CN105217583A - A kind of method preparing nano level high purity silicon nitride - Google Patents
A kind of method preparing nano level high purity silicon nitride Download PDFInfo
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- CN105217583A CN105217583A CN201510626117.5A CN201510626117A CN105217583A CN 105217583 A CN105217583 A CN 105217583A CN 201510626117 A CN201510626117 A CN 201510626117A CN 105217583 A CN105217583 A CN 105217583A
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Abstract
The present invention relates to a kind of method preparing nano level high purity silicon nitride, silicon tetrachloride and ammonia is used to be raw material, in the low temperature environment of-60 DEG C ~-35 DEG C, by being dissolved in the liquid phase reaction between silicon tetrachloride in organic hydrocarbon and ammonia, the precursor Si (NH) of synthesizing silicon nitride
2, purifying obtains Si (NH) afterwards
2powder, finally by precursor Si (NH)
2powder pyrolysis under 1000 ~ 1400 DEG C of environment prepares nano level high purity silicon nitride.Instant invention overcomes the shortcoming of silicon nitride particle slightly, at the bottom of purity prepared by existing method, prepared silicon nitride particle diameter is 50-200nm, the foreign matter contents such as Fe, Al, Ca are less than 100ppm, there is the remarkable advantage that particle diameter is little, purity is high, have broad application prospects at high-end silicon nitride arts.
Description
Technical field
The present invention relates to nano ceramic material technical field, more particularly, relate to a kind of method preparing nano level high purity silicon nitride silicon materials.
Background technology
Silicon nitride is a kind of important structural ceramic material.It is a kind of superhard material, and itself has oilness, and wear-resistant, is atomic crystal; Anti-oxidant during high temperature.And it can also resist thermal shock, be heated to more than 1000 DEG C in atmosphere, quick refrigeration sharply heats again, also can not be cracked.Have so excellent characteristic just because of silicon nitride ceramics, people usually utilize it to manufacture the mechanical components such as bearing, blade of gas turbine, mechanical seal ring, permanent mold.If manufacture the heating surface of engine parts with silicon nitride ceramics that is high temperature resistant and that do not readily conduct heat, not only can improve diesel engine quality, fuel saving, and can thermo-efficiency be improved.China and the U.S., Japan and other countries have developed this diesel engine all.
Along with the development of silicon nitride material toughening technology, the Application Areas of silicon nitride material is increasingly extensive, also constantly increases the granularity of silicon nitride and the requirement of purity.Although the preparation method of silicon nitride is developed so far existing many kinds, but because manufacturing cost is high, quality scale does not increase, efficiency is low, often be difficult to be suitable for scale operation, thus find a kind of both economical, the preparation method of dynamical industrialization scale operation silicon nitride powder, the preparation method especially producing nano level high purity silicon nitride is the problem being badly in need of at present solving.
The preparation method of current silicon nitride mainly contains silica flour direct nitridation method, carbothermic reduction titanium dioxide silicon process, self-propagating method, thermal decomposition method, sol-gel method, high temperature gas-phase reaction method, meteorological laser reaction method, plasma body meteoropathic reaction method etc.
This several method respectively has relative merits, for silica flour direct nitridation method:
Raw material: the silica flour that purity is higher and nitrogen or ammonia
Chemical equation: 3Si+2N
2→ Si
3n
4
3Si+4NH
3→Si
3N
4+6H
2
Technology point: this method requires that silica flour purity is at least more than 95%, and granularity is maximum is no more than 40 μm.The impurity <2% such as Fe, O, Ca in silica flour, Heating temperature≤1400 DEG C, and note silicon particle size and N
2purity; α-Si when 1200 ~ 1300 DEG C
3n
4content is high.The method is industrialization, although it is simple, there is reflection not easily complete, product purity is low, and particle is large, needs aftertreatment etc.The problem of other preparation methods also various degrees.
And silicon nitride particle diameter prepared by nano level is little, purity is high, has broad application prospects at high-end silicon nitride arts; The preparation method provided is based on chemical process principle, and preparation technology is simple, preparation process is continuous, operating process easily controls, and is convenient to realize low cost, serialization, large-scale production.
Summary of the invention
The object of the invention is to overcome the problem that silicon nitride particle diameter is thick, purity is low prepared by existing method, a kind of method preparing nano level high purity silicon nitride is provided, achieve the low cost of superfine high-purity silicon nitride, serialization preparation.
For reaching above object, the technical scheme that the present invention takes is:
Prepare a method for nano level high purity silicon nitride, use silicon tetrachloride and ammonia to be raw material, in the low temperature environment of-60 DEG C ~-35 DEG C, by being dissolved in the liquid phase reaction between silicon tetrachloride in organic hydrocarbon and ammonia, the precursor Si (NH) of synthesizing silicon nitride
2, purifying obtains Si (NH) afterwards
2powder, finally by precursor Si (NH)
2powder pyrolysis under 1000 ~ 1400 DEG C of environment prepares nano level high purity silicon nitride.
The speed of reaction that low temperature environment makes liquid phase synthesis react too fast is relaxed, and weakens the exothermic effect of building-up reactions, to Si (NH)
2the reunion of particle serves restraining effect with growing up.In addition, silicon tetrachloride and ammonia are not direct reaction, but react in organic hydrocarbon medium, and the organic hydrocarbon medium of liquid phase is also to Si (NH)
2the reunion of particle serves restraining effect with growing up.Above-mentioned two factors, make liquid phase synthesis obtain Si (NH)
2particle has splendid monodispersity, and the silicon nitride therefore obtained after pyrolysis is kept Nano Particle and good dispersiveness.
Concrete reaction is: with silicon tetrachloride and ammonia for raw material, with the alkane in organic hydrocarbon, alkene or aromatic hydrocarbon for reaction promoter, in the closed reactor of-60 DEG C ~-35 DEG C, 1 ± 0.2 normal atmosphere and anhydrous and oxygen-free, carries out following building-up reactions:
SiCl
4+6NH
3＝Si(NH)
2↓+4NH
4Cl
The mass ratio of above-mentioned reaction desired raw material and auxiliary agent controls in following scope:
Silicon tetrachloride: ammonia: organic hydrocarbon=50 ~ 150: 200 ~ 600: 100 ~ 300
Liquid ammonia is injected in reactor, at liquid ammonia surface sprinkling organic hydrocarbon, form organic hydrocarbon tectum, liquid ammonia is partly dissolved and reaches capacity in organic hydrocarbon tectum, at organic hydrocarbon tectum uppermost spray silicon tetrachloride, make it to react with the ammonia that dissolves in organic hydrocarbon, generate Si (NH)
2and be deposited in reactor bottom.By filtering, isolate Si (NH)
2, be then extraction agent with liquid ammonia, eccysis Si (NH)
2in residual ammonium chloride, obtain pure Si (NH)
2powder.
Afterwards, carry out pyrolytic reaction, the concrete steps of pyrolysis are as follows:
(1) atmosphere in pyrolysis oven is set as the vacuum state being better than 2Pa, or passes into 1 atmospheric shielding gas, shielding gas is one or more the combination in ammonia, nitrogen and argon gas;
(2) control at 1000 ~ 1400 DEG C by pyrolysis oven temperature, pyrolysis time controls at 10 ~ 120 minutes;
(3) Si (NH)
2under above-mentioned (1), (2) impose a condition, pyrolysis obtains target product silicon nitride.
Pyrolytic process reaction formula is as follows:
3Si(NH)
2＝Si
3N
4+2NH
3
Reacted liquid phase component is separated, by distillation, isolates pure ammonia, organic hydrocarbon and ammonium chloride; The ammonia that separation obtains and organic hydrocarbon are back to liquid phase synthesis process.
Compared with prior art, the present invention has the following advantages and beneficial effect:
Instant invention overcomes the shortcoming of silicon nitride particle slightly, at the bottom of purity prepared by existing method, prepared silicon nitride particle diameter is 50-200nm, the foreign matter contents such as Fe, Al, Ca are less than 100ppm, there is the remarkable advantage that particle diameter is little, purity is high, have broad application prospects at high-end silicon nitride arts.
The preparation method provided, based on chemical process principle, has the remarkable advantages such as preparation technology is simple, preparation process is continuous, operating process easily controls, is convenient to realize low cost, serialization, large-scale production.Ammonia, organic hydrocarbon and ammonium chloride is reclaimed out by filtering separation after building-up reactions, effectively cost-saving.
The speed of reaction that low temperature environment makes liquid phase synthesis react too fast is relaxed, and weakens the exothermic effect of building-up reactions, to Si (NH)
2the reunion of particle serves restraining effect with growing up.In addition, silicon tetrachloride and ammonia are not direct reaction, but react in organic hydrocarbon medium, and the organic hydrocarbon medium of liquid phase is also to Si (NH)
2the reunion of particle serves restraining effect with growing up.Above-mentioned two factors, make liquid phase synthesis obtain Si (NH)
2particle has splendid monodispersity, and the silicon nitride therefore obtained after pyrolysis is kept Nano Particle and good dispersiveness.
Embodiment
Embodiment 1
Raw material: silicon tetrachloride, ammonia; Reaction promoter: butylene;
Mass ratio: silicon tetrachloride: ammonia: butylene=50: 200: 100
Synthesis temperature :-60 DEG C;
Reactor pressure: 0.8 normal atmosphere;
Pyrolysis temperature: 1000 DEG C;
Pyrolysis atmosphere: ammonia;
Pyrolysis time: 10 minutes
Liquid ammonia is injected in reactor, at liquid ammonia surface sprinkling organic hydrocarbon, form organic hydrocarbon tectum, liquid ammonia is partly dissolved and reaches capacity in organic hydrocarbon tectum, at organic hydrocarbon tectum uppermost spray silicon tetrachloride, make it to react with the ammonia that dissolves in organic hydrocarbon, generate Si (NH)
2and be deposited in reactor bottom.By filtering, isolate Si (NH)
2, be then extraction agent with liquid ammonia, eccysis Si (NH)
2in residual ammonium chloride, obtain pure Si (NH)
2powder; Afterwards, carry out pyrolytic reaction, obtain target product silicon nitride.
Particle size: 50nm
Fe, Al, Ca impurity adds up to: < 100ppm
Embodiment 2
Raw material: silicon tetrachloride, ammonia; Reaction promoter: hexane;
Mass ratio: silicon tetrachloride: ammonia: hexane=150: 600: 300
Synthesis temperature :-35 DEG C;
Reactor pressure: 1.2 normal atmosphere;
Pyrolysis temperature: 1400 DEG C;
Pyrolysis atmosphere: nitrogen;
Pyrolysis time: 120 minutes
Product median size: ~ 200nm
Fe, Al, Ca impurity adds up to: < 100ppm
Preparation method is identical with embodiment 1.
Embodiment 3
Raw material: silicon tetrachloride, ammonia; Reaction promoter: toluene;
Mass ratio: silicon tetrachloride: ammonia: toluene=100: 400: 150
Synthesis temperature :-50 DEG C;
Reactor pressure: 1 normal atmosphere;
Pyrolysis temperature: 1300 DEG C;
Pyrolysis atmosphere: argon gas;
Pyrolysis time: 100 minutes
Product median size: ~ 160nm
Fe, Al, Ca impurity adds up to: < 100ppm
Preparation method is identical with embodiment 1.
Embodiment 4
Raw material: silicon tetrachloride, ammonia; Reaction promoter: normal hexane;
Mass ratio: silicon tetrachloride: ammonia: toluene=80: 400: 200
Synthesis temperature :-48 DEG C;
Reactor pressure: 1 normal atmosphere;
Pyrolysis temperature: 1350 DEG C;
Pyrolysis atmosphere: ammonia;
Pyrolysis time: 60 minutes
Product median size: ~ 150nm
Fe, Al, Ca impurity adds up to: < 100ppm
Preparation method is identical with embodiment 1.
Embodiment 5
Raw material: silicon tetrachloride, ammonia; Reaction promoter: iso-pentane;
Mass ratio: silicon tetrachloride: ammonia: toluene=100: 450: 200
Synthesis temperature :-45 DEG C;
Reactor pressure: 1 normal atmosphere;
Pyrolysis temperature: 1200 DEG C;
Pyrolysis atmosphere: ammonia;
Pyrolysis time: 90 minutes
Product median size: ~ 130nm
Fe, Al, Ca impurity adds up to: < 100ppm
Preparation method is identical with embodiment 1.
Above-mentioned embodiment is the embodiment of the best of the present invention; but embodiment of the present invention are not by the restriction of above-mentioned embodiment; other any without prejudice under the condition of the principle of the invention; the embodiment that can be produced by the form changing parameter, is all contained within protection scope of the present invention.
Claims (10)
1. prepare a method for nano level high purity silicon nitride, it is characterized in that: use silicon tetrachloride and ammonia to be raw material, under-60 DEG C ~-35 DEG C environment, synthesis obtains Si (NH)
2, purifying obtains Si (NH) afterwards
2powder, finally by Si (NH)
2powder pyrolysis under 1000 ~ 1400 DEG C of environment.
2. the method preparing nano level high purity silicon nitride according to claim 1, is characterized in that: use organic hydrocarbon as reaction promoter during synthesis.
3. the method preparing nano level high purity silicon nitride according to claim 2, is characterized in that: described organic hydrocarbon is alkane, alkene or aromatic hydrocarbon.
4. the method preparing nano level high purity silicon nitride according to claim 1,2 or 3, is characterized in that: pyrolysis carries out in vacuum or protective atmosphere.
5. the method preparing nano level high purity silicon nitride according to any one of claim 1,2 or 3, is characterized in that: synthesis carries out in closed reactor, anhydrous and oxygen-free in reactor, and pressure is 1 ± 0.2 normal atmosphere.
6. the method preparing nano level high purity silicon nitride according to claim 5, is characterized in that: during synthesis, the mass ratio of raw material and auxiliary agent is: silicon tetrachloride: ammonia: organic hydrocarbon=50 ~ 150: 200 ~ 600: 100 ~ 300.
7. the method preparing nano level high purity silicon nitride according to claim 1, is characterized in that: the concrete steps of synthesis are as follows:
(1) in reactor, liquid ammonia is injected;
(2) at liquid ammonia surface sprinkling organic hydrocarbon, organic hydrocarbon tectum is formed;
(3) liquid ammonia is partly dissolved and reaches capacity in organic hydrocarbon tectum;
(4) at organic hydrocarbon tectum uppermost spray silicon tetrachloride, make it to react with the ammonia that dissolves in organic hydrocarbon, generate Si (NH)
2and be deposited in reactor bottom.
8. the method preparing nano level high purity silicon nitride according to claim 1 or 7, is characterized in that: the concrete steps of pyrolysis are as follows:
(1) atmosphere in pyrolysis oven is set as the vacuum state being better than 2Pa, or passes into 1 atmospheric shielding gas, shielding gas is one or more the combination in ammonia, nitrogen and argon gas;
(2) control at 1000 ~ 1400 DEG C by pyrolysis oven temperature, pyrolysis time controls at 10 ~ 120 minutes;
(3) Si (NH)
2under above-mentioned (1), (2) impose a condition, pyrolysis obtains target product silicon nitride.
9. the method preparing nano level high purity silicon nitride according to claim 1 or 7, is characterized in that: the concrete steps of purifying are;
By filtering, isolate Si (NH)
2, be then extraction agent with liquid ammonia, eccysis Si (NH)
2in residual ammonium chloride, obtain pure Si (NH)
2powder.
10. according to the method preparing nano level high purity silicon nitride according to claim 8, it is characterized in that: the liquid phase after purifying, by distillation, isolates pure ammonia, organic hydrocarbon and ammonium chloride, reclaim.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107557866A (en) * | 2017-08-28 | 2018-01-09 | 青岛桥海陶瓷新材料科技有限公司 | The preparation method of silicon nitride crystal whisker |
| CN108585876A (en) * | 2018-03-26 | 2018-09-28 | 青岛桥海陶瓷新材料科技有限公司 | The preparation method of titanium nitride nanopower |
| CN110272283A (en) * | 2018-03-14 | 2019-09-24 | 江苏中能硅业科技发展有限公司 | A kind of production method of silicon nitride powder |
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| JPS60195099A (en) * | 1984-03-13 | 1985-10-03 | Kobe Steel Ltd | Production of silicon nitride whisker |
| US4795622A (en) * | 1986-04-24 | 1989-01-03 | Toa Nenryo Kogyo Kabushiki Kaisha | Method for producing silicon-imide |
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| US3959446A (en) * | 1974-03-01 | 1976-05-25 | The United States Of America As Represented By The Secretary Of The Air Force | Synthesis of high purity, alpha phase silicon nitride powder |
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| US4795622A (en) * | 1986-04-24 | 1989-01-03 | Toa Nenryo Kogyo Kabushiki Kaisha | Method for producing silicon-imide |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110272283A (en) * | 2018-03-14 | 2019-09-24 | 江苏中能硅业科技发展有限公司 | A kind of production method of silicon nitride powder |
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