JPH0365581A - Method for improving oxidation resistance of sintered carbon - Google Patents
Method for improving oxidation resistance of sintered carbonInfo
- Publication number
- JPH0365581A JPH0365581A JP19793489A JP19793489A JPH0365581A JP H0365581 A JPH0365581 A JP H0365581A JP 19793489 A JP19793489 A JP 19793489A JP 19793489 A JP19793489 A JP 19793489A JP H0365581 A JPH0365581 A JP H0365581A
- Authority
- JP
- Japan
- Prior art keywords
- sintered carbon
- carbon material
- sintered body
- carbon
- silicon carbide
- 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.)
- Pending
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 38
- 238000000034 method Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 10
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 10
- 229920001709 polysilazane Polymers 0.000 claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 17
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 17
- 239000012298 atmosphere Substances 0.000 claims abstract description 13
- 230000001590 oxidative effect Effects 0.000 claims abstract description 9
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 8
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 abstract description 11
- 239000003575 carbonaceous material Substances 0.000 abstract description 9
- 238000000576 coating method Methods 0.000 abstract description 8
- 239000002904 solvent Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 7
- 239000011248 coating agent Substances 0.000 abstract description 7
- 239000010410 layer Substances 0.000 abstract description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 229910002804 graphite Inorganic materials 0.000 abstract description 3
- 239000010439 graphite Substances 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000005245 sintering Methods 0.000 abstract description 3
- 229920000049 Carbon (fiber) Polymers 0.000 abstract description 2
- 239000005046 Chlorosilane Substances 0.000 abstract description 2
- 229910021529 ammonia Inorganic materials 0.000 abstract description 2
- 239000012300 argon atmosphere Substances 0.000 abstract description 2
- 239000006229 carbon black Substances 0.000 abstract description 2
- 239000004917 carbon fiber Substances 0.000 abstract description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011247 coating layer Substances 0.000 abstract description 2
- 239000000571 coke Substances 0.000 abstract description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract description 2
- 239000011295 pitch Substances 0.000 abstract description 2
- 238000007865 diluting Methods 0.000 abstract 1
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 15
- 239000000463 material Substances 0.000 description 7
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 238000005121 nitriding Methods 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- 238000005229 chemical vapour deposition Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- 229920002379 silicone rubber Polymers 0.000 description 2
- 239000004945 silicone rubber Substances 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 101000604590 Homo sapiens Keratin, type I cuticular Ha3-I Proteins 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 102100038185 Keratin, type I cuticular Ha3-I Human genes 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910021383 artificial graphite Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910021382 natural graphite Inorganic materials 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
この発明は炭素焼結体の耐酸化性向上方法に関するもの
である。DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] This invention relates to a method for improving the oxidation resistance of a carbon sintered body.
炭素焼結体は１０００°Ｃ以上の高温においても強度低
下がなくまた高い熱伝導性を持つところから高温材料と
して期待される。しかし、空気中で５００°Ｃを越える
と酸化し、使用に耐えなくなる。そこでこの高温におけ
る酸化を防止する方法として、高温では不活性ガス雰囲
気で使用するか、あるいは化学蒸着法により炭素焼結体
表面に炭化ケイ素を被覆して酸化保護膜を形成し、高温
の大気雰囲気での使用を可能にする方法が知られている
。後者の炭化ケイ素で被覆した炭素焼結体はシリコン単
結晶引き上げ装置のるつぼ、エピタキシャル成長装置の
サセプター等半導体関連分野で広く使用されている。Carbon sintered bodies are expected to be used as high-temperature materials because they do not decrease in strength even at high temperatures of 1000°C or higher and have high thermal conductivity. However, if the temperature exceeds 500°C in the air, it will oxidize and become unusable. Therefore, as a method to prevent oxidation at high temperatures, use an inert gas atmosphere at high temperatures, or coat the surface of the carbon sintered body with silicon carbide by chemical vapor deposition to form an oxidation protective film. Methods are known to enable use in The latter carbon sintered body coated with silicon carbide is widely used in semiconductor-related fields such as crucibles for silicon single crystal pulling equipment and susceptors for epitaxial growth equipment.
また、炭素材料の表層部を高温で一酸化ケイ素ガスと反
応させて炭化ケイ素に転換させる転換法も知られている
。Also known is a conversion method in which the surface layer of a carbon material is reacted with silicon monoxide gas at high temperature to convert it into silicon carbide.
化学蒸着法においては炭化ケイ素は炭素焼結体の表面に
積層されるので両者の密着が不十分である。また両者の
熱膨張率に差があるので使用時の加熱、冷却の繰返しに
よって被覆層が剥離したり亀裂が生じたりして基材の炭
素焼結体が酸化損傷するという問題もある。転換法によ
れば密着性の良い被膜が得られるが、１７００°Ｃ以上
の高温を必要とするので装置及び操作の両面で問題があ
る。さらに、化学蒸着法と転換法に共通の問題点として
、ケイ素源がガスで供給されるので炭化ケイ素として固
定できる割合が低いという問題もある。In the chemical vapor deposition method, silicon carbide is laminated on the surface of the carbon sintered body, so the adhesion between the two is insufficient. Further, since there is a difference in coefficient of thermal expansion between the two, there is also the problem that the coating layer peels off or cracks occur due to repeated heating and cooling during use, resulting in oxidation damage to the carbon sintered body of the base material. Although a film with good adhesion can be obtained by the conversion method, it requires a high temperature of 1700° C. or higher, which poses problems in terms of both equipment and operation. Furthermore, a problem common to the chemical vapor deposition method and the conversion method is that the silicon source is supplied in the form of a gas, so that the proportion of silicon carbide that can be fixed is low.
この発明は上記のような問題点を解決するためになされ
たものであり、密着性の良い炭化ケイ素を比較的低温で
形成する手段を提供することを目的とする。This invention was made to solve the above-mentioned problems, and an object thereof is to provide a means for forming silicon carbide with good adhesiveness at a relatively low temperature.
本発明者らは上記目的を達成するべく鋭意検討の結果、
炭素焼結体に無機ポリシラザンを被覆して非窒化性かつ
非酸化性雰囲気で加熱して炭素焼結体の表面に炭化ケイ
素の層を形成させることにより耐酸化性の高い強靭な被
膜を容易に炭素焼結体の表面に形成させることができる
ことを見出して本発明を完成するに至った。As a result of intensive studies to achieve the above object, the inventors of the present invention found that
A strong coating with high oxidation resistance can be easily formed by coating a carbon sintered body with inorganic polysilazane and heating it in a non-nitriding and non-oxidizing atmosphere to form a layer of silicon carbide on the surface of the carbon sintered body. The present invention was completed by discovering that it can be formed on the surface of a carbon sintered body.
炭素焼結体は、天然および人造黒鉛、カーボンブラック
、コークス、ピッチ、炭素繊維などを原料として底形、
焼結し、黒鉛化したものである。Carbon sintered bodies are made from natural and artificial graphite, carbon black, coke, pitch, carbon fiber, etc.
It is sintered and graphitized.
焼結助剤として炭化物（ＴｉＣ，ＺｒＣ，ＮｂＣ，Ｂ４
Ｃ等）、ホウ化物（ＴｉＢ、、ＺｒＢ、等）を添加して
もよい、さらに、必要に応じて焼結後ピッチ含浸し炭化
焼成を行って密度を高めたものでもよい。密度は高い方
が良く嵩密度で１．６ｇ／ｃ＋ｆ１以上あることが好ま
しい。この発明の方法では炭素のケイ化によって体積膨
張するとはいえ、１．６ｇ／ｃ＋ｆ１未満のように密度
が低いと雰囲気ガスとの接触面積が多く面形状が入りく
んでいるので炭化ケイ素被膜によって完全に接触を断つ
ことが困難になるからである。炭素焼結体の形状はその
使用目的等に応じて定まり、特に制限されない。炭素焼
結体には必要により予めジクロロメタン等の有機溶剤で
洗浄してから無機ポリシラザンを被覆させる。Carbide (TiC, ZrC, NbC, B4
C, etc.), borides (TiB, ZrB, etc.) may be added, and if necessary, the density may be increased by impregnating pitch after sintering and performing carbonization firing. The higher the density, the better, and preferably a bulk density of 1.6 g/c+f1 or more. In the method of this invention, although the volume expands due to silicification of carbon, if the density is low, such as less than 1.6 g/c + f1, there is a large contact area with the atmospheric gas and the surface shape is complicated, so the silicon carbide film completely expands the volume. This is because it becomes difficult to break off contact with other people. The shape of the carbon sintered body is determined depending on its intended use and is not particularly limited. If necessary, the carbon sintered body is cleaned in advance with an organic solvent such as dichloromethane, and then coated with inorganic polysilazane.
無機ポリシラザンはクロロシランＨａ−３Ｉ ＣＩ−（
ａ＝１．２．３．４）を溶剤によって希釈してアンモニ
アと反応させることによって得られるエラストマーであ
り、本発明の方法にはＨｚ Ｓ ｉ Ｃ１□単体もしく
はＨｚＳｉＣｌｚを主体とした異種のクロロシランの混
合物を原料とすることにより得られる常温で液状のもの
が好ましい。この溶剤としてはベンゼン、ジエチルエー
テル、ジクロロメタン、テトラヒドロフラン、ピリジン
等が適用できるが、合成される無機ポリシラザンの構造
、組成、分子量は溶剤の種類によって若干異なる。しか
し、いずれも水素、窒素、ケイ素からなり炭素は含まな
い。The inorganic polysilazane is chlorosilane Ha-3I CI-(
a=1.2.3.4) with a solvent and reacted with ammonia, and the method of the present invention involves the use of Hz Si C1 Preferably, it is liquid at room temperature and is obtained by using a mixture as a raw material. As the solvent, benzene, diethyl ether, dichloromethane, tetrahydrofuran, pyridine, etc. can be used, but the structure, composition, and molecular weight of the inorganic polysilazane to be synthesized differ slightly depending on the type of solvent. However, they all consist of hydrogen, nitrogen, and silicon and do not contain carbon.
例えば（Ｈ，５ｉＮＨ） ｘ （ＨｚＳｉＮＨ） ｘ
（（ＨｚＳｉ）＋、５Ｎ）ｙ等の構造を有するものが知
られている。このような液状の無機ポリシラザンを単味
もしくは溶剤で希釈して炭素焼結体の被覆に供する。こ
の溶剤としては特に制約はないが、ベンゼン、ジエチル
エーテル、ジクロロメタン、テトラヒドロフラン、ピリ
ジンが目的に適う。希釈の程度は炭素焼結体上に形成さ
れる液膜の厚さおよび液状ポリシラザンの炭素焼結体の
有する開気孔への進入のし易さに影響される。溶剤の濃
度は０〜８０重量％が適当である。８０重置方を越える
と無機ポリシラザンの膜厚が薄くなって基材の露出が起
こりやすくなる。For example, (H,5iNH) x (HzSiNH) x
Those having a structure such as ((HzSi)+, 5N)y are known. Such a liquid inorganic polysilazane is used alone or diluted with a solvent to coat a carbon sintered body. There are no particular restrictions on this solvent, but benzene, diethyl ether, dichloromethane, tetrahydrofuran, and pyridine are suitable for the purpose. The degree of dilution is influenced by the thickness of the liquid film formed on the carbon sintered body and the ease with which liquid polysilazane can enter the open pores of the carbon sintered body. The appropriate concentration of the solvent is 0 to 80% by weight. If the stacking direction exceeds 80, the film thickness of the inorganic polysilazane becomes thin and the base material is likely to be exposed.
無機ポリシラザンの乾燥膜厚は４０〜２００Ｊ！ｍ程度
が適当である。被覆は炭素焼結体の全面に行う他、炭素
焼結体が使用時に露出して酸化されやすい部位のみに対
して行ってもよい。The dry film thickness of inorganic polysilazane is 40-200J! A value of about m is appropriate. The coating may be applied to the entire surface of the carbon sintered body, or may be applied only to portions of the carbon sintered body that are exposed during use and are easily oxidized.
被覆方法に関しては特に制約はなく、刷毛塗り、炭素焼
結体の浸漬等が適用できる。浸漬し、かつ炭素焼結体を
予め脱気しあるいは浸漬中に無機ポリシラザンを加圧す
ると開気孔への無機ポリシラザンの浸透が良好となり基
材の露出のない被覆が得られる。There are no particular restrictions on the coating method, and brush coating, dipping of a carbon sintered body, etc. can be applied. If the carbon sintered body is immersed and the carbon sintered body is deaerated in advance or the inorganic polysilazane is pressurized during the immersion, the inorganic polysilazane penetrates into the open pores well, and a coating without exposing the base material can be obtained.
被覆を完了した炭素焼結体を不活性ガス中で加熱すると
、溶剤の蒸発に続いて、１５０℃あたりから無機ポリシ
ラザンの熱分解がはじまり、これは６００’Ｃ付近でほ
ぼ終了して非晶質の窒化ケイ素が得られる。引き続き、
高温下非窒化性雰囲気から非酸化性雰囲気で熱処理を施
す。非窒化性雰囲気とは、無機ポリシラザンから転化し
た非晶質の窒化ケイ素を基材の炭素と反応させて炭化ケ
イ素を生成させる際に発生する窒素ガスの放出を妨げな
い十分低い窒素分圧を意味する。この上限の窒素分圧は
１３００°Ｃで０．１ａｔｍ、１９００℃で２０ａ ｔ
ｍであり、第１図に斜線で示す範囲内に窒素分圧を保持
する必要がある。When the coated carbon sintered body is heated in an inert gas, following the evaporation of the solvent, thermal decomposition of the inorganic polysilazane begins at around 150°C, which almost ends at around 600°C, and becomes amorphous. of silicon nitride is obtained. continuation,
Heat treatment is performed at high temperature in a non-nitriding to non-oxidizing atmosphere. A non-nitriding atmosphere means a sufficiently low nitrogen partial pressure that does not prevent the release of nitrogen gas generated when silicon carbide is produced by reacting amorphous silicon nitride converted from inorganic polysilazane with carbon in the base material. do. This upper limit nitrogen partial pressure is 0.1 atm at 1300°C and 20atm at 1900°C.
m, and it is necessary to maintain the nitrogen partial pressure within the range shown by diagonal lines in FIG.
非酸化性雰囲気とは酸素ガス、水分等の酸化性ガスを実
質的に含まず、炭化ケイ素の層を形成させる加熱工程に
おいて一酸化ケイ素の生成が無視できる雰囲気をいう。A non-oxidizing atmosphere is an atmosphere that does not substantially contain oxidizing gases such as oxygen gas and moisture, and in which the production of silicon monoxide can be ignored in the heating process for forming a silicon carbide layer.
雰囲気ガスとしてはヘリウム、ネオン、アルゴン等の不
活性ガスあるいは水素ガス等が好ましい。圧力は１０−
４〜１１００ａｔ程度が適当である。非窒化性かつ非酸
化性雰囲気での加熱温度は１３００〜１９００’Ｃが適
当である。１３００°Ｃ未満では反応速度が遅く、実用
的でない。一方、１９００°Ｃを越えると雰囲気中に不
可避的に混入している微量の酸素によりケイ素が一酸化
ケイ素ガスとして揮散する現象が無視できなくなる。こ
のためケイ素の損失が大きくなる。The atmospheric gas is preferably an inert gas such as helium, neon, or argon, or hydrogen gas. The pressure is 10-
Approximately 4 to 1100 at is appropriate. The appropriate heating temperature in a non-nitriding and non-oxidizing atmosphere is 1300 to 1900'C. If the temperature is lower than 1300°C, the reaction rate is slow and it is not practical. On the other hand, when the temperature exceeds 1900°C, the phenomenon that silicon volatilizes as silicon monoxide gas cannot be ignored due to trace amounts of oxygen that are inevitably mixed in the atmosphere. Therefore, silicon loss increases.
加熱時間は炭化ケイ素の層を形成させるのに充分な時間
があればよ＜ １３００°Ｃでは５〜２０時間程度、１
９００℃では０．５〜５時間程度でよい。The heating time should be enough time to form a layer of silicon carbide.
At 900°C, it may take about 0.5 to 5 hours.
炭素焼結体に無機ポリシラザンを被覆して非窒化性かつ
非酸化性雰囲気で加熱することにより、下記の反応が起
こり、炭素焼結体表面の炭素が反応して炭化ケイ素の被
膜を形成する。By coating a carbon sintered body with inorganic polysilazane and heating it in a non-nitriding and non-oxidizing atmosphere, the following reaction occurs, and carbon on the surface of the carbon sintered body reacts to form a silicon carbide film.
Ｓ ｉ Ｎ ｘ ＋ Ｃ−Ｓ ｉ Ｃ＋ （Ｘ ／ ２
） Ｎ ｚ↑〔実施例〕
実施例１
嵩密度２．０１ｇ／ｃｆｆｌＯ高密度等方性黒鉛焼結体
（５０肋Ｘ ５０ｍｍ Ｘ １０ｍｍ ）をジクロロメ
タンに浸漬し、２４時間放置後取出して乾燥した。この
焼結体をシリコーンゴムの容器に入れ真空脱気して１０
−２Ｔｏｒｒに到達させた。液状の無機ポリシラザンを
容器内に導入して焼結体を浸漬させた。大気圧に戻し、
このゴム容器にシリコーンゴム製の蓋をして封入し、冷
間静水圧プレスでゴム容器の外側から５０００ｋｇ／ｃ
ｍ”の圧力をかけたのち処理物を取出した。これを加熱
炉で１０”Ｃ／ｍｉｎの昇温速度で６００°Ｃまで上げ
、１時間保持後放冷した。続いて、焼結炉に入れ常圧の
アルゴン雰囲気で１５００″Ｃまで３０″（／ｍｉｎで
昇温し、５時間保持後放冷した。この焼結体を１２００
’Ｃ１１００時間大気雰囲気に保持したところ、わずか
に０．２６重量％の重量増加が観察されたほか変化がな
かった。S i N x + C-S i C+ (X / 2
) N z↑ [Example] Example 1 A high-density isotropic graphite sintered body (50 ribs x 50 mm x 10 mm) with a bulk density of 2.01 g/cfflO was immersed in dichloromethane, left for 24 hours, and then taken out and dried. This sintered body was placed in a silicone rubber container and vacuum degassed for 10 minutes.
-2 Torr was reached. Liquid inorganic polysilazane was introduced into the container and the sintered body was immersed therein. return to atmospheric pressure,
This rubber container was sealed with a silicone rubber lid, and a pressure of 5000 kg/cm was applied from the outside of the rubber container using a cold isostatic press.
After applying a pressure of 1.5 m", the treated material was taken out. The material was heated to 600° C. at a heating rate of 10" C/min in a heating furnace, maintained for 1 hour, and then allowed to cool. Subsequently, the sintered body was placed in a sintering furnace and heated at a rate of 30"/min to 1500"C in an argon atmosphere under normal pressure, and after being maintained for 5 hours, it was left to cool.
When the sample was kept in the air for 1100 hours, no other changes were observed except for a slight increase in weight of 0.26% by weight.
実施例２
無機ポリシラデフ５０重景％、ジクロロメタン５０重量
％の溶液を調製し、実施例１と同様の操作を高密度等方
性黒鉛焼結体（５０ａａＸ５０鵬Ｘ１０ｍｍ）に対して
施したところ、この焼結体はわずかに０．２０重量％の
重量増加が観察されたほか変化がなかった。Example 2 A solution of 50% by weight of inorganic polysiladeph and 50% by weight of dichloromethane was prepared, and the same operation as in Example 1 was performed on a high-density isotropic graphite sintered body (50aa x 50a x 10mm). There was no change in the sintered body other than a slight increase in weight of 0.20% by weight.
［発明の効果］
以上のように、この発明によれば、液状の無機ポリシラ
ザンにより炭素焼結体表面に被膜を形成し、炭素との反
応によって表層炭素を炭化ケイ素に転化し密着性の良い
炭化ケイ素膜を効率良く形成させることができるので、
この方法によれば炭素が本来持つ耐熱性に加え、高温に
おける耐酸化性のある炭素焼結体を製造できる。[Effects of the Invention] As described above, according to the present invention, a film is formed on the surface of a carbon sintered body using liquid inorganic polysilazane, and surface carbon is converted to silicon carbide by reaction with carbon, resulting in carbonization with good adhesion. Because silicon films can be formed efficiently,
According to this method, it is possible to produce a carbon sintered body that has not only the heat resistance that carbon inherently has, but also has oxidation resistance at high temperatures.
第１図は非窒化性雰囲気を達成しうる窒素分圧と加熱温
度との関係を示すグラフである。FIG. 1 is a graph showing the relationship between nitrogen partial pressure and heating temperature that can achieve a non-nitriding atmosphere.
Claims (1)
性かつ非酸化性雰囲気で加熱することにより炭素焼結体
表面に炭化ケイ素の層を形成させることを特徴とする耐
酸化性の向上した炭素焼結体の製造方法A carbon sintered body coated with inorganic polysilazane and heated in a non-nitrogen and non-oxidizing atmosphere to form a layer of silicon carbide on the surface of the carbon sintered body, which has improved oxidation resistance. Method for manufacturing carbon sintered body
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19793489A JPH0365581A (en) | 1989-08-01 | 1989-08-01 | Method for improving oxidation resistance of sintered carbon |
| US07/554,697 US5114749A (en) | 1989-08-01 | 1990-07-18 | Method for manufacturing carbon material having good resistance to oxidation by coating the carbon material with an inorganic polysilazane and then heating |
| EP90114770A EP0411611A1 (en) | 1989-08-01 | 1990-08-01 | Method for manufacturing carbon material good in resistance to oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19793489A JPH0365581A (en) | 1989-08-01 | 1989-08-01 | Method for improving oxidation resistance of sintered carbon |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0365581A true JPH0365581A (en) | 1991-03-20 |
Family
ID=16382722
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19793489A Pending JPH0365581A (en) | 1989-08-01 | 1989-08-01 | Method for improving oxidation resistance of sintered carbon |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0365581A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013536150A (en) * | 2010-08-27 | 2013-09-19 | コミッサリア タ レネルジー アトミク エ オ エネルジー オルタネイティヴ | Crucible for solidifying silicon ingot |
| WO2014104804A1 (en) * | 2012-12-28 | 2014-07-03 | Park Myung Oh | Apparatus for connecting and releasing fishing tool |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53149194A (en) * | 1977-05-31 | 1978-12-26 | Sharp Corp | Coating method for graphite substrate with silicon carbide |
| JPS55104982A (en) * | 1979-02-07 | 1980-08-11 | Usui Kokusai Sangyo Kk | Manufacture of silicon carbideecarbon composite body |
| JPS58172295A (en) * | 1982-03-30 | 1983-10-11 | Ibiden Co Ltd | Method for pulling up silicon single crystal |
| JPH02111679A (en) * | 1988-10-20 | 1990-04-24 | Tokai Carbon Co Ltd | Production of oxidation-resistant carbon fiber-reinforced carbon material |
-
1989
- 1989-08-01 JP JP19793489A patent/JPH0365581A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS53149194A (en) * | 1977-05-31 | 1978-12-26 | Sharp Corp | Coating method for graphite substrate with silicon carbide |
| JPS55104982A (en) * | 1979-02-07 | 1980-08-11 | Usui Kokusai Sangyo Kk | Manufacture of silicon carbideecarbon composite body |
| JPS58172295A (en) * | 1982-03-30 | 1983-10-11 | Ibiden Co Ltd | Method for pulling up silicon single crystal |
| JPH02111679A (en) * | 1988-10-20 | 1990-04-24 | Tokai Carbon Co Ltd | Production of oxidation-resistant carbon fiber-reinforced carbon material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013536150A (en) * | 2010-08-27 | 2013-09-19 | コミッサリア タ レネルジー アトミク エ オ エネルジー オルタネイティヴ | Crucible for solidifying silicon ingot |
| WO2014104804A1 (en) * | 2012-12-28 | 2014-07-03 | Park Myung Oh | Apparatus for connecting and releasing fishing tool |
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