CN104803362B - The preparation method of hexagonal boron nitride powder and three-dimensional boron nitride - Google Patents
The preparation method of hexagonal boron nitride powder and three-dimensional boron nitride Download PDFInfo
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- CN104803362B CN104803362B CN201510166440.9A CN201510166440A CN104803362B CN 104803362 B CN104803362 B CN 104803362B CN 201510166440 A CN201510166440 A CN 201510166440A CN 104803362 B CN104803362 B CN 104803362B
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Abstract
The invention belongs to Inorganic synthese technical field, the preparation method of specially a kind of hexagonal boron nitride powder and three-dimensional boron nitride.The present invention uses chemical vapour deposition technique, and using transition metal elemental powders or the compound containing transition metal is catalyst, is reacted by high temperature reduction, prepares porous metal catalyst skeleton；Chemical vapour deposition technique growth hexagonal boron nitride is recycled, obtains the hexagonal boron nitride powder with catalyst backbone and three-dimensional boron nitride；The present invention is easy to operate, equipment requirement is low, yield is high；Quick, a large amount of preparations of boron nitride powder and three-dimensional boron nitride can be realized, and obtaining three-dimensional boron nitride has space small（100 nanometers 100 microns）, density is big（It is per cubic centimeter up to 100 milligrams）The advantages that, the three-dimensional boron nitride has wide practical use with boron nitride powder in space heat conduction, catalyst carrier and sound absorption are shockproof etc..
Description
Technical field
The invention belongs to Inorganic synthese technical field, and in particular to a kind of preparation of hexagonal boron nitride powder and three-dimensional structure
Method.
Background technology
Nano-hexagonal boron nitride is the two-dimensional material of a species graphene, and simultaneously and a kind of excellent performance and with very
The new ceramic material for the potentiality that develop on a large scale, because it has high-temperature oxidation resistance, radiation hardness, high thermal conductivity, high temperature lubricating, dielectric
The characteristics of performance and good insulating properties, had a wide range of applications in fields such as metallurgy, space flight and aviation, electronics and nuclear industry.Six
Square boron nitride powder material is the tridimensional network that the boron nitride nanosheet based on two dimension is cross-linked to form by space, except tool
There is the property of two-dimentional boron nitride nanosheet, three-dimensional boron nitride nanometer material is in space heat conduction, and catalyst carrier and sound absorption are shockproof etc.
Aspect has bigger advantage.
Hexagonal boron nitride remains to holding stabilization at 2500 degrees Celsius under inert atmosphere, at 850 degrees Celsius in oxidisability gas
Good stability can be kept under atmosphere.In contrast, three-dimensional grapheme and its metal array framework are higher than 600 degree of feelings in temperature
Occur under condition and cave in, decompose or aoxidize so that three-dimensional grapheme materials application field is limited.Superiority due to more than
Can, hexagonal boron nitride is preparing high heat-conducting ceramic device, high heat conduction sapecial coating, heat conductive insulating polymer composites, resistance to height
Warm kollag and lubricating oil and grease additive etc. have huge application prospect.2013, Nanjing Aero-Space University
Guo Wanlin groups use Three-dimensional boron nitride foam of the foam metal for excellent properties such as template obtained low-density, high thermal stabilities.But
It is that the network hole of foam metal is up to hundreds of microns, in the Three-dimensional boron nitride foam prepared as template, bulk density is low,
It is unfavorable for the preparation of its magnanimity.The present invention is with transition metal simple-substance or the compound containing transition metal is raw material, by high temperature
After reduction, porous catalyst template is prepared so as to substitute traditional foam metal template, than making catalysis bone using foam metal
The three-dimensional boron nitride porosity that frame obtains is higher；In addition, it can also prepare the hexagonal boron nitride powder of magnanimity high quality.
The content of the invention
Hexagonal boron nitride powder can quickly, be largely prepared it is an object of the invention to provide one kind and prepared by three-dimensional boron nitride
Method, the three-dimensional boron nitride space obtained is small, density is big.
The preparation method of hexagonal boron nitride powder provided by the invention and three-dimensional boron nitride, it is with transition metal elemental powders
Or the compound containing transition metal is catalyst, is reacted by high temperature reduction, prepares porous metal catalyst skeleton；Again
Hexagonal boron nitride is grown using chemical vapour deposition technique, the hexagonal boron nitride powder with catalyst backbone is obtained and three-dimensional nitrogenizes
Boron；Wherein, hexagonal boron nitride powder refers to the three-dimensional netted powder that two-dimentional boron nitride nanosheet is mutually lapped, nanometer length of a film
For 10 nanometers -100 microns, thickness is 1 nanometer -10 microns；Three-dimensional boron nitride refers to pass through before with solution etches catalyst
The hexagonal boron nitride obtained after polymer protection, there is the full UNICOM's network structure of three-dimensional of high porosity, be by boron nitride nanometer
With the network being connected with each other, density is 0.2 milligram -100 milligrams per cubic centimeter per cubic centimeter.
This method comprises the following steps that；
The first step, catalyst pre-treatment：The catalyst is for transition metal elemental powders and/or containing transition metal
Compound, catalyst is positioned in reaction vessel, or catalyst is filled in macrocellular foam metal form, then be placed in anti-
Answer in container；Reaction vessel vacuumizes or is passed through inert atmosphere protection, and is warming up to 500-1500 with 1-100 degree speed per minute
Container area residing for degrees Centigrade catalyst, the reducing atmospheres such as hydrogen are passed through, anneal -10 hours 1 minute, obtain porous
Metallic catalyst skeleton；
Second step, growing boron nitride：Catalyzer temperature-elevating in reaction vessel is placed on to reaction temperature（400-1200 is Celsius
Degree）, while by reaction source（That is boron, nitrogen source）It is passed through catalyst area（By the solid-state boron in heating response container, nitrogen source, or
Vapor reaction source is passed through, the atmosphere for carrying reaction source can also be passed through）, growth time is -10 hours 30 seconds, growth pressure 1
- 1 atmospheric pressure of millitorr；Then room temperature is cooled to 1-100 degree speed per minute；Obtain six side's nitrogen with catalyst backbone
Change boron powder；
3rd step, post processing：The hexagonal boron nitride powder with catalyst backbone grown is taken out, is put into solution
Middle etching catalyst, obtains hexagonal boron nitride powder；Or take out the boron nitride sample grown, using high molecular polymerization
Thing is protected, and is then put into solution and is etched catalyst, then removes high molecular polymer, then obtains three-dimensional boron nitride.
In the present invention, the reaction vessel be quartz ampoule, alundum tube or other can be with the container of input and output gas.
In the present invention, the inert atmosphere is one or more of mixed gas in the inert gases such as nitrogen, argon gas；Reduction
Property atmosphere be hydrogen or hydrogen and above-mentioned inert gas mixed gas.
In the present invention, the transition metal may be selected from but be not limited to nickel, copper, cobalt, platinum, iron or rubidium.The transition gold
It is 0.1 micron -100 microns to belong to elemental powders particle diameter.The compound containing transition metal may be selected from but be not limited to transition
Metal oxide, transition metal salt or its hydrate.
Wherein, for transition metal salt hydrate, it can be decrystallized in 50-300 degrees Celsius of drying or microwave heating
Water obtains Anhydrous transition metal salt or directly carries out high temperature reduction.
In the present invention, the reaction source can be solid phase boron, nitrogen source, or gas phase boron, nitrogen source, or liquid phase boron,
Nitrogen source, described solid phase boron, nitrogen source may be selected from but be not limited to：The boracics such as ammonia borane, nitrogen compound；Gas phase boron, nitrogen source include
The boracics such as diborane, boron chloride, nitrogen, ammonia, the one or more of of gas of nitrogen mix；Boron, nitrogen source can also with boracic,
The liquid of nitrogen（Such as inorganic benzene）Reaction vessel is brought into by inert gas boron, nitrogen source are provided.
In the present invention, the porous catalyst skeleton has three-dimensional cross-linked structure, and its aperture is 100 nanometers -100 micro-
Rice.
In the present invention, the aperture of contained hole is 100 nanometers -100 microns in the hexagonal boron nitride with catalyst backbone.
In the present invention, it is described be used for etching metallic catalyst skeleton solution it is available containing concentration be 0.05-6 moles every liter
Any one in sulfuric acid, hydrochloric acid, nitric acid, iron chloride, ferric nitrate, ammonium persulfate and Marble reagents or two or more mixing
The solution of thing.
In the present invention, in foregoing etch processes, also three-dimensional boron nitride is protected using high molecular polymer
Shield, one or several of the high molecular polymer including polymethyl methacrylate, polyethylene, polystyrene or polypropylene are mixed
Close.High-temperature calcination can be used by removing macromolecule（100-1000 degrees Celsius）, or using organic solvent（Ketone, chlorohydrocarbon, fragrance
The one or more of hydrocarbon, halogenated hydrocarbons reagent）Dissolving.
As one of scheme that can implement, the program may also include：By transition metal simple substance and/or containing transition metal member
The compound of element is filled in macrocellular foam metal form, after high temperature reduction, obtains three-dimensional porous metallic catalyst template.
The aperture of foregoing macrocellular foam metallic catalyst contained hole is 500 nanometers -500 microns.Macrocellular foam metal is main
There are nickel foam, foamed iron, foam copper or foam cobalt etc..
As more one of preferred embodiment, step（1）In, high temperature reduction reaction, it in temperature is 100- to be
Carried out in 1200 degrees Celsius of reducing atmosphere, the reducing atmosphere is mainly argon gas of the 1-500 than 10-1000 by flow-rate ratio
Formed with hydrogen, carrier gas overall flow rate is that 1-2000 milliliters are per minute.
As more one of preferred embodiment, step（2）In, the growth temperature is 1000 degrees Celsius, during growth
Between be 40 minutes, growth pressure is 1 atmospheric pressure.
Compared with prior art, the present invention at least has following advantages：It is easy to operate, equipment requirement is low, yield is high；This hair
The bright preparation that can realize boron nitride powder magnanimity high quality；The method can realize that three-dimensional boron nitride is quick, largely prepares simultaneously, and institute
Obtaining three-dimensional boron nitride has space small（100 nanometers -100 microns）, density is big（It is reachable100Milligram is per cubic centimeter）The advantages that,
The three-dimensional boron nitride is with boron nitride powder before space heat conduction, catalyst carrier and shockproof etc. be widely used that absorb sound
Scape.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of hexagonal boron nitride powder.
Fig. 2 is the scanning electron microscope (SEM) photograph of hexagonal boron nitride powder.
Fig. 3 is protected with polymethyl methacrylate, etches away the three-dimensional boron nitride scanning electron microscope (SEM) photograph of Raney nickel.
Fig. 4 is the Raman spectrogram of copper powder catalytic growth hexagonal boron nitride.
Fig. 5 is the scanning electron microscope (SEM) photograph that nickel foam is added after nickel powder.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail：
The present invention is using transition metal elemental powders, salt or its hydrate, oxide（That is, presoma）By high temperature reduction
The 3-dimensional metal skeleton with catalytic property is obtained, utilizes chemical vapour deposition technique, under appropriate atmosphere, catalytic growth nitrogen
Change boron, finally etch metallic framework and obtain boron nitride powder or three-dimensional boron nitride.Wherein, transition metal salt hydrate in high temperature also
Before original, first pass through heating, drying or microwave heats acquisition Anhydrous transition metal salt after water process of decrystallizing.
First, the preparation of hexagonal boron nitride powder
Embodiment 1, first, the preparation before reaction：By 0.5 gram of borine ammino-complex（Boron, nitrogen source）, 0.5 gram of nickel powder
（Catalyst）Loaded in same quartz ampoule, wherein, quartz ampoule front end residing for ammonia borane, and wrapped up with heating mantle, stone residing for nickel powder
English pipe portion is positioned in tube furnace.Open vavuum pump and quartz ampoule air pressure inside is evacuated to 5 × 10-3Support is following, is passed through flow velocity as 400
Air pressure refunds to normal pressure is continued to be passed through argon gas draining air by milliliter argon gas per minute（This terminates up to reaction, and air outlet valve is beaten
Open to maintain atmospheric pressure environment）, tube furnace is warming up to 1000 degrees Celsius with 50 degree of speed per minute, argon gas is closed afterwards, changes
It is passed through 200 milliliters of hydrogen reducings annealing nickel powders per minute 30 minutes, obtains porous nickel skeleton.
Secondly, the stage of reaction：By catalyst after 1000 degrees Celsius reduce 30 minutes, remain temperature-resistant, heat simultaneously
Set is warming up to 100 degrees Celsius by borine ammino-complex（Reaction source）After heating（Brought through air-flow to nickel powder）Start to grow six side's nitrogen
Change boron, it is 40 to 10 that now atmosphere, which is adjusted to argon gas with hydrogen ratio,（Milliliter is per minute）, growth time is 60 minutes.Terminate
After pluck heating mantle, open tube furnace, allow quartz ampoule to cool to room temperature with the furnace, obtain the hexagonal boron nitride powder with nickel skeleton
Body.
Again, sample post-processes：The sample grown is taken out to be put into 3 moles every liter of hydrochloric acid solution and carved
Erosion, suction filtration obtain boron nitride powder（Such as Fig. 1,2）.
Embodiment 2, preparation method are with embodiment 1, difference substantially：Using copper powder as catalyst, later stage etching
The solution of catalyst uses 1 mole every liter of ferric trichloride and 0.1 mole every liter of hydrochloric acid mixed solution, can obtain hexagonal boron nitride powder
Body.
2nd, the preparation of three-dimensional boron nitride
Embodiment 3, preparation method with embodiment 1, also make catalyst using nickel powder substantially.Difference is after being grown
Sample processing part：Before with 3 moles of every liter of salt acid etch nickel skeletons, sample is first dipped into polymethyl methacrylate（Matter
It is 4 percent to measure fraction）Methyl phenyl ethers anisole solution take out and dry after 10 minutes.After catalyst is etched, can must have macromolecule and protect
The three-dimensional boron nitride of sheath（Such as Fig. 3）, then remove polymethyl methacrylate with acetone solution and obtain three-dimensional boron nitride.
Embodiment 4, preparation method are with embodiment 1, difference substantially：Using copper powder as catalyst, later stage etching
Catalyst solution uses 1 mole every liter of ferric trichloride and 0.1 mole every liter of hydrochloric acid mixed solution.Before etching, first by sample
Product are dipped into polymethyl methacrylate（Mass fraction is 4 percent）Methyl phenyl ethers anisole solution take out and dry after 10 minutes.Etching
Afterwards, can must have the three-dimensional boron nitride of polymer protection layer, then remove polymethyl methacrylate with acetone solution and obtain three-dimensional
Boron nitride.（Such as Fig. 4）
Embodiment 5, for preparation method substantially with embodiment 1, difference is to add nickel powder (such as Fig. 5) in nickel foam to urge
Agent, and the sample processing part after growth also has difference：Before with 3 moles of every liter of salt acid etch nickel skeletons, first by sample
Product are dipped into polymethyl methacrylate（Mass fraction is 4 percent）Methyl phenyl ethers anisole solution take out and dry after 10 minutes.Etching
After catalyst, can must have the three-dimensional boron nitride of polymer protection layer, then remove polymethyl methacrylate with acetone solution and obtain
To three-dimensional boron nitride.
Claims (8)
1. the preparation method of hexagonal boron nitride powder and three-dimensional boron nitride, it is characterised in that comprise the following steps that：
The first step, catalyst pre-treatment：The catalyst is transition metal elemental powders and/or the chemical combination containing transition metal
Thing, catalyst is positioned in reaction vessel, or catalyst is filled in macrocellular foam metal form, then be placed in reaction and hold
In device；Reaction vessel vacuumizes or is passed through inert atmosphere protection, and is warming up to 500-1500 with 1-100 centigrade per minute speed
Container area residing for degrees Centigrade catalyst, reducing atmosphere is passed through, anneals -10 hours 1 minute, obtain porous metals and urge
Agent skeleton；
Second step, growing boron nitride：Catalyzer temperature-elevating in reaction vessel is placed on to 400-1200 degrees Celsius of reaction temperature, together
When by reaction source be that boron, nitrogen source are passed through catalyst area, growth time is -10 hours 30 seconds, and growth pressure is that 1 millitorr is -1 big
Air pressure；Then room temperature is cooled to the speed of 1-100 centigrade per minutes；Obtain the hexagonal boron nitride powder with catalyst backbone
Body；
3rd step, post processing：The hexagonal boron nitride powder with catalyst backbone grown is taken out, is put into solution and carves
Catalyst is lost, obtains hexagonal boron nitride powder；Or take out the boron nitride sample grown, protected using high molecular polymer
Shield, is then put into solution and etches catalyst, then removes high molecular polymer, then obtains three-dimensional boron nitride.
2. the preparation method of hexagonal boron nitride powder according to claim 1 and three-dimensional boron nitride, it is characterised in that described
Transition metal is selected from nickel, copper, cobalt, platinum, iron, gold, silver, rubidium；The transition metal elemental powders particle diameter is 0.1 micron -100
Micron；The compound containing transition metal includes transition metal oxide, transition metal salt or its hydrate.
3. the preparation method of hexagonal boron nitride powder according to claim 1 or 2 and three-dimensional boron nitride, it is characterised in that
The reaction source is the boron of solid phase, liquid phase or gas phase, nitrogen source, and the solid phase boron, nitrogen source are selected from boracic, nitrogen compound；Gas phase
Boron, nitrogen source include diborane, boron chloride, nitrogen, ammonia these boracics, nitrogen gas one or more of mixing；Liquid phase boron, nitrogen
Source is the alkane of ring boron nitrogen six；Or the boron, nitrogen source are to bring reaction vessel into by inert gas with the liquid of boracic, nitrogen to provide
Boron, nitrogen source.
4. the preparation method of hexagonal boron nitride powder according to claim 3 and three-dimensional boron nitride, it is characterised in that described
The aperture of macrocellular foam metal contained hole is 200 nanometers -500 microns, and macrocellular foam metal material is nickel foam, foamed iron, bubble
Foam copper or foam cobalt.
5. the preparation method of hexagonal boron nitride powder according to claim 1 and three-dimensional boron nitride, it is characterised in that described
Reaction vessel be quartz ampoule, alundum tube, vacuum chamber or other can be with the container of input and output gas.
6. the preparation method of hexagonal boron nitride powder according to claim 1 and three-dimensional boron nitride, it is characterised in that described
Inert atmosphere is one or more of mixed gas in nitrogen, argon gas；Reducing atmosphere is hydrogen or hydrogen and above-mentioned indifferent gas
The mixed gas of body.
7. the preparation method of hexagonal boron nitride powder according to claim 1 and three-dimensional boron nitride, it is characterised in that described
For etching the solution used in metallic catalyst skeleton to be the sulfuric acid for being 0.05-6 moles every liter containing concentration, hydrochloric acid, nitric acid, chlorination
Any one in iron, ferric nitrate, ammonium persulfate and Marble reagents, or the solution of two or more mixtures.
8. the preparation method of hexagonal boron nitride powder according to claim 1 and three-dimensional boron nitride, it is characterised in that in institute
State in etch processes, the high molecular polymer for protecting three-dimensional boron nitride is polymethyl methacrylate, polyethylene, gathered
One or several of styrene or polypropylene mix；The high molecular polymer that removes is forged using 100-1000 degrees Celsius of high temperature
Burn, or the one or more dissolving using organic solvent ketone, chlorohydrocarbon, aromatic hydrocarbon, halogenated hydrocarbons reagent.
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| CN105253874A (en) * | 2015-09-18 | 2016-01-20 | 复旦大学 | Method for preparing three-dimensional microporous graphene totally without participation of solution |
| CN105854919A (en) * | 2016-04-11 | 2016-08-17 | 广东工业大学 | Alpha-beta-unsaturated aldehyde low temperature hydrogenation catalyst, and preparation method and application thereof |
| US10781351B1 (en) * | 2016-05-25 | 2020-09-22 | Louisiana Tech Research Corporation | Hexagonal boron nitride thermal conductivity enhancing materials and method of making |
| CN106835074B (en) * | 2017-01-19 | 2018-12-25 | 杭州电子科技大学 | A kind of method of boron nitride etching |
| CN107973280A (en) * | 2017-11-17 | 2018-05-01 | 中国人民大学 | A kind of preparation method of multilayer hexagonal boron nitride |
| CN108441986B (en) * | 2018-03-07 | 2020-09-08 | 南方科技大学 | Macroporous boron nitride fiber and preparation method thereof |
| CN108384114A (en) * | 2018-03-08 | 2018-08-10 | 广东纳路纳米科技有限公司 | Polypropylene composite material and preparation method thereof |
| CN109638067A (en) * | 2018-12-19 | 2019-04-16 | 武汉华星光电半导体显示技术有限公司 | The production method and thin film transistor (TFT) of thin film transistor (TFT) |
| CN109704296B (en) * | 2019-02-22 | 2020-10-02 | 中国科学院苏州纳米技术与纳米仿生研究所 | Flexible boron nitride nanobelt aerogel and preparation method thereof |
| CN109650356A (en) * | 2019-02-27 | 2019-04-19 | 哈尔滨工业大学 | A method of boron nitride nanometer band is prepared using base metal catalysts |
| 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 |
| CN115368734B (en) * | 2022-08-29 | 2024-01-26 | 南昌大学共青城光氢储技术研究院 | Preparation method of high-heat-conductivity polyimide composite film material |
| CN116143083A (en) * | 2023-02-02 | 2023-05-23 | 浙江硼矩新材料科技有限公司 | Floating catalytic preparation method of boron nitride nanotube |
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| CN102398897B (en) * | 2011-11-07 | 2013-04-24 | 北京航空航天大学 | Method for preparing two-dimensional nano boron nitride with jet flow cavitation technology |
| CN103232027B (en) * | 2013-04-22 | 2015-05-20 | 南京航空航天大学 | Three-dimensional boron nitride foam and preparation method thereof |
| CN103213980B (en) * | 2013-05-13 | 2015-10-28 | 中国科学院苏州纳米技术与纳米仿生研究所 | The preparation method of three-dimensional grapheme or its compound system |
| CN103964403A (en) * | 2014-04-08 | 2014-08-06 | 南京航空航天大学 | Preparation method of three-dimensional porous hexagonal boron nitride |
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