CN104261360A - Silicon nitride powder based on catalytic nitridation and preparation method thereof - Google Patents
Silicon nitride powder based on catalytic nitridation and preparation method thereof Download PDFInfo
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- 229910052581 Si3N4 Inorganic materials 0.000 title claims abstract description 58
- 239000000843 powder Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 31
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 title abstract description 15
- 230000003197 catalytic effect Effects 0.000 title abstract 4
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000012298 atmosphere Substances 0.000 claims abstract description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 9
- 238000001291 vacuum drying Methods 0.000 claims abstract description 9
- 239000000725 suspension Substances 0.000 claims abstract 4
- 239000012153 distilled water Substances 0.000 claims abstract 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract 3
- 238000006555 catalytic reaction Methods 0.000 claims description 37
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 16
- 239000011812 mixed powder Substances 0.000 claims description 16
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical group [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- 238000013019 agitation Methods 0.000 claims description 8
- 235000013312 flour Nutrition 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 8
- 239000000377 silicon dioxide Substances 0.000 claims description 8
- 238000000967 suction filtration Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 5
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 5
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 5
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 5
- 238000001556 precipitation Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 25
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 6
- 239000011863 silicon-based powder Substances 0.000 abstract description 4
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 0.000 abstract 2
- 239000000203 mixture Substances 0.000 abstract 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 1
- 150000001844 chromium Chemical class 0.000 abstract 1
- 239000002270 dispersing agent Substances 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 238000001132 ultrasonic dispersion Methods 0.000 abstract 1
- 238000003828 vacuum filtration Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 239000000919 ceramic Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- -1 silicon powder nitride Chemical class 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 2
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 2
- 150000001868 cobalt Chemical class 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000010574 gas phase reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 238000006396 nitration reaction Methods 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005979 thermal decomposition reaction Methods 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000016784 immunoglobulin production Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000021715 photosynthesis, light harvesting Effects 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000001149 thermolysis Methods 0.000 description 1
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Abstract
The invention relates to a silicon nitride powder based on catalytic nitridation and a preparation method thereof. The technical scheme is as follows: the method comprises the following steps: mixing a dispersing agent, silicon powder and distilled water in a mass ratio of 1:200:(10000-16000), stirring, and carrying out ultrasonic dispersion to obtain a suspension; adding 0.88 mol/L water-soluble chromium salt into the suspension according to the Si:Cr2O3 mass ratio of 1:(0.005-0.050) to obtain a mixed solution; adding a precipitant into the mixed solution until the pH value is 7.5-8.5, and stirring for 0.5-1 hour; carrying out vacuum filtration and vacuum drying to obtain a powder mixture; and putting the powder mixture into a tubular atmosphere furnace, heating to 1250-1400 DEG C in a nitrogen atmosphere, and keeping the temperature for 2-8 hours to obtain the silicon nitride powder based on catalytic nitridation. The method has the characteristics of low synthesis temperature, short period, simple technique and high yield, and is easy to control. The silicon nitride powder based on catalytic nitridation has the advantages of high purity and small particle size, and is partially crystal whiskers.
Description
Technical field
The invention belongs to nitride powder technical field.Be specifically related to a kind of beta-silicon nitride powder based on catalysis nitrogenize and preparation method thereof.
Background technology
Silicon nitride ceramics is as a kind of high-temperature structural ceramics, there is the excellent specific properties such as intensity is high, hardness is large, high temperature creep is little, heat-resistant knocking stability is good, wear-resisting, corrosion-resistant, chemical stability is good, be widely used in the fields such as machinery, chemical industry, thermal technology and aerospace.Beta-silicon nitride powder is the basis of preparation high-performance silicon nitride ceramics, and the preparation of preparation and property to silicon nitride ceramics of beta-silicon nitride powder has very important effect.
At present, the preparation method of beta-silicon nitride powder mainly contains: carbothermic reduction titanium dioxide silicon process, self-propagating method, thermal decomposition method, gas-phase reaction method and silica flour direct nitridation method etc.
SiO in carbothermic reduction titanium dioxide silicon process
2be difficult to be completely reduced nitrogenize, in reaction, easily generate SiC, and temperature of reaction high (1400 ~ 1550 DEG C) and energy consumption large.Self-propagating legal system is high for the purity of beta-silicon nitride powder, and has energy-conservation and timesaving advantage in preparation process; But the method is higher to equipment requirements, production cost is expensive and be difficult to heavy industrialization.The beta-silicon nitride powder purity that thermal decomposition method obtains is high, particle diameter is little and sintering character good, but cost is high and energy consumption large (1400 ~ 1600 DEG C of thermolysiss), and complex process, large-scale industrialization application is restricted.Although gas-phase reaction method can obtain high-purity silicon nitride powder at short notice, cost is high, is not easy to suitability for industrialized production.
Silica flour direct nitridation method is the preparation method of most widely used beta-silicon nitride powder, and the method has that technique is simple, equipment requirements is low and the advantage such as advantage of lower cost.But also there is the problems such as the long and energy dissipation of nitriding temperature high (>=1400 DEG C), nitrogenize cycle is serious, and the pattern of silicon nitride difficulty controls, and can not obtain crystal whisker-shaped silicon nitride.In recent years, be the beta-silicon nitride powder of obtained super quality and competitive price, researchist adds catalyzer such as iron powder, iron(ic) chloride, cobalt salt etc. in silicon powder nitride process, and (Liu Song Zhe, direct nitridation method prepares Si
3n
4powder process research [J]. Rare Metals Materials and engineering. 2008,37 (1): 378-381; CN 101983947A; CN103496679A), although the method improves nitriding rate, and can difform beta-silicon nitride powder be obtained, iron add the high-temperature behavior reducing beta-silicon nitride powder, and cobalt salt price is relatively high, is difficult to suitability for industrialized production.
In a word, existing silicon nitride powder Antibody Production Techniques all comes with some shortcomings: cost is high, and temperature of reaction is high, the nitrogenize cycle is long, and purity is low, complex technical process, wayward, powder is not crystal whisker-shaped etc., and the application and the industrialization that significantly limit beta-silicon nitride powder are produced.
Summary of the invention
The present invention is intended to overcome prior art defect, and object is to provide that a kind of temperature of reaction is low, cost is low, the nitrogenize cycle is short, technological process is simple, be easy to control and the preparation method of the beta-silicon nitride powder based on catalysis nitrogenize that productive rate is high; The beta-silicon nitride powder purity based on catalysis nitrogenize prepared by the method is high, diameter of particle is little and part is crystal whisker-shaped.
For achieving the above object, the preparation process of the technical solution used in the present invention is:
Step one, be 1 ︰ 200 ︰ (10000 ~ 16000) by the mass ratio of Fen San Ji ︰ Gui Fen ︰ distilled water, dispersion agent, silica flour and distilled water mixed, stirs 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension.
Step 2, in described suspension, add the water-soluble chromic salts that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of water-soluble chromic salts is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.005 ~ 0.050).
Step 3, under agitation, in described mixed solution, add precipitation agent to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder.
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 2 ~ 8 DEG C/min, are warming up to 1250 ~ 1400 DEG C, insulation 2 ~ 8h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
Si content >=95wt% in described silica flour, particle diameter≤88 μm.
Described dispersion agent is the one in polyvinyl alcohol, Sodium dodecylbenzene sulfonate and polyvinylpyrrolidone, and the purity of the purity of polyvinyl alcohol, the purity of Sodium dodecylbenzene sulfonate and polyvinylpyrrolidone is analytical pure or is technical pure.
Described water-soluble chromic salts is chromium chloride or is chromium nitrate; The purity of chromium chloride and the purity of chromium nitrate are analytical pure or are technical pure.
Described precipitation agent is the one in urea, ammoniacal liquor and hydrazine hydrate, and the purity of the purity of urea, the purity of ammoniacal liquor and hydrazine hydrate is analytical pure or is technical pure.
Owing to adopting technique scheme, the present invention compared with prior art has following positively effect:
1, the present invention adopts chromic oxide nano-powder as catalyzer, catalysis silicon powder nitride.Silica flour at 1250 ~ 1400 DEG C by complete nitrogenize.Therefore productive rate of the present invention is high, synthesis temperature is low and the nitrogenize cycle is short.
2, the present invention utilizes nano-powder to control whisker growth, and gained is little based on the silicon nitride particle particle diameter of catalysis nitrogenize, and the diameter of whisker is 120 ~ 180nm, and length-to-diameter ratio is 15 ~ 25; The whisker of synthesis is silicon nitride.
3, the present invention only introduces the nanocatalyst of trace in reaction process, and without other impurity, product purity is high.
4, raw material sources of the present invention are extensive and cheap, and production cost is low, have very large industrialization prospect.
Therefore, the present invention has that Nitration synthesis temperature is low, cost is low, the nitrogenize cycle is short, synthesis technique is simple, be easy to the feature that controls and productive rate is high; The prepared beta-silicon nitride powder purity based on catalysis nitrogenize is high, particle diameter is little and part is crystal whisker-shaped, and industrialization prospect is large.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of a kind of beta-silicon nitride powder based on catalysis nitrogenize prepared by the present invention;
Fig. 2 is that the SEM based on the beta-silicon nitride powder of catalysis nitrogenize shown in Fig. 1 schemes.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described, the restriction not to its protection domain.
For avoiding repetition, first by as follows for the raw material Unify legislation involved by this embodiment, repeat no more in embodiment:
Si content >=95wt% in described silica flour, particle diameter≤88 μm.
The purity of described polyvinyl alcohol, Sodium dodecylbenzene sulfonate and polyvinylpyrrolidone is analytical pure or is technical pure.
The purity of described chromium chloride and the purity of chromium nitrate are analytical pure or are technical pure.
The purity of the purity of described urea, the purity of ammoniacal liquor and hydrazine hydrate is analytical pure or is technical pure.
embodiment 1
A kind of beta-silicon nitride powder based on catalysis nitrogenize and preparation method thereof.The step of described preparation method is:
Step one, be 1 ︰ 200 ︰ (10000 ~ 12000) by the mass ratio of Ju Yi Xi Chun ︰ Gui Fen ︰ distilled water, polyvinyl alcohol, silica flour and distilled water mixed, stirs 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension.
Step 2, in described suspension, add the chromium nitrate that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of chromium nitrate is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.005 ~ 0.020).
Step 3, under agitation, in described mixed solution, add urea to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder.
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 2 ~ 4 DEG C/min, are warming up to 1250 ~ 1300 DEG C, insulation 2 ~ 5h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
embodiment 2
A kind of beta-silicon nitride powder based on catalysis nitrogenize and preparation method thereof.The step of described preparation method is:
Step one, be 1 ︰ 200 ︰ (14000 ~ 16000) by the mass ratio of Shi dialkyl benzene sulfonic acids Na ︰ Gui Fen ︰ distilled water, Sodium dodecylbenzene sulfonate, silica flour and distilled water are mixed, stir 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension.
Step 2, in described suspension, add the chromium chloride that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of chromium chloride is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.025 ~ 0.040).
Step 3, under agitation, in described mixed solution, add ammoniacal liquor to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder.
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 2 ~ 4 DEG C/min, are warming up to 1350 ~ 1400 DEG C, insulation 2 ~ 5h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
embodiment 3
A kind of beta-silicon nitride powder based on catalysis nitrogenize and preparation method thereof.The step of described preparation method is:
Step one, be 1 ︰ 200 ︰ (10000 ~ 12000) by the mass ratio of Ju Yi Xi Chun ︰ Gui Fen ︰ distilled water, polyvinyl alcohol, silica flour and distilled water mixed, stirs 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension.
Step 2, in described suspension, add the chromium chloride that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of chromium chloride is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.010 ~ 0.025).
Step 3, under agitation, in described mixed solution, add hydrazine hydrate to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder.
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 4 ~ 6 DEG C/min, are warming up to 1300 ~ 1350 DEG C, insulation 3 ~ 7h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
embodiment 4
A kind of beta-silicon nitride powder based on catalysis nitrogenize and preparation method thereof.The step of described preparation method is:
Step one, be 1 ︰ 200 ︰ (12000 ~ 14000) by the mass ratio of Ju Yi Xi Bi Ka Wan Tong ︰ Gui Fen ︰ distilled water, polyvinylpyrrolidone, silica flour and distilled water mixed, stirs 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension.
Step 2, in described suspension, add the chromium nitrate that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of chromium nitrate is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.020 ~ 0.035).
Step 3, under agitation, in described mixed solution, add urea to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder.
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 4 ~ 6 DEG C/min, are warming up to 1250 ~ 1300 DEG C, insulation 3 ~ 7h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
embodiment 5
A kind of beta-silicon nitride powder based on catalysis nitrogenize and preparation method thereof.The step of described preparation method is:
Step one, be 1 ︰ 200 ︰ (12000 ~ 14000) by the mass ratio of Shi dialkyl benzene sulfonic acids Na ︰ Gui Fen ︰ distilled water, Sodium dodecylbenzene sulfonate, silica flour and distilled water are mixed, stir 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension.
Step 2, in described suspension, add the chromium nitrate that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of chromium nitrate is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.035 ~ 0.050).
Step 3, under agitation, in described mixed solution, add hydrazine hydrate to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder.
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 6 ~ 8 DEG C/min, are warming up to 1350 ~ 1400 DEG C, insulation 4 ~ 8h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
embodiment 6
A kind of beta-silicon nitride powder based on catalysis nitrogenize and preparation method thereof.The step of described preparation method is:
Step one, be 1 ︰ 200 ︰ (14000 ~ 16000) by the mass ratio of Ju Yi Xi Bi Ka Wan Tong ︰ Gui Fen ︰ distilled water, polyvinylpyrrolidone, silica flour and distilled water mixed, stirs 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension.
Step 2, in described suspension, add the chromium chloride that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of chromium chloride is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.035 ~ 0.050).
Step 3, under agitation, in described mixed solution, add ammoniacal liquor to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder.
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 6 ~ 8 DEG C/min, are warming up to 1300 ~ 1350 DEG C, insulation 4 ~ 8h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
This embodiment compared with prior art has following positively effect and outstanding feature:
1, this embodiment adopts chromic oxide nano particle as catalyzer, catalysis silicon powder nitride.The XRD figure spectrum of a kind of beta-silicon nitride powder based on catalysis nitrogenize of Fig. 1 prepared by embodiment 1, only has the diffraction peak of silicon nitride, silica flour nitrogenize completely is at such a temperature described in this XRD figure spectrum.Result shows that this embodiment productive rate is high, synthesis temperature is low and the nitrogenize cycle is short.
2, this embodiment utilizes nano particle to control whisker growth, Fig. 2 for described in Fig. 1 based on the picture of the beta-silicon nitride powder of catalysis nitrogenize, as can be seen from Figure 2, gained is little based on the silicon nitride particle particle diameter of catalysis nitrogenize, the diameter of whisker is 100 ~ 150nm, and length-to-diameter ratio is 15 ~ 25.
3, this embodiment only introduces the nanocatalyst of trace in reaction process, and without other impurity, product purity is high.
4, the raw material sources of this embodiment are extensive and cheap, and production cost is low, have very large industrialization prospect of production.
Therefore, this embodiment has that Nitration synthesis temperature is low, cost is low, the nitrogenize cycle is short, synthesis technique is simple, be easy to the feature that controls and productive rate is high; The prepared beta-silicon nitride powder particle diameter based on catalysis nitrogenize is little, part is that crystal whisker-shaped and purity are high, and the prospect that industrialization is produced is large.
Claims (6)
1., based on a preparation method for the beta-silicon nitride powder of catalysis nitrogenize, it is characterized in that the step of described preparation method is:
Step one, be 1 ︰ 200 ︰ (10000 ~ 16000) by the mass ratio of Fen San Ji ︰ Gui Fen ︰ distilled water, dispersion agent, silica flour and distilled water mixed, stirs 20 ~ 30min, then ultrasonic disperse 20 ~ 30min, obtained suspension;
Step 2, in described suspension, add the water-soluble chromic salts that concentration is 0.88mol/L, obtained mixed solution; Wherein, the add-on of water-soluble chromic salts is Si ︰ Cr
2o
3mass ratio be 1 ︰ (0.005 ~ 0.050);
Step 3, under agitation, in described mixed solution, add precipitation agent to pH value is 7.5 ~ 8.5, continues stirring 0.5 ~ 1h; Suction filtration, vacuum-drying 10 ~ 12h, obtained mixed powder;
Step 4, be placed in tube-type atmosphere furnace by described mixed powder, under nitrogen atmosphere and temperature rise rate are the condition of 2 ~ 8 DEG C/min, are warming up to 1250 ~ 1400 DEG C, insulation 2 ~ 8h, obtains the beta-silicon nitride powder based on catalysis nitrogenize.
2., according to claim 1 based on the preparation method of the beta-silicon nitride powder of catalysis nitrogenize, it is characterized in that the Si content >=95wt% in described silica flour, particle diameter≤88 μm.
3. according to claim 1 based on the preparation method of the beta-silicon nitride powder of catalysis nitrogenize, it is characterized in that described dispersion agent is the one in polyvinyl alcohol, Sodium dodecylbenzene sulfonate and polyvinylpyrrolidone, the purity of the purity of polyvinyl alcohol, the purity of Sodium dodecylbenzene sulfonate and polyvinylpyrrolidone is analytical pure or is technical pure.
4., according to claim 1 based on the preparation method of the beta-silicon nitride powder of catalysis nitrogenize, it is characterized in that described water-soluble chromic salts is chromium chloride or is chromium nitrate; The purity of chromium chloride and the purity of chromium nitrate are analytical pure or are technical pure.
5. according to claim 1 based on the preparation method of the beta-silicon nitride powder of catalysis nitrogenize, it is characterized in that described precipitation agent is the one in urea, ammoniacal liquor and hydrazine hydrate, the purity of the purity of urea, the purity of ammoniacal liquor and hydrazine hydrate is analytical pure or is technical pure.
6., based on a beta-silicon nitride powder for catalysis nitrogenize, it is characterized in that the described beta-silicon nitride powder based on catalysis nitrogenize is based on the beta-silicon nitride powder based on catalysis nitrogenize prepared by the preparation method of the beta-silicon nitride powder of catalysis nitrogenize according to any one of claim 1 ~ 5.
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| CN105036097A (en) * | 2015-07-30 | 2015-11-11 | 武汉科技大学 | One-dimensional Si3N4 nanometer powder and preparation method thereof |
| CN106478107A (en) * | 2016-10-17 | 2017-03-08 | 武汉科技大学 | A kind of silicon nitride crystal whisker silicon carbide porous ceramicss and preparation method thereof |
| CN106477538A (en) * | 2016-11-03 | 2017-03-08 | 清华大学 | Beta-silicon nitride nanowire preparation method, beta-silicon nitride nanowire, beta-silicon nitride powder and silicon nitride submicron powder |
| CN108622864A (en) * | 2018-04-13 | 2018-10-09 | 浙江东瓷新材料有限公司 | A kind of reaction system for synthesizing silicon nitride powder |
| CN109970035A (en) * | 2019-04-04 | 2019-07-05 | 天津大学 | A kind of α-siliconnitride raw powder's production technology |
| CN110937604A (en) * | 2019-12-20 | 2020-03-31 | 武汉科技大学 | Si @ SiC-Si based on catalytic nitridation method3N4Electrode material and preparation method thereof |
| CN113493191A (en) * | 2020-04-08 | 2021-10-12 | 新疆晶硕新材料有限公司 | Method for preparing high-purity alpha-silicon nitride powder and high-purity alpha-silicon nitride powder |
| CN113564687A (en) * | 2021-08-24 | 2021-10-29 | 安徽工业大学 | Chromium-catalyzed silicon carbide whisker and preparation method thereof |
| CN116216662A (en) * | 2023-02-01 | 2023-06-06 | 江苏富乐华功率半导体研究院有限公司 | Synthesis method of silicon nitride powder |
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| CN105036097A (en) * | 2015-07-30 | 2015-11-11 | 武汉科技大学 | One-dimensional Si3N4 nanometer powder and preparation method thereof |
| CN106478107B (en) * | 2016-10-17 | 2019-05-10 | 武汉科技大学 | A kind of silicon nitride crystal whisker silicon carbide porous ceramics and preparation method thereof |
| CN106478107A (en) * | 2016-10-17 | 2017-03-08 | 武汉科技大学 | A kind of silicon nitride crystal whisker silicon carbide porous ceramicss and preparation method thereof |
| CN106477538A (en) * | 2016-11-03 | 2017-03-08 | 清华大学 | Beta-silicon nitride nanowire preparation method, beta-silicon nitride nanowire, beta-silicon nitride powder and silicon nitride submicron powder |
| CN108622864B (en) * | 2018-04-13 | 2019-10-29 | 浙江东瓷新材料有限公司 | A kind of reaction system for synthesizing silicon nitride powder |
| CN108622864A (en) * | 2018-04-13 | 2018-10-09 | 浙江东瓷新材料有限公司 | A kind of reaction system for synthesizing silicon nitride powder |
| CN109970035A (en) * | 2019-04-04 | 2019-07-05 | 天津大学 | A kind of α-siliconnitride raw powder's production technology |
| CN110937604A (en) * | 2019-12-20 | 2020-03-31 | 武汉科技大学 | Si @ SiC-Si based on catalytic nitridation method3N4Electrode material and preparation method thereof |
| CN110937604B (en) * | 2019-12-20 | 2022-10-21 | 武汉科技大学 | Si @ SiC-Si based on catalytic nitridation method 3 N 4 Electrode material and preparation method thereof |
| CN113493191A (en) * | 2020-04-08 | 2021-10-12 | 新疆晶硕新材料有限公司 | Method for preparing high-purity alpha-silicon nitride powder and high-purity alpha-silicon nitride powder |
| CN113493191B (en) * | 2020-04-08 | 2022-11-22 | 新疆晶硕新材料有限公司 | Method for preparing high-purity alpha-silicon nitride powder and high-purity alpha-silicon nitride powder |
| CN113564687A (en) * | 2021-08-24 | 2021-10-29 | 安徽工业大学 | Chromium-catalyzed silicon carbide whisker and preparation method thereof |
| CN113564687B (en) * | 2021-08-24 | 2022-07-22 | 安徽工业大学 | Chromium-catalyzed silicon carbide whisker and preparation method thereof |
| CN116216662A (en) * | 2023-02-01 | 2023-06-06 | 江苏富乐华功率半导体研究院有限公司 | Synthesis method of silicon nitride powder |
| CN116216662B (en) * | 2023-02-01 | 2023-10-27 | 江苏富乐华功率半导体研究院有限公司 | Synthesis method of silicon nitride powder |
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