JPH04164861A - Graphite material and production thereof - Google Patents
Graphite material and production thereofInfo
- Publication number
- JPH04164861A JPH04164861A JP2287087A JP28708790A JPH04164861A JP H04164861 A JPH04164861 A JP H04164861A JP 2287087 A JP2287087 A JP 2287087A JP 28708790 A JP28708790 A JP 28708790A JP H04164861 A JPH04164861 A JP H04164861A
- Authority
- JP
- Japan
- Prior art keywords
- graphite
- carbon black
- carbon
- graphite material
- oxidation
- 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
- 239000007770 graphite material Substances 0.000 title claims abstract description 60
- 238000004519 manufacturing process Methods 0.000 title claims description 7
- 239000006229 carbon black Substances 0.000 claims abstract description 52
- 239000002245 particle Substances 0.000 claims abstract description 40
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 31
- 239000010439 graphite Substances 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims abstract description 12
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 abstract description 51
- 238000007254 oxidation reaction Methods 0.000 abstract description 40
- 230000003647 oxidation Effects 0.000 abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 abstract description 25
- 239000001569 carbon dioxide Substances 0.000 abstract description 24
- 238000000034 method Methods 0.000 abstract description 14
- 238000002156 mixing Methods 0.000 abstract description 8
- 239000000571 coke Substances 0.000 abstract description 7
- 239000000843 powder Substances 0.000 abstract description 5
- 239000011305 binder pitch Substances 0.000 abstract description 4
- 239000011230 binding agent Substances 0.000 abstract description 4
- 239000011329 calcined coke Substances 0.000 abstract description 4
- 229910021383 artificial graphite Inorganic materials 0.000 abstract description 2
- 238000005255 carburizing Methods 0.000 abstract description 2
- 229910021382 natural graphite Inorganic materials 0.000 abstract description 2
- 239000011347 resin Substances 0.000 abstract description 2
- 229920005989 resin Polymers 0.000 abstract description 2
- 229920001187 thermosetting polymer Polymers 0.000 abstract description 2
- 229910052751 metal Inorganic materials 0.000 description 14
- 239000002184 metal Substances 0.000 description 14
- 239000000463 material Substances 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 230000001590 oxidative effect Effects 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 241000239290 Araneae Species 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 238000000465 moulding Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 239000011295 pitch Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052580 B4C Inorganic materials 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011294 coal tar pitch Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910021385 hard carbon Inorganic materials 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 238000004898 kneading Methods 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 229910021384 soft carbon Inorganic materials 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Abstract
Description
【発明の詳細な説明】 産業上の利用分野 本発明は、新規な黒鉛材料及びその製造方法に関する。[Detailed description of the invention] Industrial applications The present invention relates to a novel graphite material and a method for producing the same.
従来の技術
黒鉛材料は、耐熱性や加工性に優れていること、ガラス
や金属に濡れないことなどの理由から、半導体製品の製
造に関連したるつぼや治具材等として利用されている。BACKGROUND OF THE INVENTION Graphite materials are used as crucibles, jig materials, etc. related to the manufacture of semiconductor products because they have excellent heat resistance and workability, and do not get wet with glass or metal.
しかしながら、その使用雰囲気が酸化性でしかも高い温
度条件下では、材料が酸化して表面にピンホール状の小
孔を発生させ、黒鉛材の使用寿命を大幅に低下させてい
る。However, when the atmosphere in which it is used is oxidizing and at a high temperature, the material oxidizes and pinhole-like pores are generated on the surface, significantly reducing the service life of the graphite material.
黒鉛材料の耐酸化性を向上させるためには、これまでピ
ッチ類を含浸して表面気孔を少な（する方法やりん酸化
合物、微粒シリカゾル、ホウケイ酸ガラスなどを含浸す
る方法（例えば特開昭６０−９２４２７号公報、特開昭
６２−２９７２８１号公報、特公昭６０−３３７９２号
公報）、炭化ケイ素や炭化ホウ素を配合する方法（例え
ば特公昭６２−１２１９１号公報）などが知られている
。しかしながら、ピッチ含浸による方法はさほど耐酸化
性を向上させることはできず、また無機系材料の含浸に
よりたとえ耐酸化性が向上した黒鉛材料でも、上記のよ
うな方法で処理された黒鉛材料は、ガラスなどと濡れた
り反応したりするので、半導体関連用の治具には不適で
ある。In order to improve the oxidation resistance of graphite materials, methods such as impregnating with pitches to reduce surface pores, or methods of impregnating with phosphoric acid compounds, fine silica sol, borosilicate glass, etc. -92427, Japanese Patent Publication No. 62-297281, Japanese Patent Publication No. 60-33792), and a method of blending silicon carbide or boron carbide (for example, Japanese Patent Publication No. 62-12191). However, However, the pitch impregnation method cannot significantly improve oxidation resistance, and even if the oxidation resistance of graphite material is improved by impregnation with an inorganic material, the graphite material treated by the above method will not be able to improve the oxidation resistance of glass. It is unsuitable for semiconductor-related jigs because it gets wet and reacts with other substances.
また、黒鉛材治具が１０００℃付近の高温下で使用され
る場合、電子部品等の金属リング（これらは鉄、ニッケ
ル、コバルト、あるいはこれらの合金からなる）と治具
との接触面より浸炭現象が発生し、製品の抵抗値を変化
させたり、短絡を発生させたりする等の問題があった。In addition, when a graphite jig is used at high temperatures around 1000°C, carburization occurs from the contact surface between the jig and the metal ring of electronic components (these are made of iron, nickel, cobalt, or alloys of these). This caused problems such as changing the resistance value of the product and causing short circuits.
この浸炭現象を防ぐために、治具の表面を酸化処理する
方法（特開昭６４−８７５３８号公報）が提案されてい
る。この方法は、黒鉛材料を加工したのちに上記処理を
施さなければならず、黒鉛材料そのものとして浸炭を防
いでいるものではない。また、表面処理にむらがあれば
浸炭を確実に防げるものではない。In order to prevent this carburization phenomenon, a method of oxidizing the surface of the jig (Japanese Unexamined Patent Publication No. 87538/1983) has been proposed. In this method, the above treatment must be performed after processing the graphite material, and the graphite material itself does not prevent carburization. Furthermore, if the surface treatment is uneven, carburization cannot be reliably prevented.
発明が解決しようとする課題
このように、上記用途に関しての黒鉛材料については、
反応性のあるものや不純物となりうる無機系の材料によ
る被覆、含浸あるいは配合などによる処理方法で耐酸化
性を向上させることは不適切である。本発明の目的は、
上記処理を施すことなく、二酸化炭素等に対して耐酸化
性のある黒鉛材料及びその製造方法を提供することにあ
る。さらには、金属等に接触した際の浸炭現象を抑制し
た黒鉛材料を提供するものである。Problems to be Solved by the Invention As described above, regarding graphite materials for the above uses,
It is inappropriate to improve oxidation resistance by coating, impregnating, or blending with reactive materials or inorganic materials that can become impurities. The purpose of the present invention is to
The object of the present invention is to provide a graphite material that is oxidation resistant to carbon dioxide and the like without the above-mentioned treatment, and a method for producing the same. Furthermore, the present invention provides a graphite material that suppresses carburization when it comes into contact with metal or the like.
課題を解決するための手段
本発明は、黒鉛粒子の表面周囲にカーボンブラックが付
着したミクロ構造を有し、嵩密度が１．５０〜１．９５
ｇ／ｃｍ”である黒鉛材料、およびカーボンブラックを
２〜２０重量％混合した粒子状の炭素材用原料を成型し
、焼成炭化、黒鉛化することを特徴とする黒鉛粒子の表
面周囲にカーボンブラックが付着したミクロ構造を有す
る黒鉛材料の製造方法である。Means for Solving the Problems The present invention has a microstructure in which carbon black is attached around the surface of graphite particles, and has a bulk density of 1.50 to 1.95.
Carbon black is added around the surface of the graphite particles by molding a particulate raw material for carbon material, which is a mixture of 2 to 20% by weight of graphite material and carbon black. This is a method for producing a graphite material having a microstructure with attached.
本発明の内容をさらに具体的に説明する。The content of the present invention will be explained in more detail.
本発明の黒鉛材料のミクロ構造は、骨材としての黒鉛粒
子の表面周囲にカーボンプラクが付着した構造を有して
いる。この様子は、黒鉛材料を破断して走査型電子顕微
鏡で観察すれば可能であるが、カーボンブラックの大部
分はバインダー成分に由来したコークス中に取り込まれ
ているので、８０００倍程度の高倍率で注意深（観察す
る必要がある。このとき、黒鉛粒子の表面周囲には、カ
ーボンブラックの凝集体が付着している。この黒鉛材料
を１０００°Ｃの二酸化炭素の雰囲気中で、表面のバイ
ンダー成分白米のコークスを酸化した後、走査型電子顕
微鏡でこの表面を見ると、１０００倍程度の倍率で明確
にカーボンブラックが黒鉛粒子の表面周囲に存在してい
ることを確認することができる。The microstructure of the graphite material of the present invention has a structure in which carbon plaques are attached around the surface of graphite particles as an aggregate. This situation can be seen by breaking the graphite material and observing it with a scanning electron microscope, but since most of the carbon black is incorporated into the coke derived from the binder component, it can be seen at a high magnification of about 8000x. Careful observation is required. At this time, aggregates of carbon black are attached around the surface of the graphite particles. This graphite material is heated in a carbon dioxide atmosphere at 1000°C, and the If you look at the surface of polished rice coke with a scanning electron microscope after oxidizing it, you can clearly see that carbon black exists around the surface of graphite particles at a magnification of about 1,000 times.
このときカーボンブラックは、黒鉛粒子の表面周囲を綿
状に毛羽立って取り囲んでおり、黒鉛材料の表面をほぼ
全面にわたってあたかも蜘蛛の巣で覆っている様な状態
で存在していることを確認することが出来る。At this time, it is confirmed that the carbon black surrounds the surface of the graphite particles in a cotton-like fluff, and exists in a state where almost the entire surface of the graphite material is covered with a spider's web. I can do it.
本発明の黒鉛材料の嵩密度は、常温において１、５０〜
１．９５ ｇ ／ ｃｍ”の範囲である。嵩密度が１．
５０ｇ／ｃｍ”未満では、材料として脆（、加工に耐え
うる強度が得られない。また、１．９５ｇ／ｃｍ”を越
える高密度材を製造しようとすれば、炭素材用原料の揮
発分を多（したりその粒径を小さくしなければならず、
実用的な大きさの成型体では焼成時に割れや発泡が起き
やす（なるので好ましくない。The bulk density of the graphite material of the present invention is 1.50 to 1.50 at room temperature.
1.95 g/cm”.The bulk density is 1.95 g/cm”.
If it is less than 50 g/cm", the material will be brittle (and will not have the strength to withstand processing. Also, if you try to manufacture a high-density material exceeding 1.95 g/cm", the volatile content of the raw material for carbon material will have to be reduced). If the particle size is large (or the particle size must be reduced,
Moldings of practical size tend to crack or foam during firing, which is undesirable.
望ましくは、１．６５〜１．８５ ｇ ／ ｃｍ”の範
囲がよい。Desirably, the range is 1.65 to 1.85 g/cm''.
この発明の黒鉛材料を製造するために使用する炭素材用
原料とは、生コークス、か焼コークス、人造黒鉛、天然
黒鉛などの骨材微粉末にカーボンブラックが混合された
ものであり、必要に応じて結合材としてバインダーピッ
チや熱硬化性樹脂などが加えられたものである。The raw material for carbon material used to produce the graphite material of this invention is a mixture of carbon black and fine aggregate powder such as raw coke, calcined coke, artificial graphite, and natural graphite. Accordingly, binder pitch, thermosetting resin, etc. are added as a binding material.
カーボンブラックの混合方法は、成型の直前において、
ヘンシェルミキサー等を用いて混合分散させる方法が最
も簡便な方法として望ましい。そのほかには、か焼コー
クス等の骨材微粉末とバインダーピッチ等の結合材を混
練する時に混合する方法や、あらかじめバインダーピッ
チ等の結合材中に混合分散しておき、これを骨材微粉末
と混練する方法があり、炭素材用原料中でカーボンブラ
ックが骨材粒子のまわりに均一に分散する方法であれば
良い。The method of mixing carbon black is to
A method of mixing and dispersing using a Henschel mixer or the like is preferred as the simplest method. Other methods include mixing fine aggregate powder such as calcined coke and a binding material such as binder pitch when kneading, or mixing and dispersing it in advance into a binding material such as binder pitch and then adding it to fine aggregate powder. There is a method in which carbon black is uniformly dispersed around aggregate particles in the raw material for carbon material.
生コークスやか焼コークスなどの骨材は、１００メツシ
ユ以下の適当な粒度に粉砕したものである。Aggregates such as raw coke and calcined coke are pulverized to a suitable particle size of 100 mesh or less.
カーボンブラックは、大別してハードカーボンとソフト
カーボンがあり、このどれを使用してもよく、これらの
平均粒径は１０〜１００ ｎｍである。従つて、骨材の
径（ａ）とカーボンブラックの径（ｂ）の比（ａ ／
ｂ ）は１００〜１０００程度がよい。Carbon black can be broadly classified into hard carbon and soft carbon, and any of these may be used, and the average particle size of these is 10 to 100 nm. Therefore, the ratio of the aggregate diameter (a) to the carbon black diameter (b) (a/
b) is preferably about 100 to 1000.
カーボンブラックは、炭素材用原料中で２〜２０重量％
（内側）配合され、２重量％未満では添加の効果が少な
い。一方、２０重量％を超えると黒鉛材料の嵩密度が上
がらず、また、カーボンブラックの酸化の影響が出るの
でかえって耐酸化性は悪くなる。望ましくは、全体量の
４〜１０重量％の配合割合とするのがよい。また、カー
ボンブラックを本発明の範囲内で多めに配合する場合に
は、炭素材用原料の揮発分を通常より多（調整すること
で嵩密度の低下を抑えることができる。Carbon black is 2 to 20% by weight in the raw material for carbon materials.
(inside) is added, and if it is less than 2% by weight, the effect of addition is small. On the other hand, if it exceeds 20% by weight, the bulk density of the graphite material does not increase, and the oxidation resistance of carbon black worsens. Desirably, the blending ratio is 4 to 10% by weight based on the total amount. Further, when a large amount of carbon black is blended within the scope of the present invention, a decrease in bulk density can be suppressed by adjusting the volatile content of the raw material for carbon material to be higher than usual.
このようにして、カーボンブラックを配合し混合したも
のは、金型ブレスあるいはラバープレスの何れで成型し
ても良く、成型後は常法通りに非酸化性雰囲気中で１０
００〜１２００℃で焼成炭化し、さらに２０００〜３０
００℃で黒鉛化することにより、二酸化炭素等に対して
耐酸化性のある黒鉛材料を製造することができる。The mixture of carbon black may be molded using either a mold press or a rubber press.
Calcined and carbonized at 00-1200℃, further heated at 2000-30℃
By graphitizing at 00°C, it is possible to produce a graphite material that is oxidation resistant to carbon dioxide and the like.
本発明の黒鉛材料は、冶金用、機械用、電気用、化学用
などの種々の分野において、治具材等として有用であり
、特に二酸化炭素等に対しての耐酸化性や電子部品等に
対しての浸炭の防止が要求される用途に好適なものであ
る。The graphite material of the present invention is useful as a jig material in various fields such as metallurgy, machinery, electricity, and chemistry, and is particularly effective in oxidation resistance against carbon dioxide, etc., and in electronic components. This is suitable for applications where prevention of carburization is required.
作用
本発明により得られた黒鉛材料は、黒鉛粒子の表面周囲
にカーボンブラックが付着したミクロ構造を有したもの
である。この黒鉛材料を二酸化炭素で酸化した表面は、
カーボンブラックが骨材の黒鉛粒子をあたかも蜘蛛の巣
で覆っている様な状態で存在していることが走査型電子
顕微鏡による観察で認められた。一方、空気で酸化した
表面は、上記のようなカーボンブラックの存在は認めら
れず、骨材の黒鉛粒子が表面に露出していた。これは、
二酸化炭素のカーボンブラックと黒鉛粒子に対する酸化
速度が比較的接近している（１０００℃において、カー
ボンブラックは、ｋ（ＣＯＩ）＝ １．７９Ｘ １０−
’ｗｔ％・ｓ−１、黒鉛粒子（平均粒径２０μｍ）は、
ｋ（Ｃｏｗ） ＝ ７．３３Ｘ １０−”ｗｔ％、５−
１）のに対して、空気のカーボンブラックに対する酸化
速度は、黒鉛粒子のそれと比較して極めて速い（１００
０”Ｃにおいて、カーボンブラックは、ｋ（Ａｉｒ）＝
７．６７ｗｔ％・ｓ −ｒ、黒鉛粒子（平均粒径２０μ
ｍ）は、ｋ（Ａｉｒ）＝８．３５Ｘ １０−”ｗｔ％、
５−１）ためであると考えられる。Function The graphite material obtained by the present invention has a microstructure in which carbon black is attached around the surface of graphite particles. The surface of this graphite material oxidized with carbon dioxide is
Observation using a scanning electron microscope revealed that carbon black existed in a state that covered the graphite particles of the aggregate as if it were covered with a spider's web. On the other hand, on the surface oxidized with air, the presence of carbon black as described above was not observed, and graphite particles of the aggregate were exposed on the surface. this is,
The oxidation rates of carbon dioxide on carbon black and graphite particles are relatively close (at 1000°C, carbon black has a
'wt%・s-1, graphite particles (average particle size 20 μm) are
k (Cow) = 7.33X 10-”wt%, 5-
1), the oxidation rate of carbon black in air is extremely fast (100%) compared to that of graphite particles.
At 0”C, carbon black has k(Air)=
7.67wt%・s-r, graphite particles (average particle size 20μ
m) is k(Air)=8.35X 10-”wt%,
5-1).
ここで、上記の酸化速度は、熱天秤による重量減少割合
から求めたものである。すなわち、二酸化炭素による酸
化の速度定数は、１０００”Ｃ保持中の時間に対する重
量減少割合を求めたものであり、空気による酸化の速度
定数は、１０℃／ｍｉｎで１０００″Ｃまで昇温したと
きに得られる重量減少割合のデジタルデータから、差分
法（Ｂ、Ｓ、Ｆｒｅｅｍａｎ、 Ｂ、Ｃａｒｒ。Here, the above-mentioned oxidation rate was determined from the weight loss rate measured on a thermobalance. In other words, the rate constant of oxidation with carbon dioxide is the rate of weight loss with respect to time while holding at 1000"C, and the rate constant of oxidation with air is when the temperature is raised to 1000"C at 10°C/min. From the digital data of the weight loss rate obtained in 2008, a differential method (B.
１、Ｊ、Ｐｈｙｓ、 Ｃｈｅｍ、、 ６２，３９４ （
１９５８））による解析手法をもちいて反応速度式を求
め、この速度式から１０００℃における速度定数を計算
したものである。1, J, Phys, Chem, 62,394 (
A reaction rate equation was obtained using the analysis method by (1958)), and a rate constant at 1000°C was calculated from this rate equation.
本発明の黒鉛材料は、二酸化炭素に対しては耐酸化性を
向上させる効果を示すが、空気に対してカーボンブラッ
クを添加することにより耐酸化性は逆に低下し効果がな
い。このような違いは、上述したように各々の酸化雰囲
気において、酸化中にカーボンブラックが骨材の黒鉛材
料を覆っているか否かに関係していると考えられる。The graphite material of the present invention exhibits the effect of improving oxidation resistance against carbon dioxide, but when carbon black is added to air, the oxidation resistance decreases and there is no effect. Such a difference is considered to be related to whether or not carbon black covers the graphite material of the aggregate during oxidation in each oxidizing atmosphere as described above.
本発明によるカーボンブラックを添加した黒鉛材料が、
二酸化炭素に対して耐酸化性に優れる理由としては、黒
鉛粒子の表面周囲をカーボンブラックが覆うことにより
、二酸化炭素の黒鉛表面への侵入が阻止され、酸化反応
が拡散律速となること、あるいは黒鉛粒子の表面で生成
する一酸化炭素の対流がすみやかに起こらず、それを生
成する平衡反応（Ｃ＋ＣＯ２＝２・ＣＯ）が右に進み難
くなることなどが考えられる。また、黒鉛材料中に含ま
れる微量金属が酸化触媒としてピンホールの形成を促進
する場合、黒鉛粒子表面を覆っているカーボンブラック
のネットワークが微量金属を補足してその凝集を防ぎ、
ピンホールの深化を抑制することなども考えられる。従
って、酸化中にカーボンブラックが黒鉛粒子の表面周囲
に存在しない空気による酸化では、本発明による黒鉛材
料は、耐酸化性を改善する効果がない。The graphite material added with carbon black according to the present invention is
The reason for the excellent oxidation resistance against carbon dioxide is that carbon black covers the surface of graphite particles, which prevents carbon dioxide from entering the graphite surface, making the oxidation reaction rate-limiting by diffusion. It is conceivable that the convection of carbon monoxide produced on the surface of the particles does not occur promptly, making it difficult for the equilibrium reaction (C+CO2=2.CO) that produces it to proceed to the right. In addition, when trace metals contained in the graphite material act as oxidation catalysts and promote the formation of pinholes, the carbon black network covering the graphite particle surface captures the trace metals and prevents their aggregation.
It is also possible to suppress the deepening of pinholes. Therefore, in air oxidation where carbon black is not present around the surface of the graphite particles during oxidation, the graphite material according to the invention is not effective in improving oxidation resistance.
本発明の黒鉛材料は、二酸化炭素と同程度に穏やかな酸
化反応を行う水蒸気に対しても、酸化中にカーボンブラ
ックが黒鉛粒子を覆うことが可能であり、水蒸気による
酸化がおこる雰囲気においても、耐酸化性が向上した黒
鉛材料として期待できる。The graphite material of the present invention is capable of covering graphite particles with carbon black during oxidation even in the case of water vapor, which undergoes an oxidation reaction as mild as that of carbon dioxide, and even in an atmosphere where oxidation by water vapor occurs. It can be expected to be a graphite material with improved oxidation resistance.
カーボンブラックは、１０００℃という高温において鉄
やニッケルなどの金属と接触しても、これらの金属に対
して浸炭することはない。従って、本発明による黒鉛材
料は、高温下で金属と接触しても、カーボンブラックが
黒鉛粒子を覆っているために、黒鉛粒子と金属の接触が
妨げられて相互に固溶し難くなり、金属表面への浸炭を
抑制することが出来る。Even if carbon black comes into contact with metals such as iron or nickel at a high temperature of 1000° C., it will not carburize these metals. Therefore, even if the graphite material according to the present invention comes into contact with metal at high temperatures, the carbon black covers the graphite particles, which prevents contact between the graphite particles and the metal, making it difficult for them to form a solid solution with each other. Carburization of the surface can be suppressed.
実施例
次いで、本発明を実施例により比較例と対比しながら具
体的に説明するが、本発明は、この実施例によって何隻
限定されるものではない。EXAMPLES Next, the present invention will be concretely explained using examples while comparing with comparative examples, but the present invention is not limited to the number of ships by these examples.
コールタールピッチに含まれるＱＩ酸成分除去した脱Ｑ
ｌピッチ（軟化点４０℃）を４７０℃の熱処理温度で５
時間保持して、揮発分１０６５重量％の焼結性のあるバ
インダーレスプレカーサーを得た。De-Q removal of QI acid components contained in coal tar pitch
l pitch (softening point 40°C) at a heat treatment temperature of 470°C.
After holding for a period of time, a sinterable binderless precursor with a volatile content of 1065% by weight was obtained.
これを振動ボールミルで平均粒径１５μｍに粉砕して成
型用の原料とした。実施例１〜３において、前述の原料
粉に第１表に示す割合でカーボンブラック（新日鐵化学
■製ニテロン＃１０）を配合し、内容量２００ｍ１のミ
キサーで３分間混合して炭素材用原料とした。This was ground to an average particle size of 15 μm using a vibrating ball mill to obtain a raw material for molding. In Examples 1 to 3, carbon black (Niteron #10 manufactured by Nippon Steel Chemical Co., Ltd.) was blended with the raw material powder described above in the proportions shown in Table 1, and mixed for 3 minutes in a mixer with a capacity of 200 m1 to prepare carbon material. It was used as a raw material.
これを直径５０φｍｍの金型に１００ｇ充填し５０ｋｇ
／ｃｍ”の圧力で教戒型した後、これをゴム袋につめて
２． Ｏｔ／ ｃｍ”の圧力で水圧等方加圧成形を行っ
て成型体を得た。この成型体を粉コークスを詰めた容器
内でアルゴン気流下１０００℃まで昇温して炭化し、さ
らに黒鉛化炉でアルゴン気流中２８００℃で黒鉛化を行
った。得られた黒鉛材料の嵩密度を第１表に示す。Fill 100g of this into a mold with a diameter of 50φmm and make 50kg.
After molding at a pressure of 2.0 t/cm", this was packed in a rubber bag and subjected to hydrostatic isostatic pressing at a pressure of 2.0 t/cm" to obtain a molded body. This molded body was carbonized by raising the temperature to 1000°C under an argon stream in a container filled with coke powder, and further graphitized at 2800°C in an argon stream in a graphitization furnace. Table 1 shows the bulk density of the graphite material obtained.
得られた黒鉛材料の耐酸化性については、このブロック
体を管状炉内で熱処理酸化した後の酸化消耗割合と、こ
の表面に発生したピンホールの数を測定することにより
評価した。つまり、黒鉛材料から１０ Ｘ １０ Ｘ
２０ｍｍのブロック体を切り出して管状炉の中に入れた
後、アルゴンガスを５０ｍ１／ｍｉｎで流しながら、２
０℃／ｍｉｎの昇温速度で１０００℃まで昇温した。ｔ
ｏｏｏ℃到達後、雰囲気ガスを窒素５０％、水素３０％
、二酸化炭素２０％の混合ガスに切り替えて、同じ＜
５０ｍ１／ ｍｉｎのガス流量で２時間保持した。この
ときの酸化消耗割合とあわせて、酸化後の黒鉛材ブロッ
クの表面に発生した直径５００μｍ以上のピンホールの
数と最大直径を同じ（第１表に示した。黒鉛材表面のピ
ンホールは、走査型電子顕微鏡で観察することにより調
べた。The oxidation resistance of the obtained graphite material was evaluated by measuring the oxidation consumption rate and the number of pinholes generated on the surface of the block after heat treatment and oxidation in a tube furnace. That is, from graphite material 10 X 10
After cutting out a 20mm block and placing it in a tube furnace, it was heated for 2 hours while flowing argon gas at a rate of 50ml/min.
The temperature was raised to 1000°C at a temperature increase rate of 0°C/min. t
After reaching ooo℃, the atmosphere gas is changed to 50% nitrogen and 30% hydrogen.
, switch to a mixed gas of 20% carbon dioxide, and the same <
The gas flow rate was maintained at 50 ml/min for 2 hours. In addition to the oxidation consumption rate at this time, the number and maximum diameter of pinholes with a diameter of 500 μm or more generated on the surface of the graphite material block after oxidation are the same (shown in Table 1. The pinholes on the graphite material surface are This was investigated by observing with a scanning electron microscope.
第１表において、カーボンブラックを配合した実施例１
〜３のものは、それを配合していない比較例１と対比し
て嵩密度が低いにもかかわらず酸化消耗割合が低（、こ
れと比較してピンホールの数と大きさも小さくなる。In Table 1, Example 1 containing carbon black
-3 has a lower oxidation consumption rate despite having a lower bulk density than Comparative Example 1 which does not contain it (and the number and size of pinholes are also smaller compared to this).
次に、実施例１〜３と比較例１の黒鉛材料を、二酸化炭
素１００％の雰囲気中で、熱天秤を用いて酸化消耗の評
価を行った。つまり、黒鉛材料から３ｘ３ｘ６ｍｍの試
料を切り出し、これを熱天秤用の白金皿に入れた後、二
酸化炭素を１００ｍ１／ ｗｉｎの流量で流しながら２
０℃／ｍｉｎの昇温速度で室温から１０００℃まで昇温
した後、１時間保持した。この時の酸化消耗割合を第２
表に示す。Next, the graphite materials of Examples 1 to 3 and Comparative Example 1 were evaluated for oxidative consumption using a thermobalance in an atmosphere of 100% carbon dioxide. In other words, a 3 x 3 x 6 mm sample was cut out from graphite material, placed in a platinum dish for a thermobalance, and then heated at a flow rate of 100 m1/win while flowing carbon dioxide at a flow rate of 2 mm.
The temperature was raised from room temperature to 1000°C at a heating rate of 0°C/min and then held for 1 hour. The oxidation consumption rate at this time is
Shown in the table.
第２表から、カーボンブラックを配合した実施例工〜３
のものは、それを配合していない比較例１と対比して、
酸化消耗割合が低い。このことよりカーボンブラックの
添加により、二酸化炭素に対する耐酸化性が向上するこ
とが明らかとなった。From Table 2, Example 3 containing carbon black
In comparison with Comparative Example 1 which does not contain it,
Oxidation consumption rate is low. This revealed that the addition of carbon black improves the oxidation resistance to carbon dioxide.
二酸化炭素により酸化された黒鉛材料を白金皿から取り
出して、その表面を走査型電子顕微鏡の１０００倍の倍
率で観察した。実施例１〜３の黒鉛材料の表面では、黒
鉛粒子の表面をカーボンブラックが蜘蛛の巣状に覆って
いる様子が確認できた。The graphite material oxidized by carbon dioxide was taken out from the platinum dish, and its surface was observed under a scanning electron microscope at a magnification of 1000 times. On the surfaces of the graphite materials of Examples 1 to 3, it was confirmed that the surfaces of the graphite particles were covered with carbon black in the form of a spider's web.
例として、実施例２の黒鉛材料を二酸化炭素で酸化した
表面を、第１図の写真に示す。一方、比較例１の黒鉛材
料を二酸化炭素で酸化した表面は、黒鉛粒子が存在する
のみであった。実施例１〜３の黒鉛材料を、酸化処理す
ることな（そのままの状態で破断してその表面を走査型
電子顕微鏡で観察すると、８０００倍の倍率で黒鉛粒子
の表面にカーボンブラックが１μｍ前後の凝集体として
島状に付着していることが観察できた。As an example, the surface of the graphite material of Example 2 oxidized with carbon dioxide is shown in the photograph of FIG. On the other hand, on the surface of the graphite material of Comparative Example 1 oxidized with carbon dioxide, only graphite particles were present. The graphite materials of Examples 1 to 3 were not subjected to oxidation treatment (when they were broken as they were and their surfaces were observed with a scanning electron microscope, it was observed that carbon black of around 1 μm was formed on the surface of the graphite particles at a magnification of 8000 times). It was observed that the particles were attached as aggregates in the form of islands.
本発明による黒鉛材料は、そのままの状態ではカーボン
ブラックの大部分はバインダー成分に由来したコークス
中に取り込まれているので、黒鉛粒子の表面周囲に付着
しているカーボンブラックを８０００倍程度０高倍率で
観察する必要がある。しかしながら、これを二酸化炭素
で表面を酸化することにより、バインダーに由来したコ
ークス部分が酸化されて、カーボンブラックが蜘蛛の巣
状に浮き上がってくるために、第１図に示したように１
０００倍程度０倍率でカーボンブラックが黒鉛粒子のま
わりを取り囲んでいる様子を明確に観察することができ
る。また、実施例１〜３および比較例１の黒鉛材料にお
いて、空気による酸化後の表面は、どれもカーボンブラ
ックの存在は認められず黒鉛粒子が存在するのみであっ
た。In the graphite material according to the present invention, most of the carbon black is incorporated into the coke derived from the binder component in its original state, so the carbon black attached around the surface of the graphite particles can be absorbed by about 8000 times. need to be observed. However, by oxidizing the surface with carbon dioxide, the coke part originating from the binder is oxidized and the carbon black floats up in a spider web shape, resulting in
It can be clearly observed that carbon black surrounds graphite particles at a magnification of about 000x. Further, in the graphite materials of Examples 1 to 3 and Comparative Example 1, no carbon black was observed on the surfaces after oxidation with air, and only graphite particles were present.
実施例１〜３および比較例１で得られた黒鉛材料を３０
Ｘ３０Ｘ８ｍｍのサイズに切り出し、この黒鉛材料の上
に金属リング（８ｍｍφ）を６個ならべ、窒素５０％、
水素３０％、二酸化炭素２０％の混合ガス雰囲気（一般
に、鋼に浸炭するときに用いられている混合ガスにおい
て、−酸化炭素の代わりに二酸化炭素を使用）で１００
０℃、５時間加熱した。ここで使用した金属リングは、
鉄にニッケルをメツキしたものである。黒鉛材と接触し
た側の金属リングの表面について、浸炭現象による表面
の白濁の発生の有無を第３表に示した。The graphite materials obtained in Examples 1 to 3 and Comparative Example 1 were
Cut out a size of X30X8mm, arrange six metal rings (8mmφ) on top of this graphite material, and heat with 50% nitrogen.
100 in a mixed gas atmosphere of 30% hydrogen and 20% carbon dioxide (in the mixed gas generally used when carburizing steel, carbon dioxide is used instead of carbon oxide).
It was heated at 0°C for 5 hours. The metal ring used here is
It is made of iron plated with nickel. Table 3 shows whether or not clouding occurred on the surface of the metal ring on the side that came into contact with the graphite material due to the carburization phenomenon.
第３表のように、実施例１〜３のカーボンブラック２重
量％以上を配合した黒鉛材料では、浸炭現象の発生がな
く、カーボンブラック無添加の比較例１では、金属リン
グの全面に白濁した浸炭現象がみられた。As shown in Table 3, in the graphite materials of Examples 1 to 3 containing 2% or more of carbon black, no carburization phenomenon occurred, and in Comparative Example 1, in which no carbon black was added, the entire surface of the metal ring was cloudy. Carburization phenomenon was observed.
（以下余白）
第１表
第２表
第３表
発明の効果
本発明の黒鉛材料は、二酸化炭素等の弱酸化性の雰囲気
において耐酸化性が向上したものであり、酸化消耗およ
びピンホールの発生を抑制する。従って、黒鉛材料が二
酸化炭素等を含む雰囲気で使用される用途において、そ
の使用寿命を長くすることができる。(The following are blank spaces) Table 1 Table 2 Table 3 Effects of the Invention The graphite material of the present invention has improved oxidation resistance in a weakly oxidizing atmosphere such as carbon dioxide, and is free from oxidative consumption and pinhole formation. suppress. Therefore, in applications where the graphite material is used in an atmosphere containing carbon dioxide or the like, its service life can be extended.
また、本発明による黒鉛材料は、１０００℃付近の高温
で長時間、金属と接触しても、浸炭現象を発生させるこ
とはない。従って、半導体などの電子部品等の浸炭によ
る不良発生率を著しく低下させることができ、また、高
品質の製品を安定して製造することができる。Further, the graphite material according to the present invention does not cause carburization even if it comes into contact with metal for a long time at a high temperature around 1000°C. Therefore, the incidence of defects due to carburization of electronic components such as semiconductors can be significantly reduced, and high-quality products can be stably manufactured.
第１図は、黒鉛材料の粒子構造を示す走査型電子顕微鏡
写真である。FIG. 1 is a scanning electron micrograph showing the particle structure of graphite material.
Claims (2)
たミクロ構造を有し、嵩密度が１．５０〜１．９５ｇ／
ｃｍ＾３である黒鉛材料。(1) It has a microstructure in which carbon black is attached around the surface of graphite particles, and the bulk density is 1.50 to 1.95 g/
Graphite material that is cm^3.
状の炭素材用原料を成型し、焼成炭化、黒鉛化すること
を特徴とする黒鉛粒子の表面周囲にカーボンブラックが
付着したミクロ構造を有する黒鉛材料の製造方法。(2) A particulate raw material for carbon material mixed with 2 to 20% by weight of carbon black is molded, fired, carbonized, and graphitized.It has a microstructure in which carbon black is attached around the surface of graphite particles. Method of manufacturing graphite material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2287087A JPH04164861A (en) | 1990-10-26 | 1990-10-26 | Graphite material and production thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2287087A JPH04164861A (en) | 1990-10-26 | 1990-10-26 | Graphite material and production thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04164861A true JPH04164861A (en) | 1992-06-10 |
Family
ID=17712887
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2287087A Pending JPH04164861A (en) | 1990-10-26 | 1990-10-26 | Graphite material and production thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04164861A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354477A (en) * | 2000-06-13 | 2001-12-25 | Toyo Tanso Kk | Low carburized graphite material, sealing jig, glass molding jig and sintered hard alloy heating jig all obtained by using the material |
| JP2020152902A (en) * | 2019-03-19 | 2020-09-24 | 関西熱化学株式会社 | Carbon black molded body and method for producing the same |
-
1990
- 1990-10-26 JP JP2287087A patent/JPH04164861A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001354477A (en) * | 2000-06-13 | 2001-12-25 | Toyo Tanso Kk | Low carburized graphite material, sealing jig, glass molding jig and sintered hard alloy heating jig all obtained by using the material |
| JP2020152902A (en) * | 2019-03-19 | 2020-09-24 | 関西熱化学株式会社 | Carbon black molded body and method for producing the same |
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