CN1554802A - Process for preparing graphite surface anti oxidation coating material silicon carbide for nuclear reactor - Google Patents
Process for preparing graphite surface anti oxidation coating material silicon carbide for nuclear reactor Download PDFInfo
- Publication number
- CN1554802A CN1554802A CNA2003101217652A CN200310121765A CN1554802A CN 1554802 A CN1554802 A CN 1554802A CN A2003101217652 A CNA2003101217652 A CN A2003101217652A CN 200310121765 A CN200310121765 A CN 200310121765A CN 1554802 A CN1554802 A CN 1554802A
- Authority
- CN
- China
- Prior art keywords
- cracking
- silicon carbide
- pcs
- sih
- gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 41
- 239000011248 coating agent Substances 0.000 title claims abstract description 39
- 238000000576 coating method Methods 0.000 title claims abstract description 39
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910002804 graphite Inorganic materials 0.000 title claims abstract description 17
- 239000010439 graphite Substances 0.000 title claims abstract description 17
- 239000000463 material Substances 0.000 title claims description 10
- 238000004519 manufacturing process Methods 0.000 title description 3
- 230000003064 anti-oxidating effect Effects 0.000 title 1
- 229920003257 polycarbosilane Polymers 0.000 claims abstract description 42
- 238000005336 cracking Methods 0.000 claims abstract description 39
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 32
- 229910052710 silicon Inorganic materials 0.000 claims description 32
- 239000010703 silicon Substances 0.000 claims description 32
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 239000011159 matrix material Substances 0.000 claims description 14
- 229910003902 SiCl 4 Inorganic materials 0.000 claims description 13
- 238000010301 surface-oxidation reaction Methods 0.000 claims description 8
- 239000008096 xylene Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000000919 ceramic Substances 0.000 abstract description 2
- 239000003963 antioxidant agent Substances 0.000 abstract 1
- 230000003078 antioxidant effect Effects 0.000 abstract 1
- 239000000758 substrate Substances 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 24
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 235000002020 sage Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- Ceramic Products (AREA)
Abstract
The present invention discloses the preparation process of antioxidant silicon carbide coating on the surface of graphite for nuclear reactor. The preparation process includes first coating polycarbosilane (PCS) solution on the surface of substrate to form PCS coating after volatizing solvent; and high temperature cracking the PCS coating in protecting gas containing Si while regulate cracking temperature and cracking atmosphere independently to realize required C/Si ratio in silicon carbide. Adding gas containing Si component into the cracking atmosphere can make cracked PCS to react with gas containing Si component to avoid free carbon in prepared SiC while maintaining the ceramic yield.
Description
Technical field
The invention belongs to nuclear reactor material manufacturing technology field.Be particularly related to a kind of method for preparing used by nuclear reactor graphite surface oxidation resistant coating material silicon carbide with the chemical constitution of control cracking Polycarbosilane (PCS) preparation silicon carbide.
Technical background
Coat of silicon carbide is the new high-tech material of graphite surface oxidation resistant coating in the nuclear reactor owing to have characteristics such as hot strength height, thermal conductivity height, high-temperature oxidation resistance are good.In the preparation method of silicon carbide, since vowing that the island sage makes professor disclose successfully synthetic Polycarbosilane in document " S.Yajima et al.; Chem.Lett.; 931; 1975 " and changed into since the SiC fiber, owing to have low, simple and easy to control, the advantages such as product purity is high, excellent performance of preparation temperature, utilize cracking PCS to prepare the focus that SiC becomes SiC preparation method research soon.
Utilize the SiC of cracking PCS preparation to contain more uncombined carbon usually, unfavorable to the high-temperature oxidation resistance of SiC, thereby the uncombined carbon among the SiC of removal cracking PCS preparation has caused people's attention.The method of uncombined carbon that at present people had studied is used for eliminating the SiC of cracking PCS preparation comprises the composition that changes PCS and structure, cracking and in the hydrogen cracking etc. in a vacuum.Change composition and the structural manufacturing process more complicated of PCS, accurately the composition of the SiC of control preparation is relatively more difficult; Cracking can be eliminated uncombined carbon in vacuum or hydrogen atmosphere, but also can reduce the productive rate of pottery, and can only be corresponding to a specific cracking temperature for the SiC that obtains definite composition, and cracking temperature can not independently be controlled.
Summary of the invention
The purpose of this invention is to provide and can independently change cracking temperature and cracking atmosphere and control a kind of method for preparing used by nuclear reactor graphite surface oxidation resistant coating material silicon carbide that the silicon carbide chemistry of cracking Polycarbosilane preparation is formed, it is characterized in that: said method comprising the steps of:
1). be Polycarbosilane concentration that the xylene solution of 10-30wt% Polycarbosilane is coated in the graphite matrix surface at first, treat that obtaining thickness at matrix surface after the solvent evaporates is the PCS coating of 0.5-2.0 μ m;
2). the sample of the above-mentioned PCS of having coating is placed on the gas that contains silicon components and Ar or the H that flow is 100-1000ml/min
2The protective reaction stove of mixed gas in; under 1000 ℃ ~ 1300 ℃ treatment temps, carried out Pintsch process 1-5 hour; realize controlling the carbon/silicon ratio of the coat of silicon carbide of preparation by the gas content that contains silicon components in independent control cracking temperature and the cracking atmosphere, its carbon/silicon mass ratio is 0.6-4.2.
The described gas that contains silicon components is SiH
4Or SiCl
4
Described gas and Ar or the H that contains silicon components
2Mixed gas be SiH
4/ Ar, SiCl
4/ Ar, SiH
4/ H
2Or SiCl
4/ H
2, SiH wherein
4Or SiCl
4Content be 2vol%-3vol%.
Beneficial effect of the present invention: in cracking atmosphere, add the gas contain silicon components, can make the uncombined carbon among the SiC that PCS avoids preparing with the gas reaction that contains silicon components in the cracked process, and not reduce ceramic yield.This method can be in certain temperature range arbitrary temp change the carbon/silicon ratio of the silicon carbide of preparation by the content that contains the gas of silicon components in the control cracking atmosphere, cracking temperature and cracking atmosphere are formed and can independently be controlled.
Embodiment
The present invention is a kind of method for preparing used by nuclear reactor graphite surface oxidation resistant coating material silicon carbide, may further comprise the steps:
1). be Polycarbosilane concentration that the xylene solution of 10-30wt% Polycarbosilane is coated in the graphite matrix surface at first, treat that obtaining thickness at matrix surface after the solvent evaporates is the PCS coating of 0.5-2.0 μ m;
2). the sample of the above-mentioned PCS of having coating is placed on the gas SiH that contains silicon components
4Or SiCi
4With Ar or H
2Mixed gas SiH
4/ Ar, SiCl
4/ Ar, SiH
4/ H
2Or SiCl
4/ H
2, SiH wherein
4Or SiCl
4Content be 2vol%-3vol%; flow is in the protective reaction stove of 100-1000ml/min; under 1000 ℃～1300 ℃ treatment temps, carried out Pintsch process 1-5 hour; realize controlling the carbon/silicon ratio of the coat of silicon carbide of preparation by the gas content that contains silicon components in independent control cracking temperature and the cracking atmosphere, its carbon/silicon mass ratio is 0.6-4.2.
The present invention will be further described below by embodiment:
Embodiment 1
At first be that to form a layer thickness be the uniform films of 2.0 μ m by graphite matrix is immersed in its surface in Polycarbosilane concentration is Polycarbosilane/xylene solution of 10wt%; Matrix surface has obtained the PCS coating in dimethylbenzene volatilization back.With the above-mentioned carbon/silicon ratio that has prepared sample SiC coating of 1000 ℃ of cracking acquisitions in Ar gas of PCS coating is 3.7, at 2vol% SiH
4SiH
4Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 1.5 in the/Ar gas, at 3vol% SiH
4SiH
4Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 0.8 in the/Ar gas.
Embodiment 2
At first be that to form a layer thickness be the uniform film of 0.5 μ m by graphite matrix is immersed in its surface in Polycarbosilane concentration is Polycarbosilane/xylene solution of 20wt%; Matrix surface has obtained the PCS coating in dimethylbenzene volatilization back.With the above-mentioned sample of PCS coating that prepared at H
2Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 3.6 in the gas, at 2vol% SiH
4SiH
4/ H
2Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 1.2 in the gas, at 3vol% SiH
4SiH
4/ H
2Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 0.6 in the gas.
Embodiment 3
At first be that to form a layer thickness be the uniform films of 1.5 μ m by graphite matrix is immersed in its surface in Polycarbosilane concentration is Polycarbosilane/xylene solution of 30wt%; Matrix surface has obtained the PCS coating in dimethylbenzene volatilization back.With the above-mentioned carbon/silicon ratio that has prepared sample SiC coating of 1300 ℃ of cracking acquisitions in Ar gas of PCS coating is 4.2, at 2vol% SiH
4SiH
4Carbon/silicon the ratio of the SiC coating of 1500 ℃ of cracking acquisitions is 1.7 in the/Ar gas, at 3vol% SiH
4SiH
4Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 0.9 in the/Ar gas.
Embodiment 4
At first be that to form a layer thickness be the uniform films of 2.0 μ m by graphite matrix is immersed in its surface in Polycarbosilane concentration is Polycarbosilane/xylene solution of 20wt%; Matrix surface has obtained the PCS coating in dimethylbenzene volatilization back.With the above-mentioned sample of PCS coating that prepared at H
2Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 3.6 in the gas, at 2vol% SiCl
4SiCl
4/ H
2Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 1.3 in the gas, at 3vol% SiH
4SiH
4/ H
2Carbon/silicon the ratio of the SiC coating of 1000 ℃ of cracking acquisitions is 0.7 in the gas.
Claims (3)
1. method for preparing used by nuclear reactor graphite surface oxidation resistant coating material silicon carbide is characterized in that: said method comprising the steps of:
1). be Polycarbosilane concentration that the xylene solution of 10-30wt% Polycarbosilane is coated in the graphite matrix surface at first, treat that obtaining thickness at matrix surface after the solvent evaporates is the PCS coating of 0.5-2.0 μ m;
2). the sample of the above-mentioned PCS of having coating is placed on the gas that contains silicon components and Ar or the H that flow is 100-1000ml/min
2The protective reaction stove of mixed gas in; under 1000 ℃～1300 ℃ treatment temps, carried out Pintsch process 1-5 hour; realize controlling the carbon/silicon ratio of the coat of silicon carbide of preparation by the gas content that contains silicon components in independent control cracking temperature and the cracking atmosphere, its carbon/silicon mass ratio is 0.6-4.2.
2. according to the described method for preparing used by nuclear reactor graphite surface oxidation resistant coating material silicon carbide of claim 1, it is characterized in that: the described gas that contains silicon components is SiH
4Or SiCl
4
3. according to the described method for preparing used by nuclear reactor graphite surface oxidation resistant coating material silicon carbide of claim 1, it is characterized in that: described gas and Ar or the H that contains silicon components
2Mixed gas be SiH
4/ Ar, SiCl
4/ Ar, SiH
4/ H
2Or SiCl
4/ H
2, SiH wherein
4Or SiCl
4Content be 2vol%-3vol%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101217652A CN1304638C (en) | 2003-12-23 | 2003-12-23 | Process for preparing graphite surface anti oxidation coating material silicon carbide for nuclear reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2003101217652A CN1304638C (en) | 2003-12-23 | 2003-12-23 | Process for preparing graphite surface anti oxidation coating material silicon carbide for nuclear reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1554802A true CN1554802A (en) | 2004-12-15 |
| CN1304638C CN1304638C (en) | 2007-03-14 |
Family
ID=34338541
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101217652A Expired - Fee Related CN1304638C (en) | 2003-12-23 | 2003-12-23 | Process for preparing graphite surface anti oxidation coating material silicon carbide for nuclear reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1304638C (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574747A (en) * | 2009-10-09 | 2012-07-11 | 信越化学工业株式会社 | Method for producing carbon material coated with silicon carbide |
| US20150017335A1 (en) * | 2012-01-30 | 2015-01-15 | Hemlock Semiconductor Corporation | Method of repairing and/or protecting a surface in a reactor |
| CN104871251A (en) * | 2012-12-19 | 2015-08-26 | 揖斐电株式会社 | Member for nuclear reactors |
| CN105506735A (en) * | 2015-12-10 | 2016-04-20 | 江西赛维Ldk太阳能高科技有限公司 | Carbon material structural part for polycrystalline silicon ingots and preparation method of carbon material structural part |
| CN105753514A (en) * | 2016-03-02 | 2016-07-13 | 石志强 | Preparation method of antioxidant SiC compound protecting layer on surface of graphite carbon material |
| CN109246977A (en) * | 2018-08-01 | 2019-01-18 | 天津大学 | A kind of preparation method of high thermal conductivity graphite composite material |
| CN112624797A (en) * | 2020-12-15 | 2021-04-09 | 湖南德智新材料有限公司 | Graphite surface gradient silicon carbide coating and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5234675A (en) * | 1989-06-30 | 1993-08-10 | Nippon Carbon Co. Ltd. | Manufacturing sintered body of silicon carbide by using SiC whiskers in a multiple heating step process |
-
2003
- 2003-12-23 CN CNB2003101217652A patent/CN1304638C/en not_active Expired - Fee Related
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102574747A (en) * | 2009-10-09 | 2012-07-11 | 信越化学工业株式会社 | Method for producing carbon material coated with silicon carbide |
| CN102574747B (en) * | 2009-10-09 | 2014-10-15 | 信越化学工业株式会社 | Method for producing carbon material coated with silicon carbide |
| US20150017335A1 (en) * | 2012-01-30 | 2015-01-15 | Hemlock Semiconductor Corporation | Method of repairing and/or protecting a surface in a reactor |
| US9687876B2 (en) * | 2012-01-30 | 2017-06-27 | Hemlock Semiconductor Corporation | Method of repairing and/or protecting a surface in a reactor |
| CN104871251A (en) * | 2012-12-19 | 2015-08-26 | 揖斐电株式会社 | Member for nuclear reactors |
| CN104871251B (en) * | 2012-12-19 | 2017-03-08 | 揖斐电株式会社 | Used by nuclear reactor part |
| CN105506735A (en) * | 2015-12-10 | 2016-04-20 | 江西赛维Ldk太阳能高科技有限公司 | Carbon material structural part for polycrystalline silicon ingots and preparation method of carbon material structural part |
| CN105506735B (en) * | 2015-12-10 | 2017-12-26 | 江西赛维Ldk太阳能高科技有限公司 | A kind of polycrystalline silicon ingot casting carbon material structural member and preparation method thereof |
| CN105753514A (en) * | 2016-03-02 | 2016-07-13 | 石志强 | Preparation method of antioxidant SiC compound protecting layer on surface of graphite carbon material |
| CN109246977A (en) * | 2018-08-01 | 2019-01-18 | 天津大学 | A kind of preparation method of high thermal conductivity graphite composite material |
| CN112624797A (en) * | 2020-12-15 | 2021-04-09 | 湖南德智新材料有限公司 | Graphite surface gradient silicon carbide coating and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1304638C (en) | 2007-03-14 |
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Granted publication date: 20070314 Termination date: 20100125 |