CN100554210C - The method of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic - Google Patents
The method of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic Download PDFInfo
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- CN100554210C CN100554210C CNB2007100577625A CN200710057762A CN100554210C CN 100554210 C CN100554210 C CN 100554210C CN B2007100577625 A CNB2007100577625 A CN B2007100577625A CN 200710057762 A CN200710057762 A CN 200710057762A CN 100554210 C CN100554210 C CN 100554210C
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Abstract
The present invention relates to a kind of method of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic.This procedure comprises: with the polysiloxane of hydrogen content 1.55wt% and tetramethyl-tetrem thiazolinyl cyclotetrasiloxane by mass ratio 1: 2-2: 1 magnetic agitation mix compound, with the mixture quality is that benchmark drips vinylsiloxane coordination platinum complex catalyst, after mixing, pour in the mould, put into vacuum drying oven cross moulding under 20 ℃ to 100 ℃ conditions, the base substrate oven dry demoulding after the moulding, then under argon gas or nitrogen atmosphere, cool to room temperature after being warming up to 600-1300 ℃ of insulation, make fine and close silicon-oxygen-carbon ceramic.The invention has the advantages that adopting the liquid phase polysiloxane is raw material, moulding process need not pressurizeed, and the technological process simple controllable can make difform silica carbon ceramic of compact.
Description
Technical field
The present invention relates to a kind of method of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic, belong to the ceramics processing field.
Background technology
It is a kind of novel method that grew up in the last few years that organic precursor prepares stupalith, compare with traditional preparation method, its have can be on molecular scale that material is designed, prepares pottery, dead size moulding, the cracking temperature of high-performance offbeat form is low, advantage such as save energy, high-temperature behavior are good.Polysiloxane is cheap and easy to get, and can handle in air, and the SiOC stupalith of preparation has good chemical stability, erosion resistance, and the good temperature resistance energy can be at 1200 ℃ of following life-time service.There is the people to be heated under 100 ℃ of pressurization 80MPa conditions at present abroad and carries out moulding, prepare SiOC ceramic of compact body 1100 ℃ of cracking by solid-state commercial polysiloxane.The technology more complicated that relates to, thickness is lower than 0.7mm, otherwise can cause the sample cracking.
Summary of the invention
The object of the present invention is to provide a kind of method of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic, can overcome the shortcoming of prior art.The present invention can easy preparation SiOC ceramic of compact, under no press strip spare, adopt liquid phase injection molding cross moulding, technology is simple, can prepare difform SiOC ceramic of compact, have that crosslinked and moulding is carried out simultaneously, preparation process need not pressurizeed, the manageable characteristics of ceramic body shape.
The step that the method for a kind of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic provided by the invention comprises:
In the presence of vinylsiloxane coordination platinum complex catalyst, hydrogen containing siloxane mixed back cross moulding in mould with tetramethyl-tetrem thiazolinyl cyclotetrasiloxane; The oven dry demoulding, then under inert atmosphere conditions, gradient increased temperature carries out cracking, insulation to 600-1300 ℃; Be cooled to 20 ℃ with same velocity gradient then, make fine and close silicon-oxygen-carbon ceramic.
The step that the method for a kind of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic provided by the invention comprises:
1) hydrogen containing siloxane is mixed with tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, mix compound, add vinylsiloxane coordination platinum complex catalyst simultaneously, mix; The viscosity at ambient temperature of hydrogeneous polyoxy alkane is 0.5Pas;
2) pour in the mould, put into vacuum drying oven cross moulding under 20-100 ℃ of condition, 6-54h;
3) base substrate after the moulding is dried the demoulding between 80-100 ℃, under argon gas or nitrogen atmosphere condition, rises to 600-1300 ℃ with temperature rise rate 0.5-2 ℃/min and carries out cracking then, insulation 1-8h;
4) reduce to 20 ℃ with rate of temperature fall 0.5-2 ℃/min then, make fine and close silicon-oxygen-carbon ceramic.
The hydrogen content of described hydrogen containing siloxane is 1.55wt%.
The mass ratio 1-2 of described hydrogen containing siloxane and tetramethyl-tetrem thiazolinyl cyclotetrasiloxane: 1-2.
Described catalyzer is mixture quality 1wt%.
The present invention can overcome the shortcoming of prior art, can easy preparation SiOC ceramic of compact, under no press strip spare, adopt liquid phase injection molding cross moulding, the technology simple controllable, can prepare difform SiOC ceramic of compact, have that crosslinked and moulding is carried out simultaneously, preparation process need not pressurizeed, the manageable characteristics of ceramic body shape.
Description of drawings
The SiOC block ceramic profile scanning Electronic Speculum figure that Fig. 1 makes for the embodiment of the invention one.
The SiOC block ceramic profile scanning Electronic Speculum figure that Fig. 2 makes for the embodiment of the invention two.
Embodiment
Agents useful for same hydrogen containing siloxane (hydrogen content 1.55wt% in the embodiment of the invention, viscosity at ambient temperature is 0.5Pas) produce by Zhejiang three Tai Youjiguicailiaochang that become civilized, tetramethyl-tetrem thiazolinyl cyclotetrasiloxane is produced by Zhejiang San Men thousand rainbow Industrial Co., Ltd.s, the vinylsiloxane platinum complex catalyst is produced by Shenzhen platinum complex company, platinum content 3000 * 10
-6
Embodiment 1:
Adopt 10g hydrogen containing siloxane and 10g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane magnetic agitation simultaneously; drip the vinylsiloxane platinum complex catalyst of 0.2g; pour mould after mixing into; under 20 ℃ of conditions, place 48h and form crosslinked body; direct demold is prepared the base substrate that round diameter is 2.3cm behind 80 ℃ of placement 6h then; under the argon gas atmosphere protection; temperature rise rate with 2 ℃/min rises to 1000 ℃, reduces to 20 ℃ with the rate of temperature fall of 2 ℃/min behind the insulation 1h and obtains fine and close silica carbon amorphous ceramic.This ceramic cross-section morphology as shown in Figure 1.
Embodiment 2:
Adopt 10g hydrogen containing siloxane and 5g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, magnetic agitation simultaneously, drip the vinylsiloxane platinum complex catalyst of 0.15g, pour into after mixing in the mould and under 50 ℃ of conditions, begin to take shape crosslinked body, then 100 ℃ place the 6h demoulding after under nitrogen atmosphere, temperature rise rate with 1 ℃/min is warmed up to 800 ℃, reduces to 20 ℃ with the rate of temperature fall of 2 ℃/min behind the insulation 2h and obtains fine and close silica carbon amorphous ceramic.This ceramic cross-section morphology as shown in Figure 2.
Embodiment 3:
Adopt 5g hydrogen containing siloxane and 10g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, magnetic agitation simultaneously, drip the vinylsiloxane platinum complex catalyst of 0.15g, pour into after mixing in the mould and place 6h at 80 ℃, after the oven dry demoulding, under nitrogen atmosphere, 2 ℃ of temperature rise rates/min to 1000 ℃, reduce to 20 ℃ with the rate of temperature fall of 2 ℃/min behind the insulation 4h and obtain fine and close SiOC amorphous ceramics.
Embodiment 4:
Adopt 5g hydrogen containing siloxane and 10g tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, magnetic agitation simultaneously, drip the vinylsiloxane platinum complex catalyst of 0.15g, pour into after mixing in the mould and place 6h at 80 ℃, after the oven dry demoulding, under nitrogen atmosphere, 2 ℃ of temperature rise rates/min to 1200 ℃, reduce to 20 ℃ with the rate of temperature fall of 2 ℃/min behind the insulation 2h and obtain fine and close silica carbon amorphous ceramics.
Claims (6)
1, a kind of method of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic, the step that it comprises is: hydrogen containing siloxane mixed back cross moulding in mould under catalyst action with vinylsiloxane; The oven dry demoulding under inert atmosphere conditions, is warming up to 600-1300 ℃ and carries out cracking then, insulation; Cooling is characterized in that described catalyzer is a vinylsiloxane coordination platinum complex then, and described vinylsiloxane is a tetramethyl-tetrem thiazolinyl cyclotetrasiloxane.
2, a kind of method of liquid polysiloxane synthesis of densified silicon-oxygen-carbon ceramic is characterized in that the step that it comprises:
1) hydrogen containing siloxane is mixed with tetramethyl-tetrem thiazolinyl cyclotetrasiloxane, mix compound, add vinylsiloxane coordination platinum complex catalyst simultaneously, mix;
2) pour in the mould, put into vacuum drying oven cross moulding under 20-100 ℃ of condition, 6-54h;
3) base substrate after the moulding is dried the demoulding between 80-100 ℃, under argon gas or nitrogen atmosphere condition, rises to 600-1300 ℃ with temperature rise rate 0.5-2 ℃/min and carries out cracking then, insulation 1-8h;
4) reduce to 20 ℃ with rate of temperature fall 0.5-2 ℃/min then, make fine and close silicon-oxygen-carbon ceramic.
3, in accordance with the method for claim 2, the viscosity at ambient temperature that it is characterized in that described hydrogen containing siloxane is 0.5Pas.
4, in accordance with the method for claim 2, the hydrogen content that it is characterized in that described hydrogen containing siloxane is 1.55wt%.
5, in accordance with the method for claim 2, the mass ratio 1-2 that it is characterized in that described hydrogen containing siloxane and tetramethyl-tetrem thiazolinyl cyclotetrasiloxane: 1-2.
6, in accordance with the method for claim 2, its feature is 1% of a mixture quality at described catalyzer.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101774814B (en) * | 2010-01-14 | 2012-11-21 | 天津大学 | Ceramic and carbon nano-fiber composite material and preparation method thereof |
| CN102040394B (en) * | 2010-11-30 | 2012-08-22 | 中国人民解放军国防科学技术大学 | Silicon oxygen carbon (SiOC) micro-mesoporous ceramic and preparation method thereof |
| CN102299338B (en) * | 2011-07-27 | 2014-06-11 | 中国人民解放军国防科学技术大学 | SiOC ceramic material used for preparing cathode of lithium ion battery, preparation method thereof and lithium ion battery |
| CN102417364B (en) * | 2011-08-02 | 2013-07-17 | 中国科学院化学研究所 | Micro-nano porous material and preparation method thereof |
| CN102417365B (en) * | 2011-08-02 | 2013-06-26 | 中国科学院化学研究所 | Micro-nano porous ceramic composite material and preparation method thereof |
| CN102311276B (en) * | 2011-08-02 | 2013-03-27 | 中国科学院化学研究所 | Si-C-O micro-nano porous ceramic and preparation method thereof |
| CN102417363B (en) * | 2011-08-02 | 2013-05-01 | 中国科学院化学研究所 | Micron-nano-sized porous composite material and preparation method thereof |
| CN102491780B (en) * | 2011-12-14 | 2014-04-02 | 天津大学 | Porous precursor ceramic and preparation method thereof |
| US20140238632A1 (en) * | 2013-02-28 | 2014-08-28 | General Electric Company | Methods for repairing ceramic cores |
| CN103265034A (en) * | 2013-05-07 | 2013-08-28 | 河南工业大学 | Preparation method of large capacity and high rate silicon base amorphous negative electrode material for lithium ion battery |
| US20150328678A1 (en) * | 2014-05-19 | 2015-11-19 | General Electric Company | Methods and compositions for formation of ceramic articles |
| CN107108234B (en) * | 2014-09-25 | 2021-04-20 | 梅里奥创新公司 | Silicon carbide materials based on polysilocarb, applications and devices |
| CN109956761A (en) * | 2017-12-22 | 2019-07-02 | 天津大学 | A kind of SiOC based high-temp-resistant high emission coating and preparation method thereof |
| CN108911752A (en) * | 2018-08-01 | 2018-11-30 | 渤海大学 | A method of synthesizing ceramic material under the conditions of extra electric field |
| CN109351205A (en) * | 2018-09-19 | 2019-02-19 | 广州中国科学院先进技术研究所 | A kind of silicon-oxygen-carbon ceramic hollow-fibre membrane and preparation method thereof |
| CN112830787B (en) * | 2021-01-15 | 2022-09-16 | 天津大学 | Preparation method of amorphous silicon-oxygen-carbon composite ceramic thermal barrier coating |
| CN113024280A (en) * | 2021-02-26 | 2021-06-25 | 天津大学 | Preparation method of double-layer silicon-oxygen-carbon composite ceramic coating for porous ceramic heat insulation matrix |
| CN115787141A (en) * | 2021-09-10 | 2023-03-14 | 苏州赛力菲陶纤有限公司 | Method for improving temperature resistance of continuous silicon carbide fiber |
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| 用作陶瓷先驱体的聚硅氧烷的交联与裂解. 马青松等.高分子材料科学与工程，第20卷第2期. 2004 |
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