JPH07118065A - Carbonaceous material excellent in oxidation resistance - Google Patents
Carbonaceous material excellent in oxidation resistanceInfo
- Publication number
- JPH07118065A JPH07118065A JP5266308A JP26630893A JPH07118065A JP H07118065 A JPH07118065 A JP H07118065A JP 5266308 A JP5266308 A JP 5266308A JP 26630893 A JP26630893 A JP 26630893A JP H07118065 A JPH07118065 A JP H07118065A
- Authority
- JP
- Japan
- Prior art keywords
- oxidation resistance
- carbonaceous material
- carbide
- strength
- carbon material
- 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
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 41
- 230000003647 oxidation Effects 0.000 title claims abstract description 39
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 39
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 11
- 229910052580 B4C Inorganic materials 0.000 claims abstract description 9
- INAHAJYZKVIDIZ-UHFFFAOYSA-N boron carbide Chemical compound B12B3B4C32B41 INAHAJYZKVIDIZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005452 bending Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 15
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 8
- 239000000463 material Substances 0.000 abstract description 10
- 150000001247 metal acetylides Chemical class 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000704 physical effect Effects 0.000 description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 9
- 239000002194 amorphous carbon material Substances 0.000 description 8
- 238000010304 firing Methods 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 239000011230 binding agent Substances 0.000 description 7
- 238000005087 graphitization Methods 0.000 description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 239000004568 cement Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 239000007770 graphite material Substances 0.000 description 4
- 230000001590 oxidative effect Effects 0.000 description 4
- 239000005011 phenolic resin Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 229910021383 artificial graphite Inorganic materials 0.000 description 2
- -1 boride Chemical class 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 238000013001 point bending Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- QYEXBYZXHDUPRC-UHFFFAOYSA-N B#[Ti]#B Chemical compound B#[Ti]#B QYEXBYZXHDUPRC-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 238000007606 doctor blade method Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- XWHPIFXRKKHEKR-UHFFFAOYSA-N iron silicon Chemical compound [Si].[Fe] XWHPIFXRKKHEKR-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229920001568 phenolic resin Polymers 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000011269 tar Substances 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
Landscapes
- Ceramic Products (AREA)
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、非鉄金属用部材、化学
機器用部材、機械部材、電極材料として使用可能な耐酸
化性に優れ、高強度、高硬度、高導電性を有する非晶質
炭素質材料に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention can be used as a non-ferrous metal member, a chemical device member, a mechanical member, and an electrode material, and is excellent in oxidation resistance and has high strength, high hardness, and high conductivity. Regarding carbonaceous materials.
【０００２】[0002]
【従来の技術】一般に炭素質材料は、酸化され易いとい
う欠点のために、高温の酸化性雰囲気下での使用は不可
能であり、高温強度、耐熱衝撃性、高熱伝導性、高導電
率、低熱膨張性など多くの優れた特性を有するにも拘わ
らず、その用途は限られたものであった。その中でも、
非晶質炭素材料は一般の黒鉛質材料に比べ諸物性におい
て劣り、その用途はさらに限られたものであった。2. Description of the Related Art Generally, carbonaceous materials cannot be used in a high-temperature oxidizing atmosphere due to the drawback that they are easily oxidized, and high-temperature strength, thermal shock resistance, high thermal conductivity, high electrical conductivity, Despite having many excellent properties such as low thermal expansion, its use was limited. Among them,
Amorphous carbon materials were inferior in physical properties to general graphite materials, and their applications were further limited.
【０００３】従来、かかる炭素質材料の欠点を解消する
ための手段として、種々の対策が提案されているが、そ
れぞれに、問題がある。Conventionally, various measures have been proposed as means for eliminating the drawbacks of such carbonaceous materials, but each has its own problems.
【０００４】（１） 炭素質基材、とくに黒鉛質基材表
面にリン酸塩やガラス被膜成分を含浸し、コーティング
する方法がある。ところが、基材である炭素質材料の耐
酸化は１００〜２００℃程度において改善されるだけで
あり、コーティングむらや使用中の剥離により局部的に
酸化が進行する恐れがあり、安定した品質を確保するこ
とが難しい。さらに、強度の向上には全く効果がない。(1) There is a method of impregnating a surface of a carbonaceous substrate, particularly a graphite substrate, with a phosphate or a glass coating component and coating the surface. However, the oxidation resistance of the carbonaceous material, which is the base material, is only improved at about 100 to 200 ° C., and there is a risk that the oxidation will progress locally due to uneven coating or peeling during use, ensuring stable quality. Difficult to do. Further, it has no effect on the improvement of strength.
【０００５】（２） 炭素質基材そのものの改質のため
に、基材に炭化けい素とけい素鉄を配合するものがあ
る。この対策によって、炭素質材料そのものの耐酸化性
はかなり改善されるが、例えば、９００℃で５時間の加
熱処理により１０〜３０％の重量減が生じ、充分とは言
い難い。また、結合剤を使用するため焼結が阻害され、
強度低下を免れない。(2) In order to modify the carbonaceous substrate itself, there is a substrate in which silicon carbide and silicon iron are blended. By this measure, the oxidation resistance of the carbonaceous material itself is considerably improved, but for example, heat treatment at 900 ° C. for 5 hours causes a weight loss of 10 to 30%, which is not sufficient. Also, the use of a binder hinders sintering,
Inevitably loses strength.
【０００６】（３）生コークス粉末と炭化ケイ素と炭化
ホウ素、さらに他のホウ化物等のセラミック化合物を配
合して、磨砕処理した後、黒鉛化処理する方法が、特公
昭６２−１２１９１号公報、特公昭６２−４６５０８号
公報、特開昭６１−２４７６６１号公報、又は窯業協会
誌、９４、４０９（１９８６）等に開示されている。こ
れによって、黒鉛材料は、高温域での耐酸化性の改善
と、１００ＭＰａを超える強度が達成されるとしてい
る。ところが、この方法は、原料生コークスの磨砕処理
によるメカノケミカル効果を利用しての焼結性の改善、
振動ボールミルによる生コークスの予備粉砕、塩酸処理
による混入金属分の除去、さらには、らいかい機による
生コークスと他の原料との充分な混合磨砕の組合せによ
って、セラミックス微粒子が分散した焼結性を有する炭
素質原料を得るものである。ところが、このように処理
工程が多段階におよび繁雑である、さらに、その特性を
発現する高密度の焼結体を作製するためには、２０００
℃以上の高温処理が必要であり、安価に高品位の炭素材
料を提供することが難しいという欠点がある。さらに
は、このようなメカノケミカル効果を非晶質炭素材に利
用できるのかについての疑問がある。(3) A method of blending raw coke powder, silicon carbide, boron carbide, and other ceramic compound such as boride, followed by grinding treatment and graphitization treatment is disclosed in Japanese Examined Patent Publication No. 62-12191. , Japanese Patent Publication No. 62-46508, Japanese Patent Laid-Open No. 61-247661, and Journal of Ceramic Industry, 94, 409 (1986). As a result, it is said that the graphite material achieves improvement in oxidation resistance in a high temperature range and strength exceeding 100 MPa. However, this method improves the sinterability by utilizing the mechanochemical effect by grinding the raw raw coke,
Preliminary crushing of raw coke with a vibrating ball mill, removal of contaminating metal components with hydrochloric acid treatment, and sufficient mixing and grinding of raw coke and other raw materials with a raking machine combine to sinter the fine ceramic particles. To obtain a carbonaceous raw material having However, in order to manufacture a high-density sintered body which has such a multi-step and complicated treatment process and exhibits its characteristics, 2000
There is a drawback that it is difficult to provide a high-quality carbon material at a low cost because a high temperature treatment of ℃ or more is required. Furthermore, there is a question as to whether such mechanochemical effect can be used for an amorphous carbon material.
【０００７】（４）ピッチを熱処理することによって得
られたメソフェーズ小球体と炭化ホウ素を混合成形後、
焼成することが特開昭６２−１０８７６７号公報に開示
され、さらに、これに黒鉛の添加することによって炭素
材そのものの強度の向上を計る方法が特開平１−１００
０６３号公報に開示されている。ところが、この方法に
よって得られた炭素材は、曲げ強度が高々５０ＭＰａで
あって、大幅な強度の向上が期待できない。また、耐酸
化性に関する効果も明確でない。(4) After mixing and molding mesophase spheres obtained by heat-treating the pitch and boron carbide,
Baking is disclosed in JP-A-62-108767, and a method for improving the strength of the carbon material itself by adding graphite thereto is disclosed in JP-A-1-100.
It is disclosed in Japanese Patent Publication No. 063. However, the carbon material obtained by this method has a bending strength of at most 50 MPa, and a significant improvement in strength cannot be expected. Also, the effect on oxidation resistance is not clear.
【０００８】さらに、原料炭素材に加熱時に溶融する低
揮発分のピッチバインダーを１５〜３５体積％添加配合
して４８０〜６００℃で加圧加熱成形することが、特開
平４−２９５０６０号公報に開示されている。これによ
って、１００ＭＰａを超す強度が得られるとしている
が、耐酸化性と導電率その他の特性についてに関して
は、どの程度効果があるのか明確でない。また、発泡の
ない緻密な炭素材を得るためには加圧下での焼成が必要
であり、特殊な装置が必要であり、プロセスが多段階に
わたるため繁雑であるため、経済的に炭素材料の耐酸化
性と高強度を併せて達成することはない。Further, Japanese Patent Laid-Open No. 4-295060 discloses that a low volatile content pitch binder that melts upon heating is added to a raw carbon material in an amount of 15 to 35% by volume, and the mixture is heated under pressure at 480 to 600 ° C. It is disclosed. Although it is said that a strength of more than 100 MPa can be obtained by this, it is not clear how effective it is with respect to oxidation resistance, conductivity and other characteristics. Further, in order to obtain a dense carbon material without foaming, it is necessary to perform firing under pressure, a special device is required, and the process is multistage and complicated, so economically, the acid resistance of the carbon material is low. It does not achieve both chemical compatibility and high strength.
【０００９】[0009]
【発明が解決しようとする課題】本発明の目的は、上記
従来の炭素質材料、とくに、実質的に非晶質炭素よりな
る炭素質材料の改質策の欠点を解消することにあって、
高強度、高導電性であり、大気中高温での使用において
も耐酸化性に優れ安定した特性を有する安価な非晶質炭
素材を提供することにある。SUMMARY OF THE INVENTION An object of the present invention is to eliminate the drawbacks of the conventional measures for modifying a carbonaceous material, particularly a carbonaceous material consisting essentially of amorphous carbon.
An object of the present invention is to provide an inexpensive amorphous carbon material which has high strength and high conductivity, and has excellent oxidation resistance and stable characteristics even when used in the atmosphere at high temperature.
【００１０】[0010]
【課題を解決するための手段】本発明の炭素質材料は、
炭化物、硼化物、硼炭化物の何れか１種以上を含む実質
的に非晶質炭素母材からなり、比抵抗が１×１０-2Ωｃ
ｍ以下、曲げ強度８０ＭＰａ以上、ショア硬さが９０以
上としたことを特徴とする。The carbonaceous material of the present invention is
Consists of a substantially amorphous carbon base material containing at least one of carbides, borides, and borocarbides, and has a specific resistance of 1 × 10 -2 Ωc
The bending strength is 80 MPa or more, and the Shore hardness is 90 or more.
【００１１】本発明で言う実質的に非晶質炭素材とは、
（００２）面反射による面間隔が３．４４Ａ以上（Ｃｕ
のＫα線による回折ピーク位置が２θ値で２５．９°以
下）である炭素材料を指す。The substantially amorphous carbon material referred to in the present invention means
The surface spacing due to (002) surface reflection is 3.44 A or more (Cu
Of the Kα ray has a 2θ value of 25.9 ° or less).
【００１２】さらに、面間隔が３．４４Ａ以下（Ｃｕの
Ｋα線による回折ピーク位置が２θ値で２５．９°以
上）である場合は、黒鉛化度が４０％以下である炭素材
料も含む。黒鉛化度が４０％を越えても本発明による炭
素材料の物性値の大幅な向上見られないため、製造条件
の経済性を考えると４０％以下で充分である。Further, when the plane spacing is 3.44 A or less (the diffraction peak position of Cu by Kα ray is 25.9 ° or more in 2θ value), a carbon material having a graphitization degree of 40% or less is also included. Even if the degree of graphitization exceeds 40%, the physical properties of the carbon material according to the present invention are not significantly improved. Therefore, 40% or less is sufficient in view of economical efficiency of manufacturing conditions.
【００１３】この黒鉛化度（Ｐ）は以下の式により計算
される。The graphitization degree (P) is calculated by the following formula.
【００１４】Ｐ＝１００×（３．４４０−ｄ）／（３．
４４０−３．３５４） 式中、３．３５４は規則配列している黒鉛結晶の面間隔
（Ａ）を、３．４４０は乱層構造部分の面間隔（Ａ）
を、また、ｄは測定試料の面間隔をを示す。P = 100 × (3.440-d) / (3.
440-3.354) In the formula, 3.354 is the interplanar spacing (A) of the regularly arranged graphite crystals, and 3.440 is the interplanar spacing (A) of the disordered layer structure portion.
And d represents the surface spacing of the measurement sample.
【００１５】本発明の炭素質材料に含有される炭化物、
硼化物、硼炭化物としては、実質的に非晶質炭素母材の
導電性を低下させなければとくに限定されないが、耐酸
化性の向上のためには、炭化ケイ素、炭化ホウ素の使用
がとくに好ましい。その総量は５〜５０容積％が適当で
ある。５容積％以下であれば、耐酸化性が大輻に低下す
るため好ましくない。炭化ホウ素は５〜５０容積％、炭
化ケイ素は５〜５０容量％の範囲であることが耐酸化性
の向上のために特に好ましい。高温域での初期酸化を抑
えるためには炭化ホウ素が５容積％以上であることがよ
り好ましい。長時間の耐酸化性を向上させるため炭化ケ
イ素の含有量は、１０容量％以上であることがより好ま
しい。強度、硬度、導電率等の物性値の向上のために、
ＩＶＡ、ＶＡ、ＶＩＡ族金属の炭化物、硼化物成分を含
むことがより有効である。A carbide contained in the carbonaceous material of the present invention,
The borides and borocarbides are not particularly limited as long as they do not substantially reduce the conductivity of the amorphous carbon base material, but it is particularly preferable to use silicon carbide or boron carbide in order to improve the oxidation resistance. . A total amount of 5 to 50% by volume is suitable. If the content is 5% by volume or less, the oxidation resistance is greatly reduced, which is not preferable. It is particularly preferable that the content of boron carbide is 5 to 50% by volume and the content of silicon carbide is 5 to 50% by volume in order to improve oxidation resistance. In order to suppress the initial oxidation in the high temperature range, the content of boron carbide is more preferably 5% by volume or more. In order to improve long-term oxidation resistance, the content of silicon carbide is more preferably 10% by volume or more. To improve the physical properties such as strength, hardness, and conductivity,
It is more effective to contain a carbide or boride component of a group IVA, VA or VIA metal.
【００１６】本発明の耐酸化性に優れた炭素質材料を得
るための炭素原料としては、焼成することで非晶質とな
るものであれば如何なる炭素材を使用でき、とくに限定
されないが、コールタール誘導のメソフェーズカーボン
類やフェノール樹脂、セルロース系樹脂に代表される難
黒鉛化材料等が好ましい。As the carbon raw material for obtaining the carbonaceous material excellent in oxidation resistance of the present invention, any carbon material can be used as long as it becomes amorphous by firing, but it is not particularly limited. Tar-derived mesophase carbons, non-graphitizable materials typified by phenolic resins, and cellulosic resins are preferable.
【００１７】本発明の炭素質材料成形体は、公知の方法
で作製される。The carbonaceous material compact of the present invention is produced by a known method.
【００１８】例えば、炭素原料と炭化物、硼化物粉末を
所定量秤量した後、湿式もしくは乾式法で混合し、続い
て、ｌ軸プレス法、ＣＩＰ法、鋳込法、射出法、ドクタ
ーブレード法などによって各種形状に成形する。成形時
には、必要に応じ、アルミナゾル、シリカゾルやアルミ
ナセメントに代表される無機系の結合剤が耐酸化性、導
電率を低下させない範囲において使用される。無機系の
結合材は、５重量％以下の使用が好ましい。得られた成
形体を、アルゴン、へリウム、窒素等の非酸化雰囲気で
１０００〜２０００℃の温度で、より好ましくは１２０
０〜１７００℃の温度で加熱する。焼成温度が低けれ
ば、密度、強度、硬さ、導電率などの物性値が小さくな
る。逆に２０００℃を越す高温での焼成では特性の向上
が見られないため非経済的である。For example, a carbon raw material, a carbide and a boride powder are weighed in predetermined amounts and then mixed by a wet or dry method, followed by a l-axis pressing method, a CIP method, a casting method, an injection method, a doctor blade method and the like. Mold into various shapes by. At the time of molding, an inorganic binder represented by alumina sol, silica sol, or alumina cement is used, if necessary, in a range that does not reduce oxidation resistance and conductivity. It is preferable to use 5% by weight or less of the inorganic binder. The obtained molded body is heated in a non-oxidizing atmosphere such as argon, helium or nitrogen at a temperature of 1000 to 2000 ° C., more preferably 120.
Heat at a temperature of 0-1700 ° C. If the firing temperature is low, the physical properties such as density, strength, hardness, and conductivity will be small. On the contrary, firing at a high temperature exceeding 2000 ° C. is uneconomical because no improvement in properties can be seen.
【００１９】[0019]
【作用】非晶質炭素を母材とし、これに硼化物、炭化物
を含有させることで耐酸化性と機械的特性、導電性等の
物性が向上する。硼化物と炭化物は、高温酸化性雰囲気
中で酸化してガラス相を生成し耐酸化被膜を炭素材表面
に生成する。[Function] By using amorphous carbon as a base material and adding boride or carbide to the base material, physical properties such as oxidation resistance, mechanical properties and conductivity are improved. Borides and carbides oxidize in a high temperature oxidizing atmosphere to form a glass phase and form an oxidation resistant film on the surface of the carbon material.
【００２０】本発明の炭素材料には開放気孔が一部存在
するが、酸化雰囲気での加熱により表面に存在する気孔
を覆うように酸化被膜が生成することで、炭素材内部の
酸化を防止することが可能となると考えられる。従っ
て、必要以上の高密度化は必要ない。もし、表面に生成
した酸化被膜が外的要因により剥離したとしても、新た
な耐酸化被膜が順次形成され全体の酸化は防止される。Although the carbon material of the present invention has some open pores, the oxidation inside the carbon material is prevented by forming an oxide film so as to cover the pores existing on the surface by heating in an oxidizing atmosphere. It will be possible. Therefore, it is not necessary to increase the density more than necessary. Even if the oxide film formed on the surface is peeled off due to an external factor, a new oxidation resistant film is sequentially formed and the entire oxidation is prevented.
【００２１】また、本発明の材質では耐酸化被膜の形成
は表面に限定されるため構造体としての導電性等の物性
値の低下が少なく、安定した特性を発揮する。Further, in the material of the present invention, since the formation of the oxidation resistant film is limited to the surface, the physical properties of the structure, such as conductivity, are not significantly reduced, and stable characteristics are exhibited.
【００２２】[0022]
【実施例】表１の実施例ｌ−１３に示す配合組成物をコ
ールタール起源の非晶質炭素に配合して、これに、バイ
ダーとして５重量％のレゾール型フェノール樹脂を炭化
珪素ボールと樹脂製ポットを用いポットミルで１０時間
混合した後、乾燥し混合粉末を得た。EXAMPLES The compounding compositions shown in Examples 1 to 13 of Table 1 were compounded with amorphous carbon originating from coal tar, and 5% by weight of a resole type phenol resin as a binder was added to the silicon carbide balls and the resin. After mixing for 10 hours in a pot mill using a pot made of a product, it was dried to obtain a mixed powder.
【００２３】[0023]
【表１】 この混合粉末を１４０ＭＰａで成形し５０×５０ｍｍ、
厚さ約ｌ０ｍｍの成形体を得た。成形体は１５０℃でフ
ェノール樹脂で硬化処理をしたのち、昇温速度５℃／分
で表に示す各温度で２時間、アルゴン気流中で焼成し
て、本発明の炭素質材料を得た。具体的な炭化物、硼化
物の容積％、焼成温度を表１にまとめた。１６００℃迄
の焼成で得られた炭素材中の炭素は、全て非晶質であっ
た。また、１８００、２０００℃の焼成で得られた炭素
材中の炭素の黒鉛化度はそれぞれ１３と３８％であっ
た。この黒鉛化度は、焼成後のサンプルを粉砕した後、
粉末Ｘ線回折パターンを測定し、その（００２）面の回
折ピークのｄ値より黒鉛化度を計算した結果である。[Table 1] This mixed powder is molded at 140 MPa and 50 × 50 mm,
A molded body having a thickness of about 10 mm was obtained. The molded body was hardened with a phenol resin at 150 ° C., and then fired in an argon stream at a temperature rising rate of 5 ° C./min for 2 hours at each temperature shown in the table to obtain a carbonaceous material of the present invention. Table 1 shows the specific volume percentages of carbides and borides and the firing temperature. The carbon in the carbon material obtained by firing up to 1600 ° C. was all amorphous. The graphitization degree of carbon in the carbon material obtained by firing at 1800 and 2000 ° C. was 13 and 38%, respectively. This degree of graphitization, after crushing the sample after firing,
This is the result of measuring the powder X-ray diffraction pattern and calculating the graphitization degree from the d value of the diffraction peak of the (002) plane.
【００２４】また、同表に示す実施例１４は、実施例７
と同量のコールタール起源の非晶質炭素、炭化物とバイ
ダーとして３重量％の高純度アルミナセメントを混合し
た後、樹脂製鋳型を用いた減圧鋳込により成形体を得
た。得られた成形体を１００℃で充分乾燥した後、昇温
速度５℃／分で１６００℃で２時間焼成し炭素質材料を
得た。得られた炭素材料は本発明で言うところの非晶質
炭素材料であった。The fourteenth embodiment shown in the table is the seventh embodiment.
After mixing the same amount of amorphous carbon and carbide derived from coal tar with 3 wt% of high-purity alumina cement as a binder, a compact was obtained by vacuum casting using a resin mold. The obtained molded body was sufficiently dried at 100 ° C., and then fired at 1600 ° C. for 2 hours at a temperature rising rate of 5 ° C./minute to obtain a carbonaceous material. The obtained carbon material was the amorphous carbon material referred to in the present invention.
【００２５】比較例１として、炭化ケイ素を２容積％、
炭化硼素２容積％となるように配合し実施例１と同様の
方法で炭素質材料を得た。As Comparative Example 1, 2% by volume of silicon carbide,
A carbonaceous material was obtained in the same manner as in Example 1 except that the content of boron carbide was 2% by volume.
【００２６】比較例２は、市販のグラッシィカーボン
（東海カーボン社製、ＣＧ２０）である。Comparative Example 2 is a commercially available glassy carbon (CG20 manufactured by Tokai Carbon Co., Ltd.).
【００２７】比較例３は、市販の人工黒鉛である。（東
海マテリアル，Ａ×２８０） また、比較例４は、特公昭６２−１２１９１号公報に記
載の方法で製造された市販の炭素材料（神戸鋳造所、Ｂ
Ｓ１１９０７）である。Comparative Example 3 is a commercially available artificial graphite. (Tokai Material, A × 280) Comparative Example 4 is a commercially available carbon material (Kobe Foundry, B manufactured by the method described in Japanese Patent Publication No. 62-12191).
S11907).
【００２８】上記の実施例と比較例に示す炭素質材料の
嵩密度、４端子法による比抵抗、ＪＩＳ３点曲げ強度、
ビッカース硬さ、ＴＭＡによる５０から１０００℃の間
での熱膨張率の測定を行った。比抵抗はｌ．５−６．６
×ｌ０-3Ωｃｍ、３点曲げ強度は９８ＭＰａ以上、ショ
ア硬さは９０以上の値を示している。耐酸化試験は、得
られた炭素質材料を７×７×５ｍｍに切り出した後、予
め所定の温度に加熱した内径６０ｍｍの電気炉に入れ、
空気を２１／分の割合で導入しながら所定の時間加熱し
た。加熱処理前後の重量変化により耐酸化性とを比較例
２と３を１００として評価した。The bulk densities of the carbonaceous materials shown in the above examples and comparative examples, the specific resistance by the four-terminal method, the JIS three-point bending strength,
The Vickers hardness and the coefficient of thermal expansion between 50 and 1000 ° C. were measured by TMA. The specific resistance is 1. 5-6.6
× 10 −3 Ωcm, 3-point bending strength is 98 MPa or more, and Shore hardness is 90 or more. The oxidation resistance test was carried out by cutting out the obtained carbonaceous material into 7 × 7 × 5 mm, and then putting it in an electric furnace having an inner diameter of 60 mm which was previously heated to a predetermined temperature.
It was heated for a predetermined time while introducing air at a rate of 21 / min. The oxidation resistance was evaluated based on the weight change before and after the heat treatment as 100 in Comparative Examples 2 and 3.
【００２９】同表から明らかなとおり、本発明の実施例
は、比較例１〜３に対して耐酸化性において各段に優れ
たものであり、比較例４に対して、非晶質炭素材料であ
るにもかかわらず、同等の耐酸化性を有する。As is clear from the table, the examples of the present invention are superior in oxidation resistance to Comparative Examples 1 to 3, and to Comparative Example 4 are amorphous carbon materials. However, it has equivalent oxidation resistance.
【００３０】また、本発明の実施例の中でも、実施例ｌ
−５は、１００時間の耐酸化試験では１０％を越す重量
減があるが、ｌ０時間程度の短時間であれば５％未満の
重量減に留まるので充分に使用可能である。また、実施
例６と７は、１０００℃迄の使用では問題なく、１２０
０℃では短時間の使用が可能である。さらに、硼化ジル
コニウム（実施例１１）、硼化チタン（実施例１２）、
炭化チタン（実施例１３）を添加した系は、未添加の実
施例８に比べ比抵抗が約１／２、強度が約ｌ．５倍と物
性が大幅に向上している。このように、硼化ジルコニウ
ム、硼化チタン、炭化チタン等の高導電性の炭化物、硼
化物の添加が物性値向上のために有効であることがわか
る。また、アルミナセメントを用い作製した実施例１４
もフェーノル樹脂を持い作製した実施例７と同程度の物
性値を有する。Among the examples of the present invention, Example l
-5 has a weight loss of more than 10% in the 100-hour oxidation resistance test, but it can be used sufficiently because it remains less than 5% in a short time of about 10 hours. In addition, Examples 6 and 7 have no problem when used up to 1000 ° C.
At 0 ° C, it can be used for a short time. Furthermore, zirconium boride (Example 11), titanium boride (Example 12),
The system to which titanium carbide (Example 13) was added had a specific resistance of about 1/2 and a strength of about l.v. The physical properties are significantly improved by 5 times. Thus, it can be seen that the addition of highly conductive carbides such as zirconium boride, titanium boride, titanium carbide and borides is effective for improving the physical properties. In addition, Example 14 produced using alumina cement
Also has a physical property value similar to that of Example 7 prepared with phenol resin.
【００３１】添付図ｌ〜図５は、本発明の炭化質材料の
耐酸化性の動向を示す。The attached FIGS. 1 to 5 show the trend of the oxidation resistance of the carbonaceous material of the present invention.
【００３２】図１は、各実施例を大気中で所定の温度で
ｌ時間、加熱処理した後の重量変化を示し、図２は実施
例６、７、８を大気中、８００℃で所定の時間加熱処理
した後の重量変化を示し、図３は実施例７、８、９を大
気中、１０００℃で所定の時間加熱処理した後の重量変
化を示し、実施例８、９、１０を大気中、１２００℃で
所定の時間加熱処理した後の重量変化を示す。FIG. 1 shows the change in weight after heat-treating each Example in the atmosphere at a predetermined temperature for 1 hour, and FIG. 2 shows Examples 6, 7 and 8 in the atmosphere at a predetermined temperature of 800 ° C. 3 shows the weight change after heat treatment for a time, FIG. 3 shows the weight change after heat treatment at 1000 ° C. for a predetermined time in the atmosphere in Examples 7, 8 and 9, and the air temperature in Examples 8, 9 and 10. The change in weight after heat treatment at 1200 ° C. for a predetermined time is shown.
【００３３】図ｌにおいて、１０００℃以下では、本発
明の炭素材料は重量減少が５重量％以下であった。特
に、実施例６、７、８は１２００℃でも３重量％以下の
減少であった。炭化物、硼化物量の少ない比較例１は耐
酸化性が大幅に劣っている。また、比較として用いたグ
ラッシィカーボン（比較例２）と人造黒鉛（比較例３）
は、７００℃で１時間の処理で完全に消失していた。In FIG. 1, at 1000 ° C. or lower, the weight loss of the carbon material of the present invention was 5% by weight or less. Particularly, in Examples 6, 7, and 8, the decrease was 3% by weight or less even at 1200 ° C. Comparative Example 1, which has a small amount of carbides and borides, is significantly inferior in oxidation resistance. Further, glassy carbon (Comparative Example 2) and artificial graphite (Comparative Example 3) used for comparison.
Completely disappeared after 1 hour of treatment at 700 ° C.
【００３４】図２は、実施例６、７、８は大気中で８０
０℃でｌ００時間加熱処埋後も３重量％以下の減少であ
り優れた耐酸化性を有することがわかる。また図３に示
すように、ｌ０００℃でｌ００時間後においても、約５
％程度の重量減少であった。さらに、表に示すように、
炭化ケイ素の添加量が１８〜３５容積％である実施例９
〜１０は１２００℃の加熱処理においてもその重量減少
率が数％以内であった。FIG. 2 shows that Examples 6, 7 and 8 are 80
Even after heat treatment at 0 ° C. for 100 hours, the decrease was 3% by weight or less, indicating that the sample has excellent oxidation resistance. Moreover, as shown in FIG. 3, even after 100 hours at 1000 ° C., about 5
It was a weight loss of about%. Furthermore, as shown in the table,
Example 9 in which the addition amount of silicon carbide is 18 to 35% by volume
The weight reduction ratios of Nos. 10 to 10 were within several percent even in the heat treatment at 1200 ° C.
【００３５】さらに、図４又は表に示すように、結合材
としてアルミナセメントを用いた実施例１４や強度、導
電性を向上させるためにチタンやジルコニウムの硼化
物、炭化物を添加した実施例１１〜１３も同様に優れた
耐酸化性を有している。Further, as shown in FIG. 4 or the table, Example 14 using alumina cement as a binder and Examples 11 to 11 containing titanium or zirconium boride or carbide in order to improve strength and conductivity. Similarly, 13 also has excellent oxidation resistance.
【００３６】[0036]
【発明の効果】本発明に係る非晶質炭素材料は、以下の
効果を奏する。The amorphous carbon material according to the present invention has the following effects.
【００３７】（１）炭化物、硼化物を適量含む非晶質炭
素は、非晶質炭素材料であっても、優れた機械的特性、
高導電率と結晶性の黒鉛質材料を凌ぐ物性を有し、さら
に優れた耐酸化性を併せ持つ。(1) Amorphous carbon containing an appropriate amount of carbides and borides has excellent mechanical properties even if it is an amorphous carbon material.
It has physical properties superior to those of highly conductive and crystalline graphite materials, and also has excellent oxidation resistance.
【００３８】（２）優れた機械的、電気的物性値を有
し、かつ耐酸化成に優れていることより、従来の黒鉛材
が使用できなかった各種溶融金属用部材、大気中高温域
で使用される導電材料等として有効である。(2) Due to its excellent mechanical and electrical properties and its excellent oxidation resistance, it can be used in various molten metal members where conventional graphite materials could not be used, and in high temperature regions in the atmosphere. It is effective as a conductive material and the like.
【００３９】（３）特殊な黒鉛質複合材や金属炭化物や
硼化物焼結体に比べその製造が容易であり安価に供給す
ることができる。(3) Compared with a special graphite composite material, metal carbide or boride sintered body, its production is easier and can be supplied at a lower cost.
【００４０】（４）従って、優れた機械的強度、耐酸化
性を利用して、ストーク、ノズル、ラドル、壁材などの
非鉄金属溶湯用部材に、優れた導電性、機械的強度、耐
酸化性を利用して、非鉄金属溶湯用湯面検知棒に、さら
に、導電性、機械的強度、耐酸化性を利用して大気中で
使用される電極材料に好適に使用できる。(4) Therefore, by utilizing the excellent mechanical strength and oxidation resistance, it is possible to obtain excellent conductivity, mechanical strength, and oxidation resistance for members for molten non-ferrous metal such as stalks, nozzles, ladles, and wall materials. It can be suitably used for a molten metal level detecting rod for molten non-ferrous metal by utilizing its property, and for an electrode material used in the atmosphere by utilizing its conductivity, mechanical strength and oxidation resistance.
【図１】 各実施例を大気中で所定の温度でｌ時間、加
熱処理した後の重量変化を示す。FIG. 1 shows changes in weight after heat-treating each example in the atmosphere at a predetermined temperature for 1 hour.
【図２】 実施例６、７、８を大気中、８００℃で所定
の時間加熱処理した後の重量変化を示す。FIG. 2 shows changes in weight of Examples 6, 7, and 8 after heat treatment in air at 800 ° C. for a predetermined time.
【図３】 実施例７、８、９を大気中、１０００℃で所
定の時間加熱処理した後の重量変化を示す。FIG. 3 shows changes in weight of Examples 7, 8 and 9 after heat treatment at 1000 ° C. for a predetermined time in the atmosphere.
【図４】 実施例８、９、１０を大気中、１２００℃で
所定の時間加熱処理した後の重量変化を示す。FIG. 4 shows changes in weight of Examples 8, 9 and 10 after heat treatment in air at 1200 ° C. for a predetermined time.
Claims (2)
であって、炭化物と硼化物の何れかの１種または両方を
含み、比抵抗が１×１０-2Ωｃｍ以下、曲げ強度８０Ｍ
Ｐａ以上、ショア硬さが９０以上である耐酸化性に優れ
た炭素質材料。1. A carbonaceous material consisting essentially of amorphous carbon, containing one or both of a carbide and a boride, having a specific resistance of 1 × 10 −2 Ωcm or less and a bending strength of 80M.
A carbonaceous material having Pa or more and Shore hardness of 90 or more and excellent in oxidation resistance.
ケイ素であって、少なくとも炭化ケイ素５〜５０容積％
と炭化ホウ素と５〜５０容積％含む耐酸化性に優れた炭
素質材料。2. The method according to claim 1, wherein the carbide is silicon carbide and at least 5 to 50% by volume of silicon carbide.
A carbonaceous material containing 5 to 50% by volume of boron carbide and excellent in oxidation resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5266308A JPH07118065A (en) | 1993-10-25 | 1993-10-25 | Carbonaceous material excellent in oxidation resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5266308A JPH07118065A (en) | 1993-10-25 | 1993-10-25 | Carbonaceous material excellent in oxidation resistance |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH07118065A true JPH07118065A (en) | 1995-05-09 |
Family
ID=17429128
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5266308A Pending JPH07118065A (en) | 1993-10-25 | 1993-10-25 | Carbonaceous material excellent in oxidation resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH07118065A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0903795A4 (en) * | 1996-11-26 | 2005-03-16 | Kao Corp | Negative electrode material for nonaqueous secondary battery |
-
1993
- 1993-10-25 JP JP5266308A patent/JPH07118065A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0903795A4 (en) * | 1996-11-26 | 2005-03-16 | Kao Corp | Negative electrode material for nonaqueous secondary battery |
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