanosheet |
| DE102014222365A1 (en) * | 2014-11-03 | 2016-05-04 | Robert Bosch Gmbh | Method for producing a seal for a sensor element of a sensor for detecting at least one property of a measuring gas in a measuring gas space |
| CN106241753A (en) * | 2015-05-19 | 2016-12-21 | 常州新墨能源科技有限公司 | A kind of preparation method of white graphite alkene nanoparticle |
| JP6657429B2 (en) * | 2016-07-22 | 2020-03-04 | 中国科学院蘇州納米技術与納米▲ファン▼生研究所 | Method for producing boron nitride nanomaterial |
| CN107686098B (en) * | 2017-08-07 | 2020-01-14 | 武汉理工大学 | Layer number controllable hexagonal boron nitride nanosheet and preparation method thereof |
| CN110386593A (en) * | 2019-07-04 | 2019-10-29 | 北京科技大学 | The method that the induction of amorphous precursor body synthesizes spherical boron nitride (BN) nano-powder |
| CN114293259A (en) * | 2021-12-06 | 2022-04-08 | 电子科技大学长三角研究院(湖州) | Boron nitride crystal and preparation method thereof |
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