JPH04164860A - Production of carbon material coated with carbon coating film - Google Patents
Production of carbon material coated with carbon coating filmInfo
- Publication number
- JPH04164860A JPH04164860A JP2290091A JP29009190A JPH04164860A JP H04164860 A JPH04164860 A JP H04164860A JP 2290091 A JP2290091 A JP 2290091A JP 29009190 A JP29009190 A JP 29009190A JP H04164860 A JPH04164860 A JP H04164860A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- resin
- carbon material
- solution
- graphite
- 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.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 25
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 22
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- 239000011248 coating agent Substances 0.000 title abstract description 12
- 238000000576 coating method Methods 0.000 title abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 45
- 239000011347 resin Substances 0.000 claims abstract description 45
- 239000003960 organic solvent Substances 0.000 claims abstract description 8
- 239000004962 Polyamide-imide Substances 0.000 claims description 16
- 229920002312 polyamide-imide Polymers 0.000 claims description 16
- 125000003118 aryl group Chemical group 0.000 claims description 11
- 230000001590 oxidative effect Effects 0.000 claims description 3
- 238000010304 firing Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 13
- 239000002245 particle Substances 0.000 abstract description 9
- 239000002184 metal Substances 0.000 abstract description 8
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 abstract description 6
- 150000002739 metals Chemical class 0.000 abstract description 5
- 230000009257 reactivity Effects 0.000 abstract description 4
- 239000004760 aramid Substances 0.000 abstract 2
- 229920003235 aromatic polyamide Polymers 0.000 abstract 2
- 150000003949 imides Chemical class 0.000 abstract 2
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 239000007770 graphite material Substances 0.000 description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 14
- 230000000694 effects Effects 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 7
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000011889 copper foil Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 239000002296 pyrolytic carbon Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004693 Polybenzimidazole Substances 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 239000002390 adhesive tape Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005219 brazing Methods 0.000 description 1
- 230000001680 brushing effect Effects 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000005183 environmental health Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229920002480 polybenzimidazole Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000009719 polyimide resin Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
- Carbon And Carbon Compounds (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は炭素被膜で被覆された炭素材料の製造方法に関
し、更に詳しくは炭素／炭素複合材製造用マンドレル又
は（及び）成形用鋳型、金属溶解るつぼ、ガラス封着用
治具、ろう付は用治具、電気炉用黒鉛材部品、又は連続
鋳造用ダイス等に極めて好適に用いられる炭素材料を製
造する方法に関する。DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to a method for manufacturing a carbon material coated with a carbon film, and more particularly to a mandrel and/or mold for manufacturing a carbon/carbon composite material, and a method for manufacturing a carbon material coated with a carbon film. The present invention relates to a method for producing a carbon material that is very suitably used in melting crucibles, glass sealing jigs, brazing jigs, graphite parts for electric furnaces, dies for continuous casting, and the like.
従来炭素乃至黒鉛材料を使用する場合これら材料の表面
から粒子が脱落し、使用場所の汚染及び粒子の粉塵の製
品への付着が生じ、製品の歩留りが低下するという大き
な問題となっている。即ちこれら材料に於いては発生す
る粉塵が大きな問題となり、上記の難点以外にも作業者
等に対する環境衛生上の問題も生じている。またこれら
材料は金属と反応して炭化物を生成するため、金属溶解
るつぼとしての使用に大きな制限がある。Conventionally, when carbon or graphite materials are used, particles fall off from the surface of these materials, causing contamination of the place of use and adhesion of particle dust to the product, which poses a major problem of lowering the yield of the product. That is, the dust generated by these materials is a major problem, and in addition to the above-mentioned problems, there are also environmental health problems for workers and the like. Furthermore, since these materials react with metals to produce carbides, there are major limitations on their use as metal melting crucibles.
このような炭素乃至黒鉛材料の粒子脱落を防ぐ手段とし
て従来熱分解炭素でこれら材料を被覆する方法も知られ
ている。しかしこの方法では複雑な装置が必要であり、
工業的実施には大きな難点となっている。また例えばダ
イオード封着用治具のように０．１〜１胴程度の細穴が
必要な場合には析出した熱分解炭素により、この細大が
埋まってしまうという難点も存在する。As a means of preventing particles of carbon or graphite materials from falling off, a method of coating these materials with pyrolytic carbon is also known. However, this method requires complicated equipment;
This poses a major difficulty in industrial implementation. Furthermore, when a narrow hole of about 0.1 to 1 diameter is required, as in the case of a jig for sealing a diode, there is also the problem that the narrow hole is filled with precipitated pyrolytic carbon.
また他の方法として、ガラス状炭素膜でこれら材料を強
固に被覆する方法も知られているが、やはり細大を埋め
てしまうという欠点を解消することはできない。Another known method is to firmly cover these materials with a glassy carbon film, but this method still cannot overcome the drawback of filling in small areas.
本発明が解決しようとする課題は、これら材料に生ずる
粒子脱落という難点を解決することであり、加えて黒鉛
材の表面を改質することにより、細穴を必要とする分野
に於いては細穴を埋めることなく、炭素粒子脱落を防止
すると共に金属との反応性を抑え黒鉛材部品の寿命を長
くするための対策を開発することである。The problem to be solved by the present invention is to solve the problem of particle shedding that occurs in these materials.In addition, by modifying the surface of graphite material, it is possible to solve the problem of fine holes in fields that require fine holes. The objective is to develop a countermeasure that can prevent carbon particles from falling off without filling the holes, suppress reactivity with metals, and extend the life of graphite parts.
この課題は芳香族ポリアミドイミド樹脂の有機溶剤溶液
を用いて炭素乃至黒鉛材の表面に該樹脂の被膜を形成せ
しめ、これを硬化後非酸化性雰囲気中で焼成して炭化又
は更に黒鉛化することによって解決される。The objective is to form a film of the resin on the surface of a carbon or graphite material using an organic solvent solution of aromatic polyamide-imide resin, and after curing, carbonize it or further graphitize it by firing it in a non-oxidizing atmosphere. solved by.
本発明者の研究に依れば炭素乃至黒鉛材の表面に芳香族
ポリアミドイミド樹脂という特定の樹脂を溶剤に溶解し
て含浸又は塗布し、これを硬化して炭化更に要すれば黒
鉛化すると得られる炭素被膜を有する目的物炭素乃至黒
鉛材は粒子脱落が大幅に改善され、殆ど粉塵を生じない
ことが明らかとなった。また炭素乃至黒鉛材に細大が存
在する場合でも上記樹脂の有機溶剤溶液は細穴中に浸入
し、細穴を表面で被覆することがないので細大が殆どそ
のまま残存することが明らかとなった。According to the research of the present inventor, it is possible to impregnate or coat the surface of a carbon or graphite material with a specific resin called aromatic polyamideimide resin dissolved in a solvent, and then harden it to carbonize it and, if necessary, graphitize it. It has become clear that the target carbon or graphite material with a carbon coating has significantly improved particle shedding and hardly generates dust. Furthermore, it has become clear that even if there are fine sizes in the carbon or graphite material, the organic solvent solution of the resin infiltrates into the pores and does not cover the pores with the surface, so that most of the fine sizes remain as they are. Ta.
更に本発明者の研究によると、上記芳香族ポリアミドイ
ミド樹脂の有機溶剤溶液を使用する際にはその溶液の濃
度を低くし、或いは使用する樹脂の分子量を低分子量と
することにより上記粒子脱落並びに細穴閉塞防止作用が
一段と大きく発揮されることが明らかとなった。Furthermore, according to research by the present inventors, when using an organic solvent solution of the aromatic polyamide-imide resin, reducing the concentration of the solution or lowering the molecular weight of the resin used can reduce the drop-off of the particles and It became clear that the effect of preventing pore clogging was even greater.
本発明に使用される樹脂としては、被覆加工される炭素
基材の深部にまで浸透し、基材を構成する炭素微粒子を
覆う必要がある。The resin used in the present invention needs to penetrate deep into the carbon base material to be coated and cover the carbon fine particles constituting the base material.
そのためには、高分子溶液の粘度を下げて浸透性をよく
する必要があるが、このような場合、粘度を下げる方法
としては、 （イ）多量の溶媒を用いて希釈する方法、
（ロ）樹脂の分子量の小さいもの、換言すればオリゴマ
ーの状態に近い状態で使用する方法、がある。To do this, it is necessary to lower the viscosity of the polymer solution to improve its permeability.
(b) There is a method in which the resin has a low molecular weight, in other words, it is used in a state close to that of an oligomer.
しかし多数の実験による試行の結果（イ）の方法による
場合、溶媒を蒸発除去した後は非常に少量の高分子成分
しか残らないうえ、高分子層そのものも溶媒の抜けた穴
が多く存在し粗いものとなるので被覆効果が実質的に低
下する欠点がある。However, as a result of numerous experiments, when method (a) is used, only a very small amount of polymer components remain after the solvent is evaporated, and the polymer layer itself has many holes through which the solvent has escaped, making it rough. This has the disadvantage that the coating effect is substantially reduced.
また（口）の方法による場合、余りに分子量が小さすぎ
ると、熱的に不安定で僅かの昇温で分解、蒸散して、被
覆効果が低くなる。また（ハ）樹脂の種類としてはでき
るだけ耐熱性を有するものが望ましいことが判った。In addition, in the case of the method (2), if the molecular weight is too small, it will be thermally unstable and will decompose and evaporate with a slight increase in temperature, reducing the coating effect. It has also been found that (c) the type of resin is preferably as heat resistant as possible.
発明者らは、使用する樹脂の種類及び分子量、及び溶媒
中に於ける濃度等を変化させ、最も含浸状態のよい条件
を探策し、本発明を完成するに至ったものである。The inventors changed the type and molecular weight of the resin used, the concentration in the solvent, etc., explored conditions for the best impregnation state, and finally completed the present invention.
本発明に使用される樹脂としては種々試験の結果、芳香
族ポリアミドイミド樹脂が最適であることを見出した。As a result of various tests, it has been found that aromatic polyamide-imide resin is the most suitable resin for use in the present invention.
その構造式は下記の通りである。Its structural formula is as follows.
この樹脂は、ポリイミド樹脂やポリベンズイミダゾール
樹脂と同じように耐熱性樹脂として知られている。−射
的に硬いながら弾力性もある表面を作り、炭素基材との
接着性もよく、−旦表層を形成すると簡単には剥離しな
い性質を有するので好都合である。This resin is known as a heat-resistant resin like polyimide resin and polybenzimidazole resin. - It is advantageous because it creates a surface that is radiationally hard but also elastic, has good adhesion to the carbon substrate, and - once the surface layer is formed, does not easily peel off.
分子量としては、１０〜１００量体（上記式に於いてｎ
がｌθ〜１００）程度が好ましく、分子量が１０００〜
１００００量体程度になると、溶媒にも溶けにくくなり
、且つ溶液も粘稠になる傾向があり、黒鉛基材への浸透
性も悪くなる。１０未満では表層硬度も低く、被覆効果
も低い。溶媒としては、ジメチルアセトアミド、ジメチ
ルフォルムアミド、ジメチルスルホキサイド、Ｎメチル
−２−ピロリドン等が好ましい溶媒として挙げられる。The molecular weight is 10 to 100 mer (n in the above formula)
is preferably lθ~100), and the molecular weight is preferably about 1000~100).
When it becomes about 10,000 mers, it becomes difficult to dissolve in solvents, the solution tends to become viscous, and the permeability into the graphite base material becomes poor. If it is less than 10, the surface hardness is low and the coating effect is also low. Preferred solvents include dimethylacetamide, dimethylformamide, dimethylsulfoxide, N-methyl-2-pyrrolidone, and the like.
溶媒中のポリアミドイミド樹脂の濃度としては溶媒によ
っても粘度が異なるが、表面処理のための、吹付けや塗
装のために好適な粘度を維持するためには、樹脂成分（
固形分）の濃度は重量比で１０〜５０％、好ましくは２
０〜３５％程度である。樹脂成分が少なすぎると粘度が
低く、浸透性もよいが、溶媒を揮散せしめた後の形成樹
脂層は粗く、基材封止性も低い。The concentration of polyamide-imide resin in a solvent varies depending on the solvent, but in order to maintain a suitable viscosity for surface treatment, spraying and painting, the resin component (
The concentration of solid content is 10 to 50% by weight, preferably 2
It is about 0 to 35%. If the resin component is too small, the viscosity will be low and the permeability will be good, but the resin layer formed after the solvent has been volatilized will be rough and the base material sealing performance will be low.
逆に樹脂成分が多すぎると、粘稠になり基材への浸透性
も悪くなる欠点があり、且つ溶媒中での安定性が悪く、
白濁減少が現れ、これで塗布すると表面に白い汚点など
が住じ好ましくない。On the other hand, if the resin component is too large, it becomes viscous and has poor permeability into the base material, and also has poor stability in solvents.
A reduction in white turbidity appears, and when applied with this, white spots appear on the surface, which is undesirable.
樹脂の分子量と溶媒中での樹脂濃度とは相関があり、良
好な作業性を維持するためには、前記のように分子量と
溶媒濃度とについて制限を設けた。There is a correlation between the molecular weight of the resin and the resin concentration in the solvent, and in order to maintain good workability, limits are set for the molecular weight and solvent concentration as described above.
以下に本発明法をその製造工程順に説明する。The method of the present invention will be explained below in the order of its manufacturing steps.
先ず炭素材料を芳香族ポリアミドイミド樹脂の有機溶剤
溶液に塗布又は浸漬して該溶液を被覆或いは一部含浸せ
しめる。この際使用される原料炭素材としては特に限定
されない。好ましいのは等方性炭素材である。また炭素
材としては炭素／炭素複合材等を用いることもできる。First, a carbon material is coated or immersed in an organic solvent solution of an aromatic polyamide-imide resin to cover or partially impregnate it with the solution. The raw carbon material used at this time is not particularly limited. Preferred is isotropic carbon material. Further, as the carbon material, a carbon/carbon composite material or the like can also be used.
上記炭素材に上記樹脂の有機溶剤溶液を塗布又は含浸す
る。これらの方法ははけぬり、スプレー噴き付は法、浸
漬等任意の方法が採用される。樹脂の塗布量は被覆層の
厚さとして通常１〜２０μｍ、好ましくは５〜１０μｍ
程度である。余りに厚くする必要はなく、むしろ有害と
なることがある。次いで３００〜４００℃で加熱して溶
媒を揮散除去すると共に該樹脂を硬化せしめ、次いで非
酸化性雰囲気中で焼成して該被膜を炭化又は更に黒鉛化
する。The carbon material is coated or impregnated with an organic solvent solution of the resin. For these methods, any method such as brushing, spraying, dipping, etc. can be adopted. The coating amount of the resin is usually 1 to 20 μm, preferably 5 to 10 μm in terms of the thickness of the coating layer.
That's about it. It does not need to be too thick; it can even be harmful. Next, the resin is heated at 300 to 400° C. to volatilize and remove the solvent, and the resin is cured, and then fired in a non-oxidizing atmosphere to carbonize or further graphitize the coating.
かくして得られる目的物炭素材は芳香族ポリアミドイミ
ド樹脂の炭化乃至黒鉛被膜が強固に形成されているため
なんら粒子剥離は侘じず粉塵も殆ど発生せず、これに基
づく各難点を未然に防止することができる。また細穴が
必要な炭素材に於いても樹脂が低分子量であり、或いは
その溶剤溶液が低濃度（低粘度）であるため、細穴中に
浸入し、その表面を被覆することが少ないので、細穴が
殆ど残存する。The target carbon material obtained in this way has a strong carbonization or graphite coating of the aromatic polyamide-imide resin, so there is no particle exfoliation and almost no dust is generated, and various problems caused by this are prevented. be able to. In addition, even in carbon materials that require pores, the resin has a low molecular weight or its solvent solution has a low concentration (low viscosity), so it is less likely to penetrate into the pores and coat the surface. , most of the small holes remain.
以下に実施例を挙げて本発明の詳細な説明する。 The present invention will be described in detail below with reference to Examples.
実施例１
炭素材料（東洋炭素株式会社製 等方性黒鉛材ｒｌＧ−
１１Ｊ）を芳香族ポリアミドイミド樹脂（小原化工■製
ｒＡ１−１０Ｊ）のｎ−メチル−２−ピロリドン溶剤溶
液（樹脂濃度２０％、粘度１．１ポイズ）に３０分間浸
漬し、引き上げた後付着液を取り除き、３００℃で乾燥
後、窒素ガス中で１０００℃で２４時間焼成して、炭素
質膜で被膜された目的物炭素材料を得た。但しこの被膜
の厚みは５μｍであった。得られた炭素製品の表面には
黒鉛粉は存在せず、素子で触っても汚れることもなかっ
た。Example 1 Carbon material (isotropic graphite material rlG- manufactured by Toyo Tanso Co., Ltd.
11J) was immersed in an n-methyl-2-pyrrolidone solvent solution (resin concentration 20%, viscosity 1.1 poise) of aromatic polyamide-imide resin (rA1-10J manufactured by Ohara Kako ■) for 30 minutes, and the adhering liquid was removed after being pulled up. was removed, dried at 300°C, and then fired in nitrogen gas at 1000°C for 24 hours to obtain a target carbon material coated with a carbonaceous film. However, the thickness of this film was 5 μm. No graphite powder was present on the surface of the obtained carbon product, and it did not become dirty even when touched with an element.
この黒鉛粉の有無は接着テープを該製品の表面に貼付し
、少時放置後このテープを剥がしテープ上に黒鉛粉が付
着したかどうかで測定することもでき、この結果も良好
であった。また該製品に存在する細穴は目詰まりを起こ
していなかった。The presence or absence of graphite powder can also be determined by pasting an adhesive tape on the surface of the product, peeling off the tape after leaving it for a while, and determining whether graphite powder has adhered to the tape, and this result was also good. Further, the pores present in the product were not clogged.
実施例２
上記実施例１に於いて芳香族ポリアミドイミド樹脂の溶
剤溶液の濃度だけを３５％となし、その他は実施例１と
同様に処理した。得られた製品を同様に黒鉛粉脱落テス
トを行った結果実施例１とほぼ同様であった。Example 2 In Example 1 above, only the concentration of the aromatic polyamide-imide resin solvent solution was changed to 35%, and the other conditions were the same as in Example 1. The obtained product was similarly subjected to a graphite powder shedding test, and the results were almost the same as in Example 1.
実施例３
黒鉛材（ｒ Ｉ Ｇ−１１Ｊ ） ２５Ｘ２５Ｘ１５輸
の片面に実施例１のポリアミドイミド樹脂を有機溶液に
て溶解（濃度３５％）した溶液を塗布、その後乾燥機に
て３００℃で硬化し、更に窒素ガス中で１０００℃１２
４時間加熱して炭化処理した。Example 3 A solution prepared by dissolving the polyamideimide resin of Example 1 in an organic solution (concentration 35%) was applied to one side of graphite material (r I G-11J) 25X25X15, and then hardened at 300°C in a dryer. , further heated at 1000℃12 in nitrogen gas.
Carbonization treatment was performed by heating for 4 hours.
得られた黒鉛材について、その鉄との反応性を測定した
。測定方法は第１図に示すように、鉄板（１）（厚さ１
０ｍ）上に、銅箔（２）（厚さ０．１ｍ）を介して、上
記黒鉛材（３）を樹脂塗布面を鉄Ｆｉ（１）側に向けて
載置し、Ｎ！ガス下１１００℃まで昇温（２０’Ｃ／分
）し、４分間保持し、その後冷却し、接合の状態を観察
した。The reactivity of the obtained graphite material with iron was measured. The measurement method is as shown in Figure 1, using an iron plate (1) (thickness 1
0 m) with the resin coated side facing the iron Fi (1) side, the graphite material (3) was placed with the copper foil (2) (thickness 0.1 m) interposed therebetween, and N! The temperature was raised to 1100°C (20'C/min) under gas, held for 4 minutes, and then cooled, and the state of bonding was observed.
またこの測定の際、ポリアミドイミド樹脂を全く使用し
ない黒鉛材についても同様に処理した。Further, during this measurement, a graphite material that did not use any polyamide-imide resin was also treated in the same way.
この結果実施例３の黒鉛材は鉄板と接合しなかった。一
方黒鉛材だけのもの（ポリアミドイミド樹脂の塗布なし
）は鉄板と強固に接合していた。As a result, the graphite material of Example 3 was not bonded to the iron plate. On the other hand, the one made of graphite material (without polyamide-imide resin coating) was firmly bonded to the iron plate.
元来、黒鉛材は第１図に示すような方法によって炉内に
て加熱すると鉄板との間に特殊な合金を析出させて強固
な接合状態を保つことが知られている。しかし乍ら上記
で述べた通りポリアミドイミド樹脂溶液を塗布、加熱処
理した面とはなんら化学反応が生じなかった。このこと
は本発明の方法による表面処理によって、黒鉛表面が改
質され、成る種の金属（例えばＦｅ系）との反応を疎外
する効果があることを示している。Originally, it is known that when graphite material is heated in a furnace using the method shown in FIG. 1, a special alloy is precipitated between the graphite material and the iron plate to maintain a strong bond. However, as mentioned above, no chemical reaction occurred with the surface coated with the polyamideimide resin solution and heat treated. This indicates that the surface treatment according to the present invention modifies the graphite surface and has the effect of eliminating reactions with other metals (eg, Fe-based).
このような効果は、実用的にはガラス封着用黒鉛治具や
金属溶融用黒鉛ルツボ等に、この処理を行うことにより
、黒鉛粉の離脱防止による製品品質の向上及びある種の
金属との反応防止効果によるルツボ材の変質防止の効果
が加味され黒鉛治具やルツボの大巾な寿命延長がなされ
るものである。In practical terms, this effect can be achieved by applying this treatment to graphite jigs for glass sealing, graphite crucibles for metal melting, etc., to improve product quality by preventing graphite powder from separating, and to prevent reactions with certain metals. In addition to the effect of preventing deterioration of the crucible material due to the prevention effect, the life of graphite jigs and crucibles can be greatly extended.
第１図は黒鉛材と金属との反応性を測定する方法の説明
図である。
１ ・・・ 鉄板
２ ・・・ 銅箔
３ ・・・ 黒鉛材
（以 上）
第１図
手続ネ甫正書（自発）
平成３年５月１６日FIG. 1 is an explanatory diagram of a method for measuring the reactivity between a graphite material and a metal. 1... Iron plate 2... Copper foil 3... Graphite material (and above) Figure 1 Procedural Negotiations (self-proposal) May 16, 1991
Claims (3)
し、この溶液を炭素材料に塗布又は含浸し、３００〜４
００℃で硬化せしめ、次いで非酸化性雰囲気中で焼成し
て、炭化又は更に黒鉛化することを特徴とする炭素被膜
で被覆された炭素材料の製造方法。(1) Dissolve aromatic polyamideimide resin in an organic solvent, apply or impregnate the carbon material with this solution,
1. A method for producing a carbon material coated with a carbon film, comprising curing at 00° C. and then firing in a non-oxidizing atmosphere to carbonize or further graphitize.
が１０〜５０％濃度である請求項（１）に記載の製造方
法。(2) The manufacturing method according to claim 1, wherein the organic solvent solution of the aromatic polyamide-imide resin has a concentration of 10 to 50%.
０量体程度の低分子量樹脂である請求項（１）に記載の
製造方法。(3) The aromatic polyamideimide resin is about 10 to 10
The manufacturing method according to claim 1, wherein the resin is a low molecular weight resin of about 0 mer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29009190A JP3245678B2 (en) | 1990-10-26 | 1990-10-26 | Method for producing carbon material coated with carbon coating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29009190A JP3245678B2 (en) | 1990-10-26 | 1990-10-26 | Method for producing carbon material coated with carbon coating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04164860A true JPH04164860A (en) | 1992-06-10 |
| JP3245678B2 JP3245678B2 (en) | 2002-01-15 |
Family
ID=17751685
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29009190A Expired - Fee Related JP3245678B2 (en) | 1990-10-26 | 1990-10-26 | Method for producing carbon material coated with carbon coating |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3245678B2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011225431A (en) * | 2010-03-30 | 2011-11-10 | Fujifilm Corp | Nitrogen-containing carbon alloy, method for producing the same, and carbon catalyst using the same |
| CN111559744A (en) * | 2020-06-19 | 2020-08-21 | 株洲时代新材料科技股份有限公司 | Preparation method of high-thermal-conductivity graphite material |
-
1990
- 1990-10-26 JP JP29009190A patent/JP3245678B2/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011225431A (en) * | 2010-03-30 | 2011-11-10 | Fujifilm Corp | Nitrogen-containing carbon alloy, method for producing the same, and carbon catalyst using the same |
| CN111559744A (en) * | 2020-06-19 | 2020-08-21 | 株洲时代新材料科技股份有限公司 | Preparation method of high-thermal-conductivity graphite material |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3245678B2 (en) | 2002-01-15 |
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