CN107557866A - The preparation method of silicon nitride crystal whisker - Google Patents
The preparation method of silicon nitride crystal whisker Download PDFInfo
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- CN107557866A CN107557866A CN201710750757.6A CN201710750757A CN107557866A CN 107557866 A CN107557866 A CN 107557866A CN 201710750757 A CN201710750757 A CN 201710750757A CN 107557866 A CN107557866 A CN 107557866A
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- silicon nitride
- organic solvent
- nitride crystal
- crystal whisker
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Abstract
The present invention proposes a kind of preparation method of silicon nitride crystal whisker, comprises the following steps：1) under the conditions of 50 DEG C~50 DEG C, organic solvent is mixed successively with liquefied ammonia, forms organic solvent in lower liquefied ammonia in upper two phase liquid；2) dichlorosilane is injected into organic solvent layer, stirs and dichlorosilane is diffused into organic solvent liquefied ammonia interface, carried out ammonolysis, be filtrated to get ammonolysis predecessor；3) in the mixed gas of inert gas, ammonia or both, ammonolysis predecessor is pyrolyzed, pyrolysis temperature is 1300~1500 DEG C, you can obtains silicon nitride crystal whisker；Wherein, the organic solvent is the organic solvent that can dissolve dichlorosilane.The silicon nitride crystal whisker that the preparation method obtains has the advantages that whisker purity is high, morphological consistency is good, product quality is stable.
Description
Technical field
The invention belongs to silicon nitride preparing technical field, and in particular to a kind of preparation method of silicon nitride crystal whisker.
Background technology
Whisker is a kind of monocrystal of the high intensity beard shape synthesized under manual control condition, and its crystal structure is completeer
Whole, internal flaw is few, and its intensity and modulus is close to ideal crystal.Therefore, whisker length as reinforcing component be added to Metal Substrate,
Ceramic base and it is polymer-based in play enhancing, toughening effect.
Silicon nitride crystal whisker has high temperature resistant, high intensity, high-modulus, low bulk and good chemical stability, is metal, pottery
The important reinforcing component of porcelain, high polymer material.Existing silicon nitride crystal whisker preparation method mainly includes solid phase method and vapor phase method two
Major class.Typical solid phase method is mainly nitriding, self- propagating method, carbothermic method, and silicon nitride crystal whisker prepared by this kind of method produces
Rate is low, with substantial amounts of silicon nitride particle in whisker.Typical vapor phase method is mainly chemical vapour deposition technique, silicon halide vapor phase ammonia
Solution, this kind of preparation method are related to transmission and the course of reaction of complexity, and equipment is complicated, technology stability is poor, it is difficult to volume production.
The content of the invention
The present invention proposes a kind of preparation method of silicon nitride crystal whisker, and the silicon nitride crystal whisker that the preparation method obtains has whisker
The advantages that purity is high, morphological consistency is good, product quality is stable.
The technical proposal of the invention is realized in this way：
A kind of preparation method of silicon nitride crystal whisker, comprises the following steps：
1) under the conditions of -50 DEG C~50 DEG C, organic solvent is mixed successively with liquefied ammonia, organic solvent is formed and exists in lower liquefied ammonia
On two phase liquid；
2) dichlorosilane is injected into organic solvent layer, stirs and dichlorosilane is diffused into organic solvent-liquefied ammonia interface, carried out
Ammonolysis, it is filtrated to get ammonolysis predecessor；
3) in the mixed gas of inert gas, ammonia or both, ammonolysis predecessor is pyrolyzed, pyrolysis temperature is
1300~1500 DEG C, you can obtain silicon nitride crystal whisker；
Wherein, the organic solvent is the organic solvent that can dissolve dichlorosilane.
Preferably, the organic solvent is toluene, n-hexane or dichloromethane, preferably dichloromethane.
Preferably, the ammonolysis time of the step 2) is 30~180min；The inert gas is nitrogen, helium, neon
Or argon gas, preferably nitrogen.
Preferably, the pyrolysis time of the step 3) is the mixed of 30~240min, the inert gas, ammonia or both
The pressure for closing gas is 0.1~0.5MPa.
Preferably, 0.1~5 micron of the diameter of the silicon nitride crystal whisker of acquisition, 10~3000 microns of length.
It is based on considered below that the present invention, which uses dichlorosilane to carry out ammonolysis to obtain stable silicon nitride crystal whisker for raw material,：
Dichlorosilane has bilateral symmetry, occurs to have generated symmetrical " handing in hand " type of amino during ammonolysis reaction
When being pyrolyzed polycondensation occurs for ammonolysis presoma, the presoma, and the amino in adjacent predecessor forms link, so as to tend to produce
The whisker structure of long fibre shape.In addition, active nitrogen gas environment during pyrolysis is one and contributes to the heat transfer of nitride growth, mass transfer
Environment, it helps the link of amino and the growth for eventually prompting silicon nitride fiber.
Beneficial effects of the present invention：
The dichlorosilane of the present invention is sufficiently separated impurity C, Cl, ensure that crystalline substance in the reaction controlling process at liquefied ammonia interface
The high-purity of palpus.Controllable pyrolysis of the ammonolysis presoma under inert gas/ammonia atmosphere, the ammonolysis in presoma occurs symmetrical
Pyrolysis crosslinking, ensure that the morphological consistency of silicon nitride crystal whisker.
Brief description of the drawings
In order to illustrate more clearly about the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
There is the required accompanying drawing used in technology description to be briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the transmission electron microscope picture of the silicon nitride crystal whisker of the embodiment of the present invention 3；
Fig. 2 is the XRD of the embodiment of the present invention 3.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
Embodiment 1
The preparation method of silicon nitride crystal whisker, comprises the following steps：
1) 2000 grams of toluene and 3000 grams of liquid ammonias are implanted sequentially reactor, toluene is formed at a temperature of 50 DEG C and is existed
Under, liquefied ammonia is in upper two phase liquid；
2) 500 grams of dichlorosilanes are injected into toluene layer, dichloromethane is diffused into toluene-liquefied ammonia interface by stirring, sent out
Raw ammonolysis reaction generation ammonolysis predecessor, the process maintain 100min；
3) ammonolysis predecessor is filtered, be then pyrolyzed in pressure 0.1MPa nitrogen, 1450 DEG C of pyrolysis temperature, during insulation
Between 180min, generate silicon nitride crystal whisker；
0.3 micron of silicon nitride crystal whisker average diameter in the present embodiment, 1500 microns of average length, impurity C content
0.15%, Cl content 30ppm.
Embodiment 2
The preparation method of silicon nitride crystal whisker, comprises the following steps：
1) 1000 grams of n-hexanes and 5000 grams of liquid ammonias are implanted sequentially reactor, toluene is formed at a temperature of 0 DEG C and is existed
Under, liquefied ammonia is in upper two phase liquid；
2) 400 grams of dichlorosilanes are injected into toluene layer, dichloromethane is diffused into toluene-liquefied ammonia interface by stirring, sent out
Raw ammonolysis reaction generation ammonolysis predecessor, the process maintain 180min；
3) ammonolysis predecessor is filtered, be then pyrolyzed in pressure 0.2MPa nitrogen, 1400 DEG C of pyrolysis temperature, during insulation
Between 200min, generate silicon nitride crystal whisker；
0.2 micron of silicon nitride crystal whisker average diameter in the present embodiment, 800 microns of average length, impurity C content
0.12%, Cl content 36ppm.
Embodiment 3
The preparation method of silicon nitride crystal whisker, comprises the following steps：
1) 800 grams of dichloromethane and 4000 grams of liquid ammonias are implanted sequentially reactor, toluene is formed at a temperature of -50 DEG C
Under, liquefied ammonia is in upper two phase liquid；
2) 300 grams of dichlorosilanes are injected into toluene layer, dichloromethane is diffused into toluene-liquefied ammonia interface by stirring, sent out
Raw ammonolysis reaction generation ammonolysis predecessor, the process maintain 180min；
3) ammonolysis predecessor is filtered, then nitrogen 0.45MPa, ammonia 0.05MPa mixed gas in be pyrolyzed, be pyrolyzed
1450 DEG C, soaking time 240min of temperature, generate silicon nitride crystal whisker；
3 microns of silicon nitride crystal whisker average diameter in the present embodiment, 3000 microns of average length, impurity C content 0.11%,
Cl contents 22ppm.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
God any modification, equivalent substitution and improvements made etc., should be included in the scope of the protection with principle.
Claims (6)
1. a kind of preparation method of silicon nitride crystal whisker, it is characterised in that comprise the following steps：
1) under the conditions of -50 DEG C~50 DEG C, organic solvent is mixed successively with liquefied ammonia, forms organic solvent in lower liquefied ammonia upper
Two phase liquid；
2) dichlorosilane is injected into organic solvent layer, stirs and dichlorosilane is diffused into organic solvent-liquefied ammonia interface, carry out ammonia
Solution, is filtrated to get ammonolysis predecessor；
3) in the mixed gas of inert gas, ammonia or both, ammonolysis predecessor is pyrolyzed, pyrolysis temperature 1300
~1500 DEG C, you can obtain silicon nitride crystal whisker；
Wherein, the organic solvent is the organic solvent that can dissolve dichlorosilane.
2. the preparation method of silicon nitride crystal whisker according to claim 1, it is characterised in that the organic solvent be toluene,
N-hexane or dichloromethane.
3. the preparation method of silicon nitride crystal whisker according to claim 1, it is characterised in that the ammonolysis time of the step 2)
For 30~180min.
4. the preparation method of silicon nitride crystal whisker according to claim 1, it is characterised in that the inert gas be nitrogen,
Helium, neon or argon gas.
5. the preparation method of silicon nitride crystal whisker according to claim 1, it is characterised in that the pyrolysis time of the step 3)
For 30~240min, the pressure of the mixed gas of the inert gas, ammonia or both is 0.1~0.5MPa.
6. the preparation method of the silicon nitride crystal whisker according to claim 1 to 5 any one, it is characterised in that the nitrogen of acquisition
0.1~5 micron of the diameter of SiClx whisker, 10~3000 microns of length.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113148966A (en) * | 2021-04-20 | 2021-07-23 | 安徽工业大学 | Method for preparing high-purity silicon nitride powder by ammonolysis method |
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| CN1092825A (en) * | 1993-12-17 | 1994-09-28 | 清华大学 | The preparation of nondefective silicon nitride crystal whisker |
| CN101318637A (en) * | 2008-07-15 | 2008-12-10 | 北京科技大学 | Process for producing nano-silicon nitride ceramics powder |
| CN104499053A (en) * | 2014-12-17 | 2015-04-08 | 青岛桥海陶瓷新材料科技有限公司 | Method for preparing silicon nitride crystal whisker |
| CN105129750A (en) * | 2015-08-19 | 2015-12-09 | 山东国瓷功能材料股份有限公司 | Method for preparing silicon nitride powder through atomization reaction process |
| CN105217583A (en) * | 2015-09-28 | 2016-01-06 | 韩召 | A kind of method preparing nano level high purity silicon nitride |
| CN105253864A (en) * | 2015-11-13 | 2016-01-20 | 宁波盛优科技服务有限公司 | Silicon nitride powder preparation method |
| CN106672922A (en) * | 2015-11-11 | 2017-05-17 | 新特能源股份有限公司 | System for producing silicon nitride |
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2017
- 2017-08-28 CN CN201710750757.6A patent/CN107557866A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1040559A (en) * | 1989-08-24 | 1990-03-21 | 国家建筑材料工业局山东工业陶瓷研究设计院 | The manufacture method of alpha-silicon nitride powders and equipment |
| CN1092825A (en) * | 1993-12-17 | 1994-09-28 | 清华大学 | The preparation of nondefective silicon nitride crystal whisker |
| CN101318637A (en) * | 2008-07-15 | 2008-12-10 | 北京科技大学 | Process for producing nano-silicon nitride ceramics powder |
| CN104499053A (en) * | 2014-12-17 | 2015-04-08 | 青岛桥海陶瓷新材料科技有限公司 | Method for preparing silicon nitride crystal whisker |
| CN105129750A (en) * | 2015-08-19 | 2015-12-09 | 山东国瓷功能材料股份有限公司 | Method for preparing silicon nitride powder through atomization reaction process |
| CN105217583A (en) * | 2015-09-28 | 2016-01-06 | 韩召 | A kind of method preparing nano level high purity silicon nitride |
| CN106672922A (en) * | 2015-11-11 | 2017-05-17 | 新特能源股份有限公司 | System for producing silicon nitride |
| CN105253864A (en) * | 2015-11-13 | 2016-01-20 | 宁波盛优科技服务有限公司 | Silicon nitride powder preparation method |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113148966A (en) * | 2021-04-20 | 2021-07-23 | 安徽工业大学 | Method for preparing high-purity silicon nitride powder by ammonolysis method |
| CN113148966B (en) * | 2021-04-20 | 2022-04-29 | 安徽工业大学 | Method for preparing high-purity silicon nitride powder by ammonolysis method |
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Application publication date: 20180109 |