JPS60195012A - Carbonaceous material - Google Patents

Abstract

PURPOSE:A carbonaceous material that is formed by sintering a mixture of aggregate and a specific binder, thus showing high density, high strength and high oxidation resistance. CONSTITUTION:A mixture composed of (a) pitch (more than 40wt% soluble in benzene, less than 20wt% insoluble in quinoline) (0.2-5pts.wt.) and an alkyl- modified phenolic resin having the basic unit of the formula (R is 1-4C alkyl) (1pt.wt.) is used as a binder. Namely, (A) aggregate such as pitich coke, graphite, carbon black, zirkonium carbide is combined with (B) about 5-50wt% of the above binder, preferably they are kneaded, while they are hot, compressed into a form desired and sintered at about 800-2,000 deg.C in a reducing atmosphere or inert atmosphere to give the objective carbonaceous material in which the carbonized texture of the binder are completely fine mosaic structure.

Description

【発明の詳細な説明】 本発明は、高密度、高強度および耐酸化性に優れた炭素
質部材に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a carbonaceous member having high density, high strength and excellent oxidation resistance.

炭素質部材は製鉄、製鋼用炉材、電鋳設備、アルミニウ
ム精錬などにおける電極、あるいはメカニカルシールな
との摺動用部材として多用されている。この炭素質部材
に要求される特性は、高密度、高強度および耐酸化性で
ある。Carbonaceous members are widely used as electrodes in iron manufacturing, steelmaking furnace materials, electroforming equipment, aluminum refining, etc., or as sliding members in mechanical seals. The characteristics required of this carbonaceous member are high density, high strength, and oxidation resistance.

従来、炭素質部材の製造においては結合剤として・ピッ
チデフエノール樹脂などが使用サレーｔｃイる。これら
は殆んどの場合、単独で使用し、両者を併用する場合も
、フェノール樹脂を併用することによって、室温で混線
できるという作業性を意図したものにすぎない。Conventionally, in the manufacture of carbonaceous members, pitch dephenol resins and the like have been used as binders. In most cases, these are used alone, and even when they are used in combination, they are merely intended to improve workability by using a phenol resin in combination to allow crosstalk at room temperature.

そこで、本発明者らは、ピッチ及びフェノール樹脂を結
合剤としての性能を向上すべく実験を重ねた結果、ＢＳ
成分（ベンゼン可溶成分）４０ｗｔ％以上、ＱＩ酸成分
キノリンネ可溶分）２０ｖｒｔ％以下であるピッチに対
して、フェノール樹脂の中でも特にアルキル変性フェノ
ール樹脂を組み合せ、かつ両者の比を特定の範囲に限定
すると、緻密。Therefore, as a result of repeated experiments to improve the performance of pitch and phenolic resin as a binder, the present inventors found that BS
For the pitch whose components (benzene soluble component) are 40wt% or more, QI acid component quinoline soluble component) 20vrt% or less, alkyl-modified phenol resin among phenolic resins is combined, and the ratio of both is set within a specific range. If you limit it, it's precise.

強固なカーボンポンドを有すると共に、耐酸化性に優れ
た炭素質部材が得られることを知り、本発明を完成させ
たものである。The present invention was completed based on the knowledge that a carbonaceous member having strong carbon pounds and excellent oxidation resistance can be obtained.

以下、本発明をさらに詳述する。The present invention will be explained in further detail below.

１ ピッチの炭化組織は、次のように分類できる。1 The carbonized structure of pitch can be classified as follows.

ピッチの炭化組織は石油系１石炭系を問わず、流れ構造
あるいは、これに近い構造を示す。一方、フェノール樹
脂はレゾール型、ノボラック型、熱硬化性、熱可塑性い
ずれにおいてもガラス状構造を示す。又、ピッチとフェ
ノール樹脂を併用した場合、上述の流れ構造、ガラス状
構造に加え、その界面附近にファインモザイク構造が現
われこれらの３層が共存した構造となる。The carbonized structure of pitch exhibits a flow structure or a structure close to this, regardless of whether it is petroleum-based or coal-based. On the other hand, phenolic resin exhibits a glass-like structure whether it is a resol type, a novolac type, a thermosetting type, or a thermoplastic type. Furthermore, when pitch and phenol resin are used together, in addition to the above-mentioned flow structure and glass-like structure, a fine mosaic structure appears near the interface, resulting in a structure in which these three layers coexist.

これらの炭化組織は、次のような特徴をもつ、まず、流
れ構造は配向しているため流れ構造に沿って、キレンを
発生し易くなシ、又これを結合材とする炭素質部材の強
度、熱伝導率等の物性に方向性が生じる。These carbonized structures have the following characteristics: first, because the flow structure is oriented, they do not easily generate chines along the flow structure; , directionality occurs in physical properties such as thermal conductivity.

ガラス状構造は均一であるが、結晶の基本単位が非常に
／トさく、炭素としての結晶度が低いため、耐酸化性に
欠ける。Although the glassy structure is uniform, the basic crystal units are very small and the crystallinity of carbon is low, so it lacks oxidation resistance.

一方、ファインモザイク構造は、比較的、基本単位の大
きい粒子の集合体であシ、結晶度も高い。On the other hand, a fine mosaic structure is an aggregate of particles having relatively large basic units and has a high degree of crystallinity.

それ故、組織として均一であシ、耐酸化性も高く、炭素
質部材の結合剤として最適である。Therefore, it has a uniform structure and high oxidation resistance, making it ideal as a binder for carbonaceous members.

本発明は、アルキル変性フェノール樹脂とＢＳ成分４０
％以上、ＱＩ成分２０チ以下のピッチを組合せ、両者の
比を特定の範囲内に限定することで、結合剤の炭化組織
を全面ファインモザイク構造にした炭素質部材を得たも
のである。The present invention uses an alkyl-modified phenol resin and a BS component of 40%.
By combining a pitch of % or more and a QI component of 20 inches or less and limiting the ratio of the two within a specific range, a carbonaceous member is obtained in which the carbonized structure of the binder has a fine mosaic structure on the entire surface.

アルキル変性フェノール樹脂は基本単位をＨ とするものである。これ以外のフェノール樹脂は、ピッ
チと併用した場合、両者のなじみが乏しく全面ファイン
モザイク構造の炭化組織が得られない。The basic unit of the alkyl-modified phenol resin is H 2 . When other phenol resins are used in combination with pitch, they are not compatible with each other and a carbonized structure with a fine mosaic structure on the entire surface cannot be obtained.

ピッチは石油系２石炭系いずれでもよいが、ＢＳ成分（
ベンゼン可溶成分）４０ｗｔ％、ＱＩ酸成分キノリンネ
可溶分）　２０　ｗｔ％以下のものを使用しなければな
らない。ＢＳ、ＱＩ酸成分、この範囲外のものは、溶融
後の粘度が高く、バインダーとしての分散性に欠けてい
たシする。第１図、第２図は、上記ピッチ／アルキル変
性フェノール樹脂の併用比（混合比）を変化させ、他の
条件は、下記゛のとおり同一とした場合の炭素質部材の
物性を示したものである。The pitch may be either petroleum-based or coal-based, but the BS component (
Benzene soluble component) 40 wt%, QI acid component quinoline soluble component) 20 wt% or less must be used. BS and QI acid components outside this range had high viscosity after melting and lacked dispersibility as a binder. Figures 1 and 2 show the physical properties of carbonaceous members when the combination ratio (mixing ratio) of the above-mentioned pitch/alkyl modified phenol resin is changed and other conditions are the same as shown below. It is.

骨材　；ピッチコークス１６Ｍ− 結合材；ピッチ及びアルキル変性フェノール樹脂の合計
量として外掛２０　ｗｔ４ 混　練；１５０℃Ｘ３０分、熱間混練 酸　形；　１０００　ｋｇ／ｃｍ”、−軸加圧焼　成；
　１２００℃ｘ１６Ｈ，還元焼成このようにピッチ／ア
ルキル変成フェノール樹脂の併用比（重量比）が０．２
〜５の範囲を外れると、緻密性２強度、または耐酸化性
に劣る。Aggregate: Pitch coke 16M - Binder: Total amount of pitch and alkyl modified phenolic resin: 20 wt4 Kneading: Hot kneading at 150°C for 30 minutes, acid form: 1000 kg/cm'', - Axial pressure firing;
1200℃ x 16H, reduction firing As shown above, the combination ratio (weight ratio) of pitch/alkyl modified phenolic resin is 0.2
If it is out of the range of ~5, the compactness 2 strength or oxidation resistance will be poor.

０．２未満では結合剤の炭化組織が全面ファインそディ
ジとならず、フェノール樹脂特有の炭化組織であるガラ
ス状構造が一部存在し、前述したように耐酸化が欠ける
という欠点がある。又、５．０を越えると、ピッチ特有
の炭化組織である流れ構造が一部存在し、前述したよう
に、強度レベル。If it is less than 0.2, the carbonized structure of the binder will not be finely grained over the entire surface, and a glass-like structure, which is the carbonized structure peculiar to phenolic resins, will be present in some parts, resulting in the disadvantage of lacking oxidation resistance as described above. Moreover, when it exceeds 5.0, there is a part of the flow structure which is a carbonized structure peculiar to the pitch, and as mentioned above, the strength level.

不均一性の面から好しくない。This is not desirable in terms of non-uniformity.

本発明で使用する骨材は、ピッチコークス、土状黒鉛、
リン状黒鉛、カーゼンブラック、カーデンフィイパー等
の炭素及び炭化珪素、炭化硼素。The aggregate used in the present invention is pitch coke, earthy graphite,
Carbon, silicon carbide, boron carbide such as phosphorous graphite, Kazen black, Kaden fiper.

炭化ジルコニウム等の炭化物、で一種するいは２種以上
複合して用いる。さらに部材の用途に応じは、骨材に対
して好ましくは、外掛で５〜５０　ｗｔ％である。５　
ｗｔ％未満では、結合材の残炭量の少なさから、焼成後
、カーゲンポンドの生成量が少なく、部材の強度が低く
なる。５０　ｗｔ％を超えると、焼成中において結合材
からの揮発分の発生量が多く焼成キレンを生じ易い。又
、仁のキレン発生を防止するために、昇温速度を遅くす
ると焼成に時間を要し、生産性を低下させる。Carbides such as zirconium carbide are used singly or in combination of two or more. Furthermore, depending on the intended use of the member, the amount of the outer layer is preferably 5 to 50 wt% based on the aggregate. 5
If the amount is less than wt%, the amount of carbon remaining in the binder is small, so the amount of coal pounds produced after firing is small, and the strength of the member becomes low. If it exceeds 50 wt%, a large amount of volatile matter is generated from the binder during firing, which tends to cause firing burns. In addition, if the heating rate is slowed down to prevent the formation of kerosene in the kernels, it will take time for firing, which will reduce productivity.

結合材の添加法は、上述範囲内のピッチとアルキル変性
フェノール樹脂を予め熱間で混合し、溶融状態として添
加するか、これを冷却後、解砕したものを添加するか、
または、両者別々に添加し混線中に混合するという方法
がある。混線は骨材と結合剤とのなじみを考慮して、熱
間で行うのが好ましい０冷間で行、５場合は、結合材を
微細化し、分散性をよくする。さらに分散性をよくする
ためニ、コレニ、アルコール、ベンゼン、クレオンート
油、無水タール等の有機溶媒を適量添加してもよ　□焼
成は、還元雰囲気下、不活性雰囲気下で８００〜２００
０℃程度で行う。又、必要に応じてピッチ。The method of adding the binder is to mix the pitch within the above range and the alkyl-modified phenol resin in advance in a hot state and add it in a molten state, or to cool it down and then add it in a crushed form.
Alternatively, there is a method of adding both separately and mixing them during crosstalk. In consideration of the compatibility between the aggregate and the binder, cross-wiring is preferably carried out hot, but in the case of 5, the binder is made fine and its dispersibility is improved. Furthermore, in order to improve the dispersibility, an appropriate amount of organic solvent such as alcohol, alcohol, benzene, creonate oil, anhydrous tar, etc. may be added.
Perform at around 0℃. Also, pitch if necessary.

樹脂等を含浸、コーキング処理、さらに黒鉛化処理を行
ってもよい。Impregnation with a resin or the like, caulking treatment, and further graphitization treatment may be performed.

以下、従来例と本発明実施例を示す。Below, a conventional example and an example of the present invention will be shown.

配合の種類は、下記の２種を選んだ。The following two types of formulations were selected.

■）ピッチコークス　６０メツシュ以下１００部結合材
　外掛　２０部 ■）ピッチコークス　６０メツシユ以下　７０部炭化珪
素　３２５メツシユ以下　３０部結合材　外掛　２０部 バインダーのｆｔＭは、下記４種を選んだ０１）ＢＳ成
分５０　ｗｔ％、ＱＩ成分１２　ｗｔ％のピッチ１００
チ 従来例 ２）通常のフェノール樹脂１００係 従来例 ３）　１）のピッチ／２）の樹脂＝１／１従来例 ４）　１）のピッチ／アルキル変性フェノールｍ脂＝１
／１本発明例 混線は、１５０℃×４５分行い、冷却後、１０００に９
７ｃｍ”で静水圧成形し、１２００℃Ｘ８Ｈ還元焼成し
た。■) Pitch coke 60 mesh or less 100 parts Binding material Outer hook 20 parts ■) Pitch coke 60 mesh or less 70 parts Silicon carbide 325 mesh or less 30 parts Binding material Outer hook 20 parts The ftM of the binder is the following 4 types selected 01) BS component 50 wt%, QI component 12 wt% pitch 100
H Conventional example 2) Normal phenolic resin 100 Conventional example 3) Pitch of 1) / Resin of 2) = 1/1 Conventional example 4) Pitch of 1) / Alkyl modified phenol m resin = 1
/1 Example of the present invention Crosstalk was carried out at 150°C for 45 minutes, and after cooling, the temperature was 9 to 1000.
It was subjected to isostatic pressure molding to a size of 7 cm" and reduced and fired at 1200°C for 8 hours.

その結果を次表１に示す。The results are shown in Table 1 below.

以上実施例が示すように、本発明で得られた炭素質部材
は、高密度、高強度及び耐酸化性に優れているため、製
鉄用炉材をはじめ、メカニカルシール、軸受等機械構造
用部材としても有用である。As shown in the examples above, the carbonaceous member obtained by the present invention has high density, high strength, and excellent oxidation resistance, so it can be used as a material for mechanical structures such as steelmaking furnace materials, mechanical seals, and bearings. It is also useful as

図である。It is a diagram.

第１図 ピッ手／アルモル変Ａ先フェノール頗寸市比（ｗｆ、比
）第２図Figure 1 Pitch/alumol change A point phenol size ratio (wf, ratio) Figure 2

Claims (1)

【特許請求の範囲】[Claims] 結合材として、ＢＳ成分（ベンゼン可溶分）４０　ｗｔ
％以上、Ｑ　’Ｉ酸成分キノリンネ可溶分）２０　ｗｔ
係以下のピッチとアルキル変性フェノール樹脂を重量比
でピッチ／アルキル変性フェノール樹脂が０．２〜５に
組み合せて使用し、焼成してなる炭素質部材。As a binder, 40 wt of BS component (benzene soluble content)
% or more, Q'I acid component quinoline soluble content) 20 wt
A carbonaceous member obtained by firing a pitch and an alkyl-modified phenol resin in a weight ratio of pitch/alkyl-modified phenol resin of 0.2 to 5.