CN1115301A - Organic silane laser gas phase synthesis of silica-base micro powder - Google Patents
Organic silane laser gas phase synthesis of silica-base micro powder Download PDFInfo
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- 239000000843 powder Substances 0.000 title claims abstract description 50
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 13
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 title abstract description 6
- 229910000077 silane Inorganic materials 0.000 title abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000007789 gas Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910021529 ammonia Inorganic materials 0.000 claims abstract description 4
- 239000000376 reactant Substances 0.000 claims description 19
- 229910052710 silicon Inorganic materials 0.000 claims description 16
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000010703 silicon Substances 0.000 claims description 15
- 230000035484 reaction time Effects 0.000 claims description 10
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 9
- 150000001282 organosilanes Chemical class 0.000 claims description 9
- 239000012495 reaction gas Substances 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 230000002194 synthesizing effect Effects 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 2
- 229910010271 silicon carbide Inorganic materials 0.000 description 23
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 9
- 229910052581 Si3N4 Inorganic materials 0.000 description 8
- 239000002245 particle Substances 0.000 description 8
- 239000012071 phase Substances 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 6
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229910021419 crystalline silicon Inorganic materials 0.000 description 3
- 238000010494 dissociation reaction Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 238000010574 gas phase reaction Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910018540 Si C Inorganic materials 0.000 description 2
- 229910003818 SiH2Cl2 Inorganic materials 0.000 description 2
- 229910003822 SiHCl3 Inorganic materials 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229910010293 ceramic material Inorganic materials 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000012808 vapor phase Substances 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910007991 Si-N Inorganic materials 0.000 description 1
- 229910008329 Si-V Inorganic materials 0.000 description 1
- 229910003910 SiCl4 Inorganic materials 0.000 description 1
- 229910006294 Si—N Inorganic materials 0.000 description 1
- 229910006768 Si—V Inorganic materials 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000000280 densification Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011863 silicon-based powder Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
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Abstract
The process for laser gas-phase synthesis of ultra-fine Si-base powder features that said ultra-fine Si-base powder is synthesized up by reaction of organic silane on hydrogen and/or ammonia at 600-1800 deg.C, 500-6000 W/cm2 laser power density, 0.2-1 atm and 1200-6000 cm3/min gas flow for 0.2-4 ms. Its advantages include very low cost and high quality of Si-base powder.
Description
The invention relates to a synthesis process of silicon-based ultrafine powder, in particular to a method for synthesizing silicon-based ultrafine powder by using organosilane as a raw material through laser gas phase.
The silicon-based ultrafine powder mainly refers to Si3N4SiC, Si/N/C, which have important structural and functional applications. Wherein the superfine Si is3N4The powder can be used as optical ultra-precision polishing and wave-absorbing material and transmission materialA sensor material; si3N4SiC is a typical special ceramic system, has high hardness, high strength, high toughness and high temperature strength, and is superfine Si3N4The SiC powder as sintering precursor powder can obviously reduce sintering temperature, accelerate diffusion and enhance densification, and is used for preparing high-density Si3N4An ideal raw material of SiC material; as an additive, ultra-fine Si3N4SiC can be used as a superfine toughening and reinforcing component to be added into a common ceramic body or medical ceramic to improve the mechanical property of the ceramic; the superfine Si/N/C powder is sintered conventionally to produce nano composite Si3N4SiC ceramic materials which have outstanding toughness and high-temperature strength and the superplasticity which is uniquely found in covalently bonded ceramic materials. The applications of the above silicon-based ultrafine powders all require high-purity powders with excellent properties. The laser-induced gas phase reaction adopts high-energy laser to act with the reaction gas flow, energy resonance is generated between the high-energy laser and the reaction gas flow, and the particle nucleation growth is completed instantly. Because the method can form a stable, uniform and controllable small reaction zone without a wall and can accurately control the reaction process through process parameters, the technologyis particularly suitable for preparing ceramic ultrafine powder with high purity, no agglomeration, uniform particle size, small particle size, component particle size and controllable crystal type. The preparation technology is the most promising synthesis technology of the nano ceramic powder internationally recognized at present, and has various advantages compared with the traditional preparation technologies such as a plasma heating method, a chemical vapor phase method and a heat pipe furnace heating method. Laser gas phase reaction is mainly used for preparing high-quality Si since MIT was established in the end of 70 s3N4Fine powder of SiC, Si/N/C, the raw material is silane-SiH4E.g. with SiH4＋NH3Preparation of Si3N4，SiH4＋C2H2(or C)2H2) For preparing SiC from (CH)3)2NH (or CH)3NH2)＋SiH4To prepare Si/N/C. The price of silane is high (between 6000 yuan/kg at home and 200 yuan/kg at abroad), so that the cost of powder is high, the cost of raw materials is a key problem for limiting the commercial application of the method,also limiting this technology to laboratory levels. In addition, the silane is flammable and explosive gasIt is not easy to be processed and to synthesize Si/N/C powder with various components.
In recent years, the search for inexpensive alternative reactants has been a focus of research in this field. The reactant selected is mainly SiHCl3、SiH2Cl2、SiCl4And the chlorine-containing reactants have the following disadvantages: (1) poor absorbance of reactants (CO)2Laser λ 10.6 μm); (2) easily cause solid by-products such as NH4Cl; (3) high corrosivity, wherein SiHCl3、SiH2Cl2The price is high, and the gas belongs to flammable and explosive gas;(5) because the raw materials contain chlorine, the micro detention of the chlorine has serious influence on the structure pottery and is difficult to remove subsequently.
The invention aims to provide a method for synthesizing silicon-based ultrafine powder by laser gas phase, which can greatly reduce the cost and synthesize the silicon-based ultrafine powder with high quality.
The invention provides a method for synthesizing silicon-based ultrafine powder by laser gas phase, which is characterized by comprising the following steps:
the organosilane is taken as a main reactant, and the structural general formula is as follows: (R)a 1Rb 2Si)2NR3Wherein R isa 1、Rb 2、R3Both are alkyl or hydrogen, a and b are alkyl or hydrogen, and a + b is 3;
-with hydrogen and/or ammonia as additional reactant gas, the molar ratio of the main reactant to the additional reactant gas is: 1: 1-10;
-laser gas-phase synthesis of silicon-based ultrafine powder under the following process conditions:
laser power density (P): 500-6000W/cm2
Reaction pressure (Pe): 0.2 to 1atm
Total reaction gas flow rate (Φ t): 1200-6000 cm3/min
Reaction time (t): 0.2 to 4ms
Reaction temperature (T): 600-1800 DEG C
The invention selects the materials with low price (less than 100 yuan/kg) and strong strengthThe light-absorbing, low-boiling point, chlorine-sulfur-free and virulent-corrosive organosilane is used as main reactant in laser gas-phase reaction, and through the addition of additionalreaction gas and process control, Si can be prepared from the same main reactant under different conditions3N4SiC and Si/N/C powder. The organosilicon has a macromolecular structure and has a dense vibration energy state, and gaseous reactants and CO of the organosilicon2The laser action leads to the dissociation of a certain bond of the molecule through the V-T/R energy transfer in the molecule or between the molecules. The formed organic radicals generate a crosslinking reaction with double control of thermodynamic dynamics, new Si-V or Si-C bonds are formed, and excess C, N, H is in C2H4、C2H2、NH3The micromolecular gas is removed to finally obtain the superfine powder with certain chemical composition and certain granularityAnd (3) pulverizing. Therefore, the formation of solid particles by macromolecular reaction is accompanied by the discharge of byproduct gas during the growth of intermolecular direct crosslinking nucleation, and the reaction time, the reaction temperature and the additional gas are the main factors for determining the components of the powder product, wherein the reaction time can be controlled by the total reaction gas flow, and the reaction temperature is determined by the reaction gas flow and the laser power density.
Introducing NH into the organosilane at a certain temperature (950-1100 ℃) for 1.2-1.6 ms3(organosilane: NH)31: 1-6), organosilicon and NH3Sufficient crosslinking, e.g. Si-CH3Bond dissociation to form new Si-N bond with simultaneous evolution of CH4、C2H2Etc. to form Si3N4The reaction can be expressed as:
when the temperature is higher (more than 1400 ℃), the reaction time is longer (1.5-4 ms), which is favorable for Si-C bondreconstruction and excessive free carbon formation, because of C-H bond dissociation, and a certain amount of H is introduced into the organic silicon under the condition2([H2]/[ organosilicon]]The molar ratio is as follows: 5 to 10) can suppress formation of free carbon and NH3Expulsion, favours the formation of SiC, the reaction of which can be expressed as:
when the temperature is lower than 950 ℃, such as 650-950 ℃, the reaction is carried outThe time is shorter (0.6-1.5 ms), and part of C and H are removed, so that amorphous Si/N/C powder with a certain chemical composition is formed; the reaction formula is as follows: when the temperature is high (1000-1300 ℃), the reaction time is (1.6-2.4 ms), the formed powder is amorphous Si/N/C and β -SiC mixed powder, and the reaction is summarized as follows:
the powder prepared by the method has strong oxygen adsorption characteristics, such as air exposure, [ O]: 5-10 wt%; for example, the operation in a glove box is [ O]<1 wt%. In addition, the main impurities are part of organic group retention powder, the lower the temperature is, the higher the organic impurities are, generally 1-5 wt%, but the existence of the impurities is beneficial to powder sintering application. The yield of the powder is generally 40-150 g/h, and the particle size of the powder is 5-50 nm. The present invention will be described in detail below by way of examples with reference to the accompanying drawings.
FIG. 1 is an X-ray diffraction pattern of laser gas-phase synthesis of silicon-based powder;
FIG. 2 is a laser vapor phase synthesis silica-based pink external absorption spectrum;
FIG. 3 shows the morphology of the powder.
(1) Example (b): the reactants are as follows: ((CH)3)3Si)2NH(HMDS)
Table 1 experimental fixed parameters
The diameter of the light spot: 5mm
Nozzle diameter: 4mm
Spot center distance nozzle: 2mm
Other parameters are shown in Table 2
Will ((CH)3)3Si)2NH (b.p.125 ℃) is vaporized and evaporated at 130 ℃ with NH3By [ NH]3]/[((CH3)Si)2NH]Mixing at a ratio of 4 to obtain Si at T of 1.5ms and T of 1000 deg.C3N4: 98 Wt%, 15nm particle size ultrafine powder, infrared absorption as shown in figure 2, and X-ray diffraction as shown in figure 1 to confirm that the powder is amorphous, and TEM morphology as shown in figure 3.
(2) EXAMPLE (4)
Reactants, fixed parameters such as (1) [ NH]3]/[HMDS]When T is 0.6-1.5 ms and T is 650-900 ℃, 8-10 nm amorphous Si/N/C powder (C/N is 0.6-15) is obtained, and infrared absorption and X-ray diffraction are shown in fig. 1 and 2.
(5) EXAMPLE 7
The reactants and the fixed parameters are the same as those in (1). (5) Adding ammonia, hydrogenating [ NH]3]/[HMDS]＝2，[H2]/[HMDS](ii) 5; (6) addition of NH3Without addition of H2，[NH3]/[HMDS]2, wherein (5) and (6) form Si/N/C powder containing β -SiC at 1200 to 1250 ℃, and the C content of (6) is increased compared with that of (5), and (7) H2]/[HMDS]The reaction temperature was higher than 5, and 95 wt% of β -SiC was obtained, which had an average particle size of 30nm, and infrared absorption and X-ray diffraction of β -SiC were shown in FIGS. 1 and 2.
(8) Example (10)
Reactant (H (CH)3)2Si)2NH, fixed parameters as in (1), adding NH3，[NH3]/[H(CH3)2Si)2NH]96 wt% Si is obtained at 950 deg.C under 4, T under 1.1ms3N4(8) (ii) a Addition of NH3，[NH3]/[H(CH3)2Si)2NH]15nmSi/N/C powder (9) was prepared at 620 ℃ T4; adding H2Without addition of NH3，[H]/[H(CH3)2Si)2NH]35nm β -SiC powder (10) was obtained when T is 5, 4.0ms and T is 1650
The laser reaction total reaction powder forms a grain diameter crystal form main phase
Time pressure temperature (wt%) of power gas flow
(W/cm2) (cm6(iv) min) (ms) (atm) (. degree.C.) Si NC (nm) (1) 152036001.50.910005939215 amorphous Si3N4：98wt％(2) 152042001.10.980050302010 amorphous Si/N/C (C/N ═ 0.6) (3) 152048000.60.46504522338 amorphous Si/N/C (C/N ═ 15) (4) 500048000.60.47504335228 amorphous Si/N/C (C/N ═ 2.5) (5) 152018004.00.6120056232118 amorphous + crystalline Si/N/C + β -SiC (6) 152018004.00.6125052202830 crystalline Si/N/C + β -SiC (7) 500018004.01.017506743030 crystalline β -SiC (97 wt%) (8) 152042001.11.07505739410 amorphous Si/N/C + β -SiC (6) 500018004.01.017506743030 crystalline Si/N/C + β -SiC (7) 500018004.01.0175067430303N4(97.5 wt%) (9) 152048000.61.062042283010 amorphous Si/N/C (10) 152018004.01.016506842835 crystalline β -SiC
Claims (5)
1. A method for synthesizing silicon-based ultrafine powder by laser gas phase is characterized in that:
the organosilane is taken as a main reactant, and the structural general formula is as follows: (R)a 1Rb 2Si)2NR3Wherein R isa 1、Rb 2、R3Both are alkyl or hydrogen, a and b are alkyl or hydrogen, and a + b is 3;
-with hydrogen and/or ammonia as additional reactant gas, the molar ratio of the main reactant to the additional reactant gas is: 1: 1-10;
-laser gas-phase synthesis of silicon-based ultrafine powder under the following process conditions:
laser power density (P): 500-6000W/cm2
Reaction pressure (Pe): 0.2 to 1atm
Total reaction gas flow rate (Φ t): 1200-6000 cm3/min
Reaction time (t): 0.2 to 4ms
Reaction temperature (T): 600-1800 DEG C
2. A process for the laser gas phase synthesis of silicon-based ultrafine powders according to claim 1, characterized by:
when the reaction temperature is 950-1100 ℃, the reaction time is 1.2-1.6 ms, and the molar ratio of organosilane to ammonia gas is 1: 1-6, Si can be generated3N4The reaction equation of the nanometer ultrafine powder is as follows:
3. a process for the laser gas phase synthesis of silicon-based ultrafine powders according to claim 1, characterized by:
when the reaction temperature is 650-950 ℃ and the reaction time is 0.6-1.5ms, amorphous Si/N/C powder is generated, and the reaction equation is as follows:
4. a process for the laser gas phase synthesis of silicon-based ultrafine powders according to claim 1, characterized by:
when the reaction temperature is 1000-1300 ℃ and the reaction time is 1.6-2.4 ms, mixed powder of Si/N/C and β -SiC is generated, and the reaction equation is as follows:
5. a process for the laser gas phase synthesis of silicon-based ultrafine powders according to claim 1, characterized by:
when the reaction temperature is 1400-1800 ℃ and the reaction time is 1.5-4 ms, and the molar ratio of organosilane to hydrogen is 1: 5-10, the reaction equation of the generated SiC ultrafine powder is as follows:
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| Application Number | Priority Date | Filing Date | Title |
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| CN94110393A CN1038124C (en) | 1994-07-19 | 1994-07-19 | Organic silane laser gas phase synthesis of silica-base micro powder |
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|---|---|---|---|
| CN94110393A CN1038124C (en) | 1994-07-19 | 1994-07-19 | Organic silane laser gas phase synthesis of silica-base micro powder |
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| CN1115301A true CN1115301A (en) | 1996-01-24 |
| CN1038124C CN1038124C (en) | 1998-04-22 |
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| CN106698436A (en) * | 2017-01-10 | 2017-05-24 | 山东天岳晶体材料有限公司 | Preparation method of high-purity silicon carbide powder |
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| US4613490A (en) * | 1984-05-08 | 1986-09-23 | Mitsubishi Gas Chemical Company, Inc. | Process for preparing silicon nitride, silicon carbide or fine powdery mixture thereof |
| JPH01131100A (en) * | 1987-11-12 | 1989-05-23 | Toyota Motor Corp | Production of silicon carbide whisker |
| CN1021808C (en) * | 1991-03-18 | 1993-08-18 | 中国科学院安徽光学精密机械研究所 | Novel method and device for preparing silicon nitride powder by laser |
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