CN102674848A - Method for preparing SiC ceramic precursor for chemical liquid-vapor deposition process - Google Patents
Method for preparing SiC ceramic precursor for chemical liquid-vapor deposition process Download PDFInfo
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- CN102674848A CN102674848A CN2012101393329A CN201210139332A CN102674848A CN 102674848 A CN102674848 A CN 102674848A CN 2012101393329 A CN2012101393329 A CN 2012101393329A CN 201210139332 A CN201210139332 A CN 201210139332A CN 102674848 A CN102674848 A CN 102674848A
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Abstract
The invention belongs to the field of inorganic chemistry, and relates to a method for preparing a SiC ceramic precursor for a chemical liquid-vapor deposition process, in particular to a method in which polydimethylsilane is taken as a raw material and which is used for preparing a liquid SiC ceramic precursor for the chemical liquid-vapor deposition process by pyrolysis and distillation processes. The SiC ceramic precursor with the boiling point of 100 to 200 DEG C is obtained by performing pyrolysis and fractionation on the polydimethylsilane at different temperatures. The invention has the advantages that the prepared SiC ceramic precursor for the chemical liquid-vapor deposition process is stable at normal temperature, has low boiling point (below 200 DEG C), is high in flowability and deposition efficiency, and is noncorrosive to the environment, a pyrolysis product is near-stoichiometric beta-SiC, byproducts generated in the deposition and pyrolysis process are noncorrosive and pollution-free to the environment, and the like; and meanwhile, the preparation process is simple, short in preparation period and low in cost.
Description
Technical field:
The present invention relates to a kind of method for preparing the chemical liquids gas-phase deposition with the SiC ceramic precursor.Being particularly related to a kind of is raw material with polydimethyl silane, adopts pyrolysis, the distillatory prepared chemical liquids gas-phase deposition method with liquid Si C ceramic precursor.
Background technology:
The C/SiC ceramic matric composite is owing to have good characteristics such as low density, HS, H.T., high temperature resistant, anti-thermal shock, high abrasion, resistance to chemical attack, thermal expansivity be low; Can be used as high-temperature structural material, thermally protective materials, brake material; Like C/SiC larynx lining, jet pipe and combustion chamber; The C/SiC heat exchanger, C/SiC brake flange and brake facing etc. and be applied to fields such as aerospace, the energy, traffic.
The method for preparing at present the C/SiC ceramic matric composite mainly is precursor infiltration and pyrolysis method (PIP) and chemical vapor infiltration (CVI).Wherein the precursor infiltration and pyrolysis method needs repeated impregnations---and cracking could realize densification more than 10 times; And chemical vapor infiltration owing to the too fast time surface of sedimentation rate easily " crust " cause the prefab inside can't be fine and close, need the reduction sedimentation rate, and its surface working opened the densification of hole to realize that it is inner.Therefore these the two kinds technologies that prepare the C/SiC ceramic matric composite all have the long and high shortcoming of production cost of production cycle.
Chemical liquids gas-phase deposition (CLVD) is a kind of fast densified metallization processes; It is that prefabricated carbon fiber spare is immersed in the cvd furnace that fills liquid precursor; Adopt the mode of induction heating or resistive heating; Make liquid precursor gasification, cracking generate ceramic matrix and be deposited on prefab inside, accomplish densification from inside to outside, thereby obtain the carbon fibre reinforced ceramics based composites.Compare with traditional CVD/CVI technology, the equipment of CLVD is simple, need not carrier gas equipment and exhaust gas processing device; And this technology has the characteristics of efficient dipping and successive sedimentation, and its sedimentation rate is not controlled by diffusion process.Therefore, adopt this prepared C/SiC ceramic matric composite greatly to shorten preparation cycle, reduce production costs.According to the characteristics of chemical liquids gas-phase deposition, the SiC ceramic precursor needs that satisfy its working conditions possess following characteristic: (1) is liquid state at normal temperatures, and good fluidity is nontoxic and stable; (2) moderate boiling point generally should be lower than 200 ° of C; (3) can gasification cracking be the SiC matrix at high temperature; (4) obtain easily.Therefore, the SiC precursor that existing P IP, CVI technology are used such as Polycarbosilane solution etc. can't satisfy the requirement of chemical liquids gas-phase deposition, need develop the novel precursor that is applicable to this technology.People such as Qiao Shengru (Chinese patent CN 1884205A) have reported with the hexamethyldisilazane precursor, adopt the chemical liquids gas-phase deposition to prepare the C/C-SiC ceramic matric composite, but the matrix that this precursor cracking obtains are by pyrolysis C, SiC, Si
3N
4Mixture form.Foreign literature (U.S. Pat 5981002) has reported that dimethyldichlorosilane(DMCS) and monomethyl dichlorosilane can be used as the precursor that the chemical liquids gas-phase deposition prepares the C/SiC ceramic matric composite; But in the precursor of these SiC pottery owing to contain the chlorine atom; Raw material and split product thereof (HCl, other polycondensation chlorosilanes etc.) can cause serious pollution to environment and equipment.
To environmentally friendly SiC gas-phase deposition, people (U.S. Pat 6370802B2) such as Shen Qionghua have developed a kind of chain carbon silane (TMTSH), and molecular weight is about 190, and the about 45 ° of C of boiling point can be used for the deposition of SiC coating.But this method synthetic route is long, raw materials cost is high, and molecular weight is lower, and most of volatilization is overflowed when being applied to the chemical liquids vapour deposition, and sedimentation effect is very low.Li Bin etc. (with liquid carbon silane is that precursor prepares CVD SiC coating. Materials science and technology; 2007; 15 (6): 848-850) reported a kind of low molecule silicon-carbon alkane (LPS), non-corrosiveness just can deposit the SiC coating of stoichiometric ratio under 900 ° of C.Adopt LPS to carry out the chemical liquids vapour deposition, have the low deficiency of sedimentation effect equally.
Therefore, need exploitation to satisfy the SiC ceramic precursor of chemical liquids gas-phase deposition, have characteristics such as (closely) stoichiometric ratio, nothing corrosion after making it to have efficient deposition and deposition.
Summary of the invention:
The objective of the invention is to production cycle of prior art long with the production cost height or problems such as sedimentation effect is low, contaminate environment and equipment; Develop and a kind ofly be applicable to the chemical liquids gas-phase deposition and, and then prepare the C/SiC ceramic matric composite fast the free from corrosion SiC ceramic precursor of environment.It is to be raw material with polydimethyl silane, adopt that pyrolysis, distillatory mode prepare that boiling point is low, good fluidity, have have (closely) stoichiometric ratio after efficient deposition and the deposition, to the free from corrosion SiC ceramic precursor of environment.
For achieving the above object, the present invention takes following technical scheme to be achieved:
(1) pyrolysis of polydimethyl silane: the polydimethyl silane powder of certain molecular weight is placed the there-necked flask that prolong and receiving trap are housed, at N
2Be heated to the certain temperature insulation under the protection and decompose, finally obtain liquid carbon silane.Wherein holding temperature is 350～450 ° of C, and soaking time is 0.5～10h.
(2) pyrolysis of carbon silane: at first the carbon silane with the liquid state in (1) filters, and obtains purified carbon silane, is placed on then in the normal-pressure reaction kettle, at N
2Be heated to the certain temperature insulation under the protection and decompose, finally obtain the liquid thick finished product of carbon silane precursor.Wherein holding temperature is 450～500 ° of C, and soaking time is 1～20h.
(3) fractionation of the thick finished product of liquid carbon silane precursor: the thick finished product of liquid carbon silane precursor places normal-pressure reaction kettle with filtrating, at N through after filtering
2Be heated to certain temperature (160～200 ° of C) under the atmosphere, and the insulation certain hour (1～3h), under vacuum, carry out underpressure distillation, collect the cut of boiling point between 100 ℃～200 ℃, promptly get precursor---the liquid carbon silane of SiC pottery.
With the liquid carbon silane that makes is precursor, adopts the chemical liquids gas-phase deposition to deposit 3～8 hours at 1000～1600 ° of C, and can make density is 1.72～1.86g/cm
3, flexural strength is 110～180MPa, the precursor split product is the C/SiC ceramic matric composite of the β-SiC of near stoichiometric proportion.Wherein, the utilization ratio of precursor (sedimentation effect) is more than 50%.
The invention has the advantages that: at first, the SiC ceramic precursor of the present invention preparation is stable at normal temperatures, boiling point low (100～200 ° of C), good fluidity and environment do not had corrosion; Secondly, the split product of the SiC ceramic precursor of the present invention's preparation is the β-SiC of near stoichiometric proportion; Once more, the boiling point of precursor adapts to the chemical liquids gas-phase deposition, and sedimentation effect is high; At last, the SiC ceramic precursor of the present invention's preparation, it is pollution-free that the by product in subsequent deposition and cracking process does not have corrosion to environment.
Description of drawings
Fig. 1 is the XRD figure of SiC ceramic precursor sedimentary product of cracking under 1200 ° of C of preparation in the embodiment of the invention 1.
Embodiment:
Embodiment 1:
Adopting the present invention to prepare the chemical liquids gas-phase deposition may further comprise the steps with the SiC ceramic precursor:
1, polydimethyl silane powder is placed the there-necked flask that prolong and receiving trap are housed, at N
2Be heated to 350 ° of C insulation 4h under the protection, obtain liquid carbon silane.
2, the carbon silane with the liquid state in (1) filters, and obtains purified carbon silane, is placed on then in the normal-pressure reaction kettle, at N
2Be heated to 450 ° of C insulation 8h under the protection, obtain the liquid thick finished product of carbon silane precursor.
3, the liquid thick finished product of carbon silane precursor places normal-pressure reaction kettle with filtrating, at N through after filtering
2Be heated to 200 ° of C under the atmosphere, insulation 1h carries out underpressure distillation then under vacuum, collect the cut of boiling point between 100～200 ℃, and yield 45.8% promptly gets liquid carbon silane precursor.
Embodiment 2:
Adopting the present invention to prepare the chemical liquids gas-phase deposition may further comprise the steps with the SiC ceramic precursor:
1, polydimethyl silane powder is placed the there-necked flask that prolong and receiving trap are housed, at N
2Be heated to 450 ° of C insulation 10h under the protection, obtain liquid carbon silane.
2, the carbon silane with the liquid state in (1) filters, and obtains purified carbon silane, is placed on then in the normal-pressure reaction kettle, at N
2Be heated to 500 ° of C insulation 20h under the protection, obtain the liquid thick finished product of carbon silane precursor.
3, the liquid thick finished product of carbon silane precursor places normal-pressure reaction kettle with filtrating, at N through after filtering
2Atmosphere
Under be heated to 200 ° of C, the insulation 1h, under vacuum, carry out underpressure distillation then, collect the cut of boiling point between 100～200 ℃, yield 38.2% promptly gets liquid carbon silane precursor.
Embodiment 3:
Adopting the present invention to prepare the chemical liquids gas-phase deposition may further comprise the steps with the SiC ceramic precursor:
1, polydimethyl silane powder is placed the there-necked flask that prolong and receiving trap are housed, at N
2Be heated to 350 ° of C insulation 0.5h under the protection, obtain liquid carbon silane.
2, the carbon silane with the liquid state in (1) filters, and obtains purified carbon silane, is placed on then in the normal-pressure reaction kettle, at N
2Be heated to 450 ° of C insulation 1h under the protection, obtain the liquid thick finished product of carbon silane precursor.
3, the liquid thick finished product of carbon silane precursor places normal-pressure reaction kettle with filtrating, at N through after filtering
2Be heated to 160 ° of C under the atmosphere, insulation 3h carries out underpressure distillation then under vacuum, collect the cut of boiling point between 100～160 ℃, and yield 52.4% promptly gets liquid carbon silane precursor.
Claims (1)
1. a chemical liquids gas-phase deposition is characterized in that with the preparation method of SiC ceramic precursor:
(1) pyrolysis of polydimethyl silane: polydimethyl silane powder is placed the there-necked flask that prolong and receiving trap are housed, at N
2Be heated to the certain temperature insulation under the protection and decompose, finally obtain liquid carbon silane; Wherein holding temperature is 350～450 ° of C, and soaking time is 0.5～10h;
(2) pyrolysis of carbon silane: at first the carbon silane with the liquid state in (1) filters, and obtains purified carbon silane, is placed on then in the normal-pressure reaction kettle, at N
2Be heated to the certain temperature insulation under the protection and decompose, finally obtain the liquid thick finished product of carbon silane precursor; Wherein holding temperature is 450～500 ° of C, and soaking time is 1～20h;
(3) fractionation of the thick finished product of liquid carbon silane precursor: the thick finished product of liquid carbon silane precursor places normal-pressure reaction kettle with filtrating, at N through after filtering
2Be heated to certain temperature under the atmosphere, insulation for some time, under vacuum, carry out underpressure distillation, collect the cut of boiling point between 100 ℃～200 ℃, promptly obtain the SiC ceramic precursor---liquid carbon silane; Wherein holding temperature is 160～200 ° of C, and soaking time is 1～3h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116408252A (en) * | 2021-12-29 | 2023-07-11 | 南昌中微半导体设备有限公司 | Workpiece processing method, workpiece and plasma processing apparatus |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224988A (en) * | 2008-01-29 | 2008-07-23 | 中国人民解放军国防科学技术大学 | Low-temperature preparation method of C/SiC ceramic matrix composite material |
| CN101265105A (en) * | 2008-04-11 | 2008-09-17 | 中国人民解放军国防科学技术大学 | Method for preparing niobium-containing SiC ceramic precursor |
| CN101659548A (en) * | 2009-09-02 | 2010-03-03 | 中钢集团洛阳耐火材料研究院有限公司 | Method for preparing aluminiferous nitride in-situ composite aluminum-carbon refractory material |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101224988A (en) * | 2008-01-29 | 2008-07-23 | 中国人民解放军国防科学技术大学 | Low-temperature preparation method of C/SiC ceramic matrix composite material |
| CN101265105A (en) * | 2008-04-11 | 2008-09-17 | 中国人民解放军国防科学技术大学 | Method for preparing niobium-containing SiC ceramic precursor |
| CN101659548A (en) * | 2009-09-02 | 2010-03-03 | 中钢集团洛阳耐火材料研究院有限公司 | Method for preparing aluminiferous nitride in-situ composite aluminum-carbon refractory material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116408252A (en) * | 2021-12-29 | 2023-07-11 | 南昌中微半导体设备有限公司 | Workpiece processing method, workpiece and plasma processing apparatus |
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