JPH0331756B2 - - Google Patents
Info
- Publication number
- JPH0331756B2 JPH0331756B2 JP60210202A JP21020285A JPH0331756B2 JP H0331756 B2 JPH0331756 B2 JP H0331756B2 JP 60210202 A JP60210202 A JP 60210202A JP 21020285 A JP21020285 A JP 21020285A JP H0331756 B2 JPH0331756 B2 JP H0331756B2
- Authority
- JP
- Japan
- Prior art keywords
- coke
- carbon black
- pitch
- isotropic
- oil absorption
- 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.)
- Expired - Lifetime
Links
- 239000000571 coke Substances 0.000 claims description 43
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 30
- 239000006229 carbon black Substances 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 19
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 241000872198 Serjania polyphylla Species 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 238000010000 carbonizing Methods 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000011295 pitch Substances 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 239000002245 particle Substances 0.000 description 10
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000000465 moulding Methods 0.000 description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 8
- 230000005484 gravity Effects 0.000 description 8
- 239000000654 additive Substances 0.000 description 6
- 239000011294 coal tar pitch Substances 0.000 description 5
- 229920001971 elastomer Polymers 0.000 description 5
- 239000007770 graphite material Substances 0.000 description 5
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 239000011305 binder pitch Substances 0.000 description 4
- 238000004898 kneading Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- 238000003763 carbonization Methods 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 239000006253 pitch coke Substances 0.000 description 3
- 238000001907 polarising light microscopy Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000002006 petroleum coke Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- 239000006237 Intermediate SAF Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000006230 acetylene black Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- -1 aromatic nitro compounds Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000006231 channel black Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000009760 electrical discharge machining Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 239000012433 hydrogen halide Substances 0.000 description 1
- 229910000039 hydrogen halide Inorganic materials 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910021470 non-graphitizable carbon Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000011973 solid acid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007514 turning Methods 0.000 description 1
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は放電加工用電極、シリコン単結晶引き
上げ用るつぼ及びヒーター、シーリング等の機械
用、更に原子炉の炉材用など極めて広範囲にわた
つて利用されている等方性高密度黒鉛に適した原
料コークスを製造する方法に関するものである。[Detailed Description of the Invention] (Field of Industrial Application) The present invention is applicable to a very wide range of applications, such as electrodes for electrical discharge machining, crucibles and heaters for pulling silicon single crystals, machinery such as sealing, and furthermore, for use in reactor materials for nuclear reactors. The present invention relates to a method for producing raw material coke suitable for the isotropic high-density graphite used.
（従来の技術）
高密度等方性黒鉛製品は、〓焼したピツチコー
クス、石油コークスなどを骨材とし、これを粉砕
機により20〜30μm以下に微粉砕し、これにコー
ルタールピツチの様な結合剤を添加し、混〓した
後、押出し法又は型込め法で成型し、約1000℃で
焼成した後、更に約3000℃で黒鉛化してつくられ
る。然るに市販のピツチコークス、石油コークス
は、コークスの光学的異方性組織が大きいため、
これらのコークスを粉砕した時、コークス粒子が
針状に近い形状を呈している。(Prior technology) High-density isotropic graphite products are made by using baked pitch coke, petroleum coke, etc. as aggregate, which is pulverized to 20 to 30 μm or less using a crusher, and then bonded with coal tar pitch. After adding the agent and mixing, it is molded by extrusion or molding, fired at about 1000℃, and then graphitized at about 3000℃. However, commercially available pitch coke and petroleum coke have a large optically anisotropic structure, so
When these cokes are crushed, the coke particles have a nearly needle-like shape.
従つて、これらの粉砕コークスを用いて混〓物
を成型する際には、コークス粒子が一定方向に配
向するため、かかるコークスを使用すると高密
度、等方性炭素成型体を得ることが困難であつ
た。このため、成型物の異方性を小さくする目的
で、コークスの組織を微細にする方法が種々提案
されている。 Therefore, when molding a mixture using such pulverized coke, the coke particles are oriented in a certain direction, making it difficult to obtain a high-density, isotropic carbon molded body using such coke. It was hot. For this reason, various methods have been proposed to make the coke structure finer in order to reduce the anisotropy of the molded product.
例えば、空気、酸素あるいはオゾンを用いて瀝
青物質の酸化処理を行なう方法、あるいは瀝青物
質に種々の添加物を添加した後、炭化する方法な
どがある。添加物として、固体酸、固体塩基、硫
黄、ポリ弗化ビニリデン、フエノール樹脂、アル
カリ金属あるいはアルカリ金属の酸化物、芳香族
ニトロ化合物、カーボン微粉末などがある（特公
昭47−22931号、特開昭51−131496号、特公昭53
−35792号公報）。 For example, there is a method of oxidizing the bituminous material using air, oxygen or ozone, or a method of adding various additives to the bituminous material and then carbonizing the material. Additives include solid acids, solid bases, sulfur, polyvinylidene fluoride, phenolic resins, alkali metals or oxides of alkali metals, aromatic nitro compounds, fine carbon powder, etc. No. 131496, Special Publication No. 1982-131496
-35792).
これらの方法のうち、酸化処理は溶融した瀝青
物質あるいは瀝青物質の粉末に酸化性のガスを流
して酸化する方法（特開昭49−193号、特開昭51
−50302号各公報）であるが、この反応は発熱反
応であるため、高温度で長時間空気吹込みを行な
うと、局部加熱が起り易く部分的に〓焼し、この
ピツチを炭化して出来るコークスの光学的異方性
組織にはむらが出来、酸化処理だけでは、等方性
黒鉛材料用原料コークスを製造することは困難で
ある。 Among these methods, oxidation treatment is a method of oxidizing molten bituminous material or bituminous material powder by flowing oxidizing gas (Japanese Patent Application Laid-open No. 49-193, JP-A No. 51
However, since this reaction is an exothermic reaction, if air is blown at high temperatures for a long period of time, local heating tends to occur, resulting in partial burning and carbonization of this pitch. The optically anisotropic structure of coke is uneven, and it is difficult to produce raw material coke for isotropic graphite material only by oxidation treatment.
また、添加剤を混合する方法においては次のよ
うな欠点がある。無機化合物や金属などを添加す
る場合、生成するコークスに無機化合物、金属な
どが残存するので、このコークスを使用して作成
した成型体を、焼成、黒鉛化する際、金属が飛散
し環境上好ましくない。又ハロゲン、あるいは硫
黄を用いると、炭化時にハロゲン化水素、あるい
は硫化水素が発生するので、除去装置を設置する
必要があり経済的でない。 Furthermore, the method of mixing additives has the following drawbacks. When inorganic compounds and metals are added, the inorganic compounds and metals remain in the coke that is produced, so when molded bodies made using this coke are fired and graphitized, the metals scatter, which is not environmentally friendly. do not have. Furthermore, when halogen or sulfur is used, hydrogen halide or hydrogen sulfide is generated during carbonization, which requires the installation of a removal device, which is not economical.
これらのことから、フエノール樹脂、ポリエー
テルが添加剤として望ましいとされているが、共
炭化のみの場合は、添加剤の添加量を多くしない
と（例えば50wt％以上）、微細な組織のコークス
が得られないため経済的でない。又カーボンブラ
ツクを添加して粒径のそろつたメソフエース球体
を溶剤により抽出し、これをバインダーを使わな
いで成型するバインダレス炭素材とする方法（特
開昭49−23792号公報）があるが、メソフエース
球体の収率が10〜20％と低いうえ、溶剤抽出と言
う煩雑な作業を繰り返すことを必要とするため経
済的でない。 For these reasons, phenolic resins and polyethers are considered desirable as additives, but in the case of only co-carbonization, unless the amount of additives added is large (for example, 50 wt% or more), coke with a fine structure may be formed. It is not economical because it cannot be obtained. There is also a method of adding carbon black and extracting mesophase spheres with a uniform particle size using a solvent, and molding this into a binderless carbon material without using a binder (Japanese Patent Laid-Open No. 49-23792). The yield of mesophase spheres is low at 10 to 20%, and it is not economical because it requires repeating the complicated process of solvent extraction.
そして従来の等方性高密度黒鉛材の製法は、光
学的異方性組織の大きなピツチコークスを微粉砕
し、これを粘結剤と混合し成型焼成して、全体と
してほぼ等方性となる様にしていたが、粉砕コー
クスの異方性組織はいぜんとして大きかつた。 The conventional manufacturing method for isotropic high-density graphite material involves finely pulverizing pitch coke with a large optically anisotropic structure, mixing it with a binder, molding and firing it, and making the material almost isotropic as a whole. However, the anisotropic structure of the crushed coke was still large.
（発明が解決しようとする問題点）
本発明は添加剤としてジブチルフタレート
（D.B.P.）吸油量の多いカーボンブラツクを添加
することにより、経済的で微細な光学的異方性組
織を有する原料コークスを製造しようとするもの
である。本発明の原料コークスは、等方性高密度
黒鉛材を製造する場合の素材として適している。(Problems to be Solved by the Invention) The present invention produces raw coke that is economical and has a fine optically anisotropic structure by adding carbon black with a high dibutyl phthalate (DBP) oil absorption as an additive. This is what I am trying to do. The raw material coke of the present invention is suitable as a material for producing isotropic high-density graphite material.
（問題点を解決するための手段）
本発明はコールタールピツチ、石油系ピツチ等
の瀝青物質に、ジブチルフタレート（D.B.P.）吸
油量90ml／100mg以上のカーボンブラツクを添加
し、次いでこの混合物を二軸混練装置等で混〓し
た後、炭化して等方性炭素材用の用途に適した微
細組織を有するコークスを製造する方法である。(Means for Solving the Problems) The present invention involves adding carbon black having a dibutyl phthalate (DBP) oil absorption of 90 ml/100 mg or more to a bituminous substance such as coal tar pitch or petroleum pitch, and then turning this mixture into a biaxial This is a method of producing coke having a fine structure suitable for use as an isotropic carbon material by mixing it in a kneading device or the like and then carbonizing it.
本発明で使用する瀝青物質には特に制限はない
が、主としてコールタールピツチ、石油系アスフ
アルト、炭化水素の熱分解によつて生成するピツ
チなど工業的に製造されている瀝青物質が用いら
れる。 The bituminous substance used in the present invention is not particularly limited, but industrially produced bituminous substances such as coal tar pitch, petroleum-based asphalt, and pitch produced by thermal decomposition of hydrocarbons are mainly used.
また本発明で言うカーボンブラツクとは、ジブ
チルフタレート（D.B.P.）吸油量が90ml／100ｇ
以上のHAF，FEF，SAF，ISAF，IISAF−HS、
などのゴム用フアーネスカーボンブラツク及びア
セチレンブラツク、カラー用チヤンネルブラツク
などである。 In addition, the carbon black referred to in the present invention has a dibutyl phthalate (DBP) oil absorption of 90ml/100g.
HAF, FEF, SAF, ISAF, IISAF-HS,
Furnace carbon black and acetylene black for rubber, channel black for color, etc.
D.B.P.吸油量は、カーボンブラツク粒子間の化
学的、物理的結合による複雑なストラクチヤーの
発達を知るための指標であり、カーボンブラツク
粒子の表面官能基（カルボキシル基、キノン基な
ど）とも関連があるが、官能基の測定は極めて困
難で一般には行なわれていない。 DBP oil absorption is an indicator for understanding the development of a complex structure due to chemical and physical bonds between carbon black particles, and is also related to the surface functional groups (carboxyl groups, quinone groups, etc.) of carbon black particles. However, measurement of functional groups is extremely difficult and is not generally carried out.
カーボンブラツクをピツチへ少量添加して炭化
したコークスは、異方性組織にむらが出来る。従
つて、D.B.P.吸油量の低いカーボンブラツクで
は、30wt％以上の添加が必要である。しかし、
カーボンブラツクの添加量を増加させると、マト
リツクスであるピツチの粘度が急激に増加し、混
〓が困難になる。また、カーボンブラツクをピツ
チへ多量に混合すると、この混合物から得たコー
クスは、難黒鉛化性の炭素になる。 Coke that is carbonized by adding a small amount of carbon black to the pitch has an uneven anisotropic structure. Therefore, for carbon black with low DBP oil absorption, it is necessary to add 30 wt% or more. but,
When the amount of carbon black added increases, the viscosity of the pitch matrix increases rapidly, making mixing difficult. Furthermore, when a large amount of carbon black is mixed into the pitch, the coke obtained from this mixture becomes non-graphitizable carbon.
ところが、D.B.P.吸油量90ml／100ｇ以上のカ
ーボンブラツクであれば、ピツチとの分散性が良
いため、該カーボンブラツクを瀝青物質に少量添
加（10〜40wt％）し、共炭化して得られるコー
クスの光学的異方性組織単位は、数μ〜十数μと
非常に微細化する。また、該カーボンブラツクを
使用すれば、添加量が少なくてすむため経済的で
あるばかりでなく、これから得られるコークスの
黒鉛化性はあまり悪くならない。 However, if carbon black has a DBP oil absorption of 90 ml/100 g or more, it has good dispersibility with pitch, so a small amount (10 to 40 wt%) of the carbon black is added to the bituminous material, and the resulting coke is co-carbonized. The optically anisotropic structural unit becomes very fine, ranging from several microns to more than ten microns. Further, if the carbon black is used, it is not only economical since only a small amount of carbon black is added, but also the graphitization properties of the coke obtained from the carbon black do not deteriorate so much.
コークスの光学的異方性組織単位を、数μ〜十
数μにするために必要なD.B.P.吸油量90ml／100
ｇ以上のカーボンブラツクの添加量は10〜40wt
％であり、10wt％未満では効果が少ない。40wt
％を超えて添加し、共炭化した場合は、ガラス状
コークスの様になり、微細な異方性組織は認めら
れにくくなる。実用的には異方性組織単位が10μ
以下にすることが望ましく、この場合のカーボン
ブラツクの添加量は、20〜30wt％とすることが
好ましい。 DBP oil absorption required to make the optically anisotropic structural unit of coke from several microns to several tens of microns is 90 ml/100
The amount of carbon black added is 10 to 40wt.
%, and less than 10wt% has little effect. 40wt
If it is added in excess of % and co-carbonized, it becomes like glassy coke and a fine anisotropic structure becomes difficult to recognize. Practically speaking, the anisotropic structure unit is 10μ.
The amount of carbon black added is preferably 20 to 30 wt%.
この様にして、カーボンブラツクを添加した瀝
青物質を、アルゴン、窒素などの不活性ガスの雰
囲気下150℃／Hrの昇温速度で、例えば500℃〜
600℃で炭化し、この温度で２時間保持してコー
クスを得る。これが本発明の等方性炭素材用コー
クスで、これは微細構造を有している。 In this way, the bituminous material doped with carbon black is heated, for example, from 500°C to
Carbonize at 600°C and hold at this temperature for 2 hours to obtain coke. This is the isotropic carbon material coke of the present invention, which has a fine structure.
このコークスを粉砕してから結合剤を混ぜて成
型し、この成型体を、コークスブリーズ中に埋め
込み、不活性ガス雰囲気中で例えば1000〜1100℃
の温度で焼成し、必要に応じて約2600℃の温度で
黒鉛化して、等方性高密度炭素材又は黒鉛材とす
る。 This coke is crushed, mixed with a binder and molded, and this molded body is embedded in a coke breeze and heated to, for example, 1000 to 1100°C in an inert gas atmosphere.
The material is fired at a temperature of approximately 2,600°C and graphitized as necessary to produce an isotropic high-density carbon material or graphite material.
（実施例）
実施例 １
コールタールピツチからキノリン不溶分を除去
したピツチにD.B.P.吸油量126ml／100ｇのカーボ
ンブラツクを20wt％添加し、鋳込みヒーター付
き二軸混練装置で試料温度100℃で30分間混〓し
た。このピツチを150℃／Hrの昇温速度で600℃
迄昇温し、600℃で２時間保持して炭化した。(Example) Example 1 20 wt% of carbon black with a DBP oil absorption of 126 ml/100 g was added to pitch from which quinoline insoluble matter had been removed from coal tar pitch, and the mixture was mixed for 30 minutes at a sample temperature of 100°C using a twin-screw kneading device equipped with a casting heater. 〓I did. This pitch was heated to 600℃ at a heating rate of 150℃/Hr.
The temperature was raised to 600°C for 2 hours to carbonize.
得られたコークスの備光顕微鏡観察結果では、
その光学的異方性組織の単位は数μmと非常に微
細なものであつた。このコークスをアトライター
で粉砕し、平均粒径10μmとした。この粉砕コー
クス100重量部に対し、バインダーピツチを45重
量部添加した後、250℃に加熱したニーダーで１
時間混練した。 According to the observation results of the obtained coke using a light microscope,
The unit of the optically anisotropic structure was extremely minute, several μm. This coke was pulverized with an attritor to give an average particle size of 10 μm. After adding 45 parts by weight of binder pitch to 100 parts by weight of this pulverized coke, it was
Kneaded for hours.
この混練物を再粉砕し、平均粒径10μmにした。
これを直径30φmmの金型に40ｇ充填し、50Kg／cm2
の圧力で一次成型した後ラバーに詰め、2t／cm2の
圧力でラバープレス成型した。得られた成型体は
直径24φmm、長さ30mmであつた。この成型体をコ
ークスブリーズでパツキングし、窒素気流下0.5
℃／minの昇温速度で1100℃まで昇温した。 This kneaded material was re-pulverized to have an average particle size of 10 μm.
Fill 40g of this into a mold with a diameter of 30φmm, and make 50Kg/cm 2
After primary molding at a pressure of 2 t/cm 2 , it was packed into rubber and rubber press molded at a pressure of 2 t/cm 2 . The obtained molded body had a diameter of 24φmm and a length of 30mm. This molded body was packed with coke breeze, and 0.5
The temperature was raised to 1100°C at a heating rate of °C/min.
この焼成体は、カサ比重1.72ｇ／cm3であつた。
この焼成体を10℃／minの昇温速度で2600℃迄昇
温し、この温度で20分間保持して黒鉛化した。こ
の黒鉛化物の性状は、カサ比重1.88ｇ／cm3、曲げ
強度700Kg／cm2、シヨアー強度83，電気抵抗
2700μΩcmであつた。 This fired body had a bulk specific gravity of 1.72 g/cm 3 .
This fired body was heated to 2600°C at a heating rate of 10°C/min, and maintained at this temperature for 20 minutes to graphitize it. The properties of this graphitized material are bulk specific gravity 1.88g/cm 3 , bending strength 700Kg/cm 2 , shore strength 83, and electrical resistance.
It was 2700μΩcm.
実施例 ２
コールタールピツチからキノリン不溶分を除去
したピツチに、D.B.P.吸油量126ml／100ｇのカー
ボンブラツクを40wt％添加し、鋳込みヒーター
付き二軸混練装置で、試料温度120℃で30分間混
練した。このピツチを150℃／Hrの昇温速度で
600℃迄昇温し、600℃で２時間保持して炭化し
た。Example 2 40 wt% of carbon black with a DBP oil absorption of 126 ml/100 g was added to coal tar pitch from which the quinoline insoluble matter had been removed, and the mixture was kneaded for 30 minutes at a sample temperature of 120°C using a twin-screw kneading device equipped with a casting heater. This pitch was heated at a heating rate of 150℃/Hr.
The temperature was raised to 600°C and held at 600°C for 2 hours to carbonize.
得られたコークスの偏光顕微鏡観察結果では、
その光学的異方性組織の単位が認めにくいほど微
細で、クラツシーカーボンに近い状態であつた。 According to the polarized light microscopy observation results of the coke obtained,
The units of the optically anisotropic structure were so fine that they were difficult to recognize, and the state was close to that of crusty carbon.
このコークスを粉砕機で粉砕し、平均粒径
10μmとした。この粉砕コークス100重量部に対
し、バインダーピツチ45重量部添加し、実施例１
と同様の手順で成型、焼成を行なつた。得られた
焼成体は、カサ比重1.75ｇ／cm3であつた。この焼
成体を実施例１と同じ条件で黒鉛化した。 This coke is crushed with a crusher and the average particle size is
It was set to 10 μm. Example 1 45 parts by weight of binder pitch was added to 100 parts by weight of this pulverized coke.
Molding and firing were carried out in the same manner as above. The obtained fired body had a bulk specific gravity of 1.75 g/cm 3 . This fired body was graphitized under the same conditions as in Example 1.
この黒鉛化物の性状は、カサ比重1.89、曲げ強
度715Kg／cm2、シヨアー硬度90、電気抵抗2920μ
Ωcmであつた。 The properties of this graphitized material are bulk specific gravity 1.89, bending strength 715Kg/cm 2 , shore hardness 90, and electrical resistance 2920μ.
It was Ωcm.
実施例 ３
実施例１で用いたピツチにD.B.P.吸油量126
ml／100ｇのカーボンブラツクを10wt％添加し、
鋳込みヒーター付き二軸混練装置で試料温度100
℃で30分間混練した。このピツチを150℃／Hrの
昇温速度で600℃迄昇温し、この温度で２時間保
持して炭化した。Example 3 The pitch used in Example 1 had a DBP oil absorption of 126
Add 10wt% of carbon black in ml/100g,
The sample temperature is 100 with a twin-screw kneading device equipped with a cast-in heater.
The mixture was kneaded for 30 minutes at ℃. This pitch was heated to 600°C at a heating rate of 150°C/Hr, and maintained at this temperature for 2 hours to carbonize.
得られたコークスの偏光顕微鏡観察結果では、
その光学的異方性組織には若干むらが出来たもの
の、ほぼ均一な微細組織となつており、その光学
的異方性組織の単位としては、大部分が十数μm
であつた。このコークスを粉砕機で粉砕し、平均
粒径10μmとした。この粉砕コークス100重量部に
対し、バインダーピツチを45重量部に添加し、実
施例１と同様の手順で成型焼成を行なつた。得ら
れた焼成体は、カサ比重1.67ｇ／cm3であつた。 According to the polarized light microscopy observation results of the coke obtained,
Although there was some unevenness in the optically anisotropic structure, it was a nearly uniform microstructure, and the unit of the optically anisotropic structure was mostly about 10 or more μm.
It was hot. This coke was pulverized using a pulverizer to give an average particle size of 10 μm. 45 parts by weight of binder pitch was added to 100 parts by weight of this pulverized coke, and molding and firing was performed in the same manner as in Example 1. The obtained fired body had a bulk specific gravity of 1.67 g/cm 3 .
この焼成体を実施例１と同じ条件で黒鉛化し
た。この黒鉛化物の性状は、カサ比重1.81ｇ／
cm3、曲げ強度625Kg／cm2、シヨアー硬度78、電気
抵抗2340μΩcmであつた。 This fired body was graphitized under the same conditions as in Example 1. The properties of this graphitized material are bulk specific gravity 1.81g/
cm 3 , bending strength 625 Kg/cm 2 , Shore hardness 78, and electrical resistance 2340 μΩcm.
比較例
実施例１で使用したコールタールピツチにD.
B.P.吸油量85ml／100ｇのカーボンブラツクを
20wt％添加し、鋳込みヒーター付き二軸混練装
置で、試料温度90℃で30分間混練した。このピツ
チを150℃／Hrの昇温速度で600℃迄昇温し、600
℃で２時間保持して炭化した。Comparative example D.
Carbon black with BP oil absorption of 85ml/100g
20 wt% was added and kneaded for 30 minutes at a sample temperature of 90°C using a twin-screw kneader equipped with a cast heater. This pitch was heated to 600℃ at a heating rate of 150℃/Hr.
It was held at ℃ for 2 hours to carbonize.
得られたコークスの偏光顕微鏡観察結果では、
その光学的異方性組織は、流れ組織の部分とモザ
イク組の部分とが混存しており、均一な微細組織
ではなかつた。このコークスを粉砕機で平均粒径
10μmに粉砕した。 According to the polarized light microscopy observation results of the coke obtained,
The optically anisotropic structure contained a flow structure part and a mosaic set part, and was not a uniform microstructure. The average particle size of this coke is
It was ground to 10 μm.
この粉砕コークス100重量部に対し、バインダ
ーピツチを45重量部添加した後、250℃に加熱し
たニーダーで１時間混練した。これを直径30φmm
の金型に40ｇ充填し、50Kg／cm2の圧力で一次成型
した後ラバーに詰め2t／cm2の圧力でラバープレス
成型した。 After adding 45 parts by weight of binder pitch to 100 parts by weight of this pulverized coke, the mixture was kneaded for 1 hour in a kneader heated to 250°C. This has a diameter of 30φmm
40g was filled into a mold, and after primary molding at a pressure of 50Kg/cm 2 , it was packed into rubber and rubber press molded at a pressure of 2t/cm 2 .
得られた成型体は直径23φmm、長さ28mmであつ
た。この成型体をコークスブリーズでパツキング
し、窒素気流下0.5℃／minの昇温速度で1100℃
まで昇温した。この焼成体は、カサ比重1.54ｇ／
cm3であつた。この焼成体を10℃／minの昇温速度
で2600℃で黒鉛化した。この黒鉛化物の性状は、
カサ比重1.72ｇ／cm3、曲げ強度500Kg／cm2、シヨ
アー硬度64、電気抵抗2100μΩcmであつた。 The obtained molded body had a diameter of 23φmm and a length of 28mm. This molded body was packed with coke breeze and heated to 1100℃ at a heating rate of 0.5℃/min under nitrogen flow.
The temperature rose to . This fired body has a bulk specific gravity of 1.54g/
It was warm at cm3 . This fired body was graphitized at 2600°C at a heating rate of 10°C/min. The properties of this graphitized material are
The bulk specific gravity was 1.72 g/cm 3 , the bending strength was 500 Kg/cm 2 , the Shore hardness was 64, and the electrical resistance was 2100 μΩcm.
（発明の効果）
本発明によつて等方性高密度黒鉛材の原料に適
した微細な組織を有するコークスを製造すること
が出来る。従来の方法のものに比べ成型密度の高
い強度の高い高密度、高強度等方性黒鉛製品を作
ることが出来、特に機械用治具材のような強度を
要求されるものの材料として最適である。(Effects of the Invention) According to the present invention, coke having a fine structure suitable as a raw material for isotropic high-density graphite material can be produced. It is possible to produce high-density, high-strength isotropic graphite products with a higher molding density than those made using conventional methods, making it particularly suitable as a material for items that require strength, such as mechanical jig materials. .
Claims (1)
油量90ml／100ｇ以上のカーボンブラツクを10〜
40wt％添加し、混〓した後、この混合物を不活
性雰囲気中で炭化することを特徴とする等方性炭
素材用コークスの製造方法。1 Add carbon black with a dibutyl phthalate (DBP) oil absorption of 90ml/100g or more to the bituminous material.
A method for producing coke for isotropic carbon material, which comprises adding 40 wt% of coke, mixing, and then carbonizing the mixture in an inert atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60210202A JPS6270216A (en) | 1985-09-25 | 1985-09-25 | Production of coke for isotropic carbon material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP60210202A JPS6270216A (en) | 1985-09-25 | 1985-09-25 | Production of coke for isotropic carbon material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6270216A JPS6270216A (en) | 1987-03-31 |
| JPH0331756B2 true JPH0331756B2 (en) | 1991-05-08 |
Family
ID=16585479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP60210202A Granted JPS6270216A (en) | 1985-09-25 | 1985-09-25 | Production of coke for isotropic carbon material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6270216A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01179713A (en) * | 1988-01-07 | 1989-07-17 | Denki Kagaku Kogyo Kk | Carbon black for electrode |
| US6787029B2 (en) | 2001-08-31 | 2004-09-07 | Cabot Corporation | Material for chromatography |
| CN114702316B (en) * | 2022-03-23 | 2023-05-30 | 湖南大学 | Preparation method and application of low-cost high-purity graphite material |
-
1985
- 1985-09-25 JP JP60210202A patent/JPS6270216A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6270216A (en) | 1987-03-31 |
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