JPH01239064A - Production of carbon material and carbon/carbon composite material - Google Patents
Production of carbon material and carbon/carbon composite materialInfo
- Publication number
- JPH01239064A JPH01239064A JP63063172A JP6317288A JPH01239064A JP H01239064 A JPH01239064 A JP H01239064A JP 63063172 A JP63063172 A JP 63063172A JP 6317288 A JP6317288 A JP 6317288A JP H01239064 A JPH01239064 A JP H01239064A
- Authority
- JP
- Japan
- Prior art keywords
- carbon
- iron
- pitch
- pressure
- heat
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 28
- 239000002131 composite material Substances 0.000 title claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011203 carbon fibre reinforced carbon Substances 0.000 title description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910052742 iron Inorganic materials 0.000 claims abstract description 27
- 239000000835 fiber Substances 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 22
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 12
- 239000000956 alloy Substances 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims description 23
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 20
- 239000004917 carbon fiber Substances 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000005087 graphitization Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 239000011521 glass Substances 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 3
- 229910000831 Steel Inorganic materials 0.000 abstract description 2
- 229910052804 chromium Inorganic materials 0.000 abstract description 2
- 239000010439 graphite Substances 0.000 abstract description 2
- 229910002804 graphite Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 239000010959 steel Substances 0.000 abstract description 2
- 229910000640 Fe alloy Inorganic materials 0.000 abstract 3
- 230000002706 hydrostatic effect Effects 0.000 abstract 2
- 239000003245 coal Substances 0.000 abstract 1
- 239000003208 petroleum Substances 0.000 abstract 1
- 239000011295 pitch Substances 0.000 description 25
- 239000007789 gas Substances 0.000 description 17
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 239000004744 fabric Substances 0.000 description 10
- 239000011888 foil Substances 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- 239000011301 petroleum pitch Substances 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000000919 ceramic Substances 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000011261 inert gas Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000011337 anisotropic pitch Substances 0.000 description 3
- 238000009924 canning Methods 0.000 description 3
- 229910001873 dinitrogen Inorganic materials 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- 238000010000 carbonizing Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000000280 densification Methods 0.000 description 2
- 238000001513 hot isostatic pressing Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229920000297 Rayon Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- -1 aluminum Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 238000009792 diffusion process 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
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000011810 insulating material Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000011225 non-oxide ceramic Substances 0.000 description 1
- 229910052575 non-oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002964 rayon Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 210000002268 wool Anatomy 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Abstract
Description
【発明の詳細な説明】
本発明は、炭素材料および炭素／炭素複合材料の製造法
に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing carbon materials and carbon/carbon composite materials.
炭素質ピッチは、その炭化収率が高いことから高密度炭
素材料の原料として利用されている。しかしながら、炭
化時にガス発生による気泡や亀裂などを生成するという
問題があり、これを解決する方法としてピッチを高圧下
で炭化する方法、Ｈｏｔ ｌ５ｏｓｔａｔｉｃ Ｐｒ
ｅｓｓｉｎｇ （熱間静水圧加圧、ＨＩＰ）が用いられ
ている。この場合、炭化時に発生するガスがヒーターや
断熱材などの炉内部材を汚染し、場合によっては装置破
損をきたす恐れがある。このため、炭素材料の製造を目
的としたＨＩＰでは、原料をガラスあるいはステンレス
など密閉型の容器（コンテナ）に入れる、いわゆるキャ
ニングが行われる。またこのコンテナは、熱処理中に被
処理物の形状を維持するという目的も兼ねている。一方
、炭素／炭素複合材料は、１０００℃以上の高温におい
ても高強度、高弾性率を維持し、かつ熱膨張率カレトさ
い等の特異な性質を有する材料であり、航空宇宙機器の
部品、ブレーキ、炉材等への利用が期待されている。炭
素質ピッチは、前記の特性から、炭素／炭素複合材料の
マトリックス用プリカーサとしても使用されているが、
この炭化過程においてもＨＩｉ：用いられており、この
場合にも原料をガラスあるいはステンレス製のコンテナ
に入れる、いわゆるキャニングが行われる。Carbonaceous pitch is used as a raw material for high-density carbon materials because of its high carbonization yield. However, there is a problem that bubbles and cracks are generated due to gas generation during carbonization.To solve this problem, a method of carbonizing pitch under high pressure, Hot l5ostatic Pr.
essing (hot isostatic pressing, HIP) is used. In this case, the gas generated during carbonization may contaminate internal materials such as the heater and heat insulating material, possibly causing damage to the equipment. For this reason, in HIP for the purpose of manufacturing carbon materials, so-called canning is performed in which raw materials are placed in a closed container such as glass or stainless steel. This container also serves the purpose of maintaining the shape of the object to be processed during heat treatment. On the other hand, carbon/carbon composite materials maintain high strength and high elastic modulus even at high temperatures of 1000°C or higher, and have unique properties such as a low coefficient of thermal expansion. It is expected to be used in furnace materials, etc. Due to the above characteristics, carbonaceous pitch is also used as a matrix precursor for carbon/carbon composite materials.
HIi: is also used in this carbonization process, and in this case as well, so-called canning, in which the raw materials are placed in a glass or stainless steel container, is performed.
しかしながら、密閉型の容器（コンテナ）を用いる場合
には、シール機能を付与するために、真空封入などのキ
ャニング工程が必要となり、さらに緻密化のための再含
浸時にはコンテナ削除と再キャニングが必要となる。こ
のため製造プロセスが煩雑になるという問題があり、さ
らに発生ガスの内圧により、処理物にクラックが入った
り、コンテナの圧力により炭素繊維の織物が変形するこ
とがある。However, when using a sealed container, a canning process such as vacuum sealing is required to provide a sealing function, and when re-impregnating for densification, the container must be removed and re-canned. Become. This poses the problem of complicating the manufacturing process, and furthermore, the internal pressure of the generated gas may cause cracks in the processed material, and the pressure of the container may deform the carbon fiber fabric.
本発明者らは、前記問題点を解決し、簡便かつ高性能な
炭素材料および炭素／炭素複合材料の製造プロセスを確
立すべく研究した結果、本発明の完成に至った。The present inventors conducted research to solve the above-mentioned problems and establish a simple and high-performance manufacturing process for carbon materials and carbon/carbon composite materials, and as a result, the present invention was completed.
本願発明者らの検討結果によれば、前記炭素質ピッチを
熱間静水圧加圧によυ熱処理する場合には、密閉型容器
を使用せずとも、被処理物の形状が維持でき、しかも開
放型容器を使用する場合には、発生ガスの内圧により、
処理物にクラックが入るのを防止できることがわかった
（特願昭６２−３３００１８号）。According to the study results of the present inventors, when heat-treating the carbonaceous pitch by hot isostatic pressing, the shape of the object to be treated can be maintained without using a closed container. When using an open container, due to the internal pressure of the generated gas,
It has been found that cracks can be prevented from forming in the treated product (Japanese Patent Application No. 330018/1982).
開放型容器とは、シール機能のない容器である。材質と
しては、アルミニウム、軟鋼、ステンレスなどの金属、
ガラス、黒鉛あるいはセラミックスなどが使用温度ある
いは使用目的などによって適宜選択できる。容器の形状
は特に限定されないが、蓋付き、蓋なしのいずれでも良
く、金属フォイルで被処理物を包むだけでも良い。An open container is a container without a sealing function. Materials include metals such as aluminum, mild steel, and stainless steel.
Glass, graphite, ceramics, etc. can be selected as appropriate depending on the operating temperature or purpose of use. The shape of the container is not particularly limited, but it may be with or without a lid, and the object to be processed may be simply wrapped in metal foil.
本発明者らはさらに検討を重ねた結果、炭化時に生成す
る分解ガス、特に炭化水素ガスの捕獲に耐火物繊維、鉄
および鉄系合金よりなる群より選ばれる少なくとも一種
の物質がきわめて有効であることを見いだした。本発明
はこれらの物質（捕獲材）を被処理物と共存させること
によシ達成される。As a result of further studies, the present inventors have found that at least one substance selected from the group consisting of refractory fibers, iron, and iron-based alloys is extremely effective in capturing decomposed gases generated during carbonization, especially hydrocarbon gases. I found out. The present invention is achieved by allowing these substances (capturing materials) to coexist with the object to be treated.
すなわち、本発明は、（１）炭素質ピッチを開放型容器
に入れ、耐火物繊維、鉄および鉄系合金よりなる群よシ
選ばれる少なくとも一種の物質の共存下において熱間静
水圧加圧下で熱処理し、必要に応じてさらに炭化あるい
は黒鉛化することを特徴とする炭素材料の製造法、およ
び（２）炭素繊維のトウに炭素質ピンチを含浸し、との
含浸物を開放型容器に入れ、耐火物繊維、鉄および鉄系
合金よりなる群より選ばれる少なくとも一種の物質の共
存下において熱間静水圧加圧下で熱処理し、必要に応じ
てさらに炭化あるいけ黒鉛化することを特徴とする炭素
／炭素複合材料の製造法に関する。That is, the present invention provides (1) carbonaceous pitch placed in an open container and heated under hot isostatic pressure in the coexistence of at least one substance selected from the group consisting of refractory fibers, iron, and iron-based alloys. A method for producing a carbon material characterized by heat treatment and further carbonization or graphitization as necessary, and (2) impregnating a carbon fiber tow with a carbonaceous pinch and placing the impregnated material in an open container. , heat-treated under hot isostatic pressure in the coexistence of at least one substance selected from the group consisting of refractory fibers, iron, and iron-based alloys, and further carbonized or graphitized as necessary. This invention relates to a method for producing carbon/carbon composite materials.
以下、本発明による炭素材料および炭素／炭素複合材料
の製造法について詳述する。Hereinafter, the method for producing carbon materials and carbon/carbon composite materials according to the present invention will be described in detail.
本発明で用いる炭素質ピッチとは、軟化点１００〜４０
０℃、好ましくは１５０〜３５０℃を有する石炭系ある
いは石油系のピッチである。炭素質ピッチは、光学的に
等方性のピッチあるいは異方性のピッチのいずれも使用
できるが、光学的異方性相の含量が６０〜１００ ｖｏ
ｔ％、好ましくは８０〜１００ ｖａｔ％の光学的異方
性ピッチが特に好ましく用いられる。The carbonaceous pitch used in the present invention has a softening point of 100 to 40.
It is a coal-based or petroleum-based pitch having a temperature of 0°C, preferably 150 to 350°C. As the carbonaceous pitch, either an optically isotropic pitch or an anisotropic pitch can be used.
An optically anisotropic pitch of t%, preferably 80 to 100 vat% is particularly preferably used.
本発明で用いる炭素繊維としては、ピッチ系、ポリアク
リロニトリル系あるいはレーヨン系のいずれも使用でき
るが、ピッチ系炭素繊維が好ましい。また炭素繊維のト
ウとは、直径５〜１００μｍの炭素繊維の５００〜］、
０ＱＯＯＯ本の繊維束を一方向積層物、２次元織物あ
るいはその積層物、３次元織物、マット状成形物、フェ
ルト状成形物など２次元あるいは３次元に成型したもの
をいう。The carbon fibers used in the present invention may be pitch-based, polyacrylonitrile-based, or rayon-based carbon fibers, but pitch-based carbon fibers are preferred. Furthermore, carbon fiber tow refers to carbon fiber tow with a diameter of 5 to 100 μm.
It refers to a two-dimensional or three-dimensional product formed from 0QOOO fiber bundles, such as a unidirectional laminate, a two-dimensional fabric or its laminate, a three-dimensional fabric, a mat-like molded product, or a felt-like molded product.
ここでいうピッチ系炭素繊維とは、炭素質ピッチを溶融
紡糸し、これを不融化、炭化および必要に応じて黒鉛化
することにより得られる繊維である。The pitch-based carbon fibers referred to herein are fibers obtained by melt-spinning carbonaceous pitch, making it infusible, carbonizing it, and graphitizing it if necessary.
炭素繊維のトウに炭素質ピッチを含浸する方法は、例え
ば炭素質ピッチを真空下および／または加圧下で加熱、
溶融して炭素繊維トウに含浸する方法が用いられるが、
含浸時の粘度を下げるために、溶剤でカット・ノくツク
することもできる。溶剤としては、芳香族炭化水素、ピ
リジン、キノリンなどが使用できる。また緻密化のため
、含浸と後記ＨＩＰ処理とのサイクルを必要回数行うこ
とができる。A method for impregnating carbon fiber tow with carbonaceous pitch is, for example, heating carbonaceous pitch under vacuum and/or pressure.
A method of melting and impregnating carbon fiber tow is used,
To reduce the viscosity during impregnation, it can also be cut and punched with a solvent. As the solvent, aromatic hydrocarbons, pyridine, quinoline, etc. can be used. Further, for densification, a cycle of impregnation and HIP treatment described below can be performed as many times as necessary.
本発明においては炭素質ピッチまたは炭素繊維のトウに
炭素質ピッチを含浸して得られる含浸物の被処理物を開
放型容器に入れ、耐火物繊維、鉄および鉄系合金よりな
る群よシ選ばれる少なくとも一種の物質を共存させる。In the present invention, the impregnated material obtained by impregnating carbonaceous pitch or carbon fiber tow with carbonaceous pitch is placed in an open container, and a material selected from the group consisting of refractory fibers, iron, and iron-based alloys is prepared. coexist with at least one kind of substance.
耐火物繊維としては、例えばカーボン、酸化物系セラミ
ックス、非酸化物系セラミックス等の長繊維、短繊維あ
るいはフェルトなどを使用することができる。具体的に
はカーボン、シリカ、アルミナあるいはこれらの混合物
の短繊維が好ましい。As the refractory fibers, for example, long fibers or short fibers of carbon, oxide ceramics, non-oxide ceramics, or felt can be used. Specifically, short fibers of carbon, silica, alumina, or a mixture thereof are preferred.
鉄としては純度９９％以上のものが用いられ、鉄系合金
としては鉄に対してニッケル、クロム、モリブデン、バ
ナジウム、タングステン、シリカおよびマンガンから選
ばれる１種又は２種の金属を１０％以下含有するものが
用いられる。The iron used is one with a purity of 99% or more, and the iron-based alloy contains 10% or less of one or two metals selected from nickel, chromium, molybdenum, vanadium, tungsten, silica, and manganese. The one that does is used.
鉄および鉄系合金は、粉状、細線、メツシュあるいは多
孔質成形体などのかたちで使用することができる。Iron and iron-based alloys can be used in the form of powder, fine wire, mesh, or porous compacts.
捕獲材を共存させる態様は特に限定されないが、例えば
被処理物を開放型容器に入れその上部に捕獲材を充填す
る方法、被処理物を金属フォイルで包み、さらにその外
側を捕獲材のフェルトで包む方法、被処理物を捕獲材と
共に金属フォイルで包む方法等が例示できる。また捕獲
材が被処理物中に混入するのを防止するため金属フォイ
ルなどを両者の間に設置することもできる。The manner in which the capture material is coexisting is not particularly limited, but examples include a method in which the object to be treated is placed in an open container and the upper part is filled with the capture material, a method in which the object to be treated is wrapped in metal foil, and the outside is further covered with felt of the capture material. Examples include a method of wrapping, a method of wrapping the object to be treated together with a capture material in metal foil, and the like. Furthermore, a metal foil or the like may be placed between the two to prevent the capture material from being mixed into the object to be processed.
耐火物繊維、鉄および鉄系合金の２種以上を併用する場
合には、これらを混合、積層などすれば良い。耐火物繊
維、鉄および鉄系合金よりなる群より選ばれる少なくと
も一種の物質の使用量は処理条件によって任意に決定さ
れる力ζ通常は被処理物１００！量部に対して、耐火物
繊維は１０〜１０００重量部、好ましくは５０〜５００
重１部、鉄および鉄系合金は１０〜５０００重量部、好
ましくは５００〜１０００重量部である。なお、水素の
捕獲材、例えばチタン、ジルコニウム、マグネシウム等
を共存させることもできる。When two or more of refractory fibers, iron, and iron-based alloys are used together, they may be mixed or laminated. The amount of at least one substance selected from the group consisting of refractory fibers, iron, and iron-based alloys is arbitrarily determined depending on the processing conditions. The amount of refractory fiber is 10 to 1000 parts by weight, preferably 50 to 500 parts by weight.
The amount of iron and iron-based alloys is 10 to 5000 parts by weight, preferably 500 to 1000 parts by weight. Note that a hydrogen trapping material such as titanium, zirconium, magnesium, etc. may also be present.
被処理物は熱間静水圧加圧下で熱処理し、必要に応じて
さらに炭化あるいは黒鉛化を行うことにより炭素材料あ
るいは炭素／炭素複合材料を製造する。The object to be treated is heat treated under hot isostatic pressure, and if necessary, further carbonized or graphitized to produce a carbon material or a carbon/carbon composite material.
熱間静水圧加圧下での熱処理の条件は、不活性ガスによ
り５０〜１００００にν１２、好ましくは２００〜２０
００ｋｙ／ｃｍ２に加圧し、１００−３０００℃、好ま
しくは、４００〜２０００℃において実施することがで
きる。圧媒ガスとしては、アルゴン、窒素、ヘリウムな
どの不活性ガスが使用できる。The conditions for heat treatment under hot isostatic pressure are ν12 of 50 to 10,000 with inert gas, preferably 200 to 20.
It can be carried out at a temperature of 100-3000°C, preferably 400-2000°C, under a pressure of 00ky/cm2. As the pressure medium gas, inert gas such as argon, nitrogen, helium, etc. can be used.
本発明において、開放型容器を用いることにより、その
目的は十分達成できるが、必要に応じ、例えば多量の被
処理物を熱処理する場合には、排気機構付ＨＩＰ装置を
好ましく用いることができる。排気機構付ＨＩＰとは、
高圧を維持したままＨＩＰ中に被処理物から発生するガ
ス成分を連続制御して排出できる機構を有する装置であ
り、具体的には、発生するガスをその生成量および／ま
たは拡散速度応じて除去量を調節できる排出機構をそな
えた装置である。In the present invention, the purpose can be sufficiently achieved by using an open type container, but if necessary, for example, when heat treating a large amount of objects to be treated, a HIP apparatus with an exhaust mechanism can be preferably used. What is HIP with exhaust mechanism?
It is a device that has a mechanism that can continuously control and discharge gas components generated from the processed material during HIP while maintaining high pressure. Specifically, the generated gas is removed according to the amount of generation and/or diffusion rate. This device is equipped with a discharge mechanism that allows the amount to be adjusted.
このガス排出機構は、炉内圧媒ガスとの熱交換器および
炉外での冷却器、減圧装置、流量調節弁などよりなる。This gas discharge mechanism includes a heat exchanger with the pressure medium gas inside the furnace, a cooler outside the furnace, a pressure reducing device, a flow rate control valve, and the like.
この排気機構付ＨＩＰ装置の詳細は本願出願人の一名が
すでに出願した特願昭６２−２５３１７１に記載されて
いる。排気機構付ＨＩＰ装置における加圧熱処理の条件
も前記のＨＩＰ条件に準する。Details of this HIP device with an exhaust mechanism are described in Japanese Patent Application No. 62-253171 filed by one of the applicants of the present application. The conditions for the pressurized heat treatment in the HIP device with an exhaust mechanism also conform to the above-mentioned HIP conditions.
ＨＩ Ｐ処理後の処理物は、必要に応じ、常圧下、不活
性ガス雰囲気中、４００〜２０００℃において炭化おる
いは２０００〜３０００℃において黒鉛化処理すること
ができる。The treated product after the HIP treatment can be carbonized at 400 to 2000°C or graphitized at 2000 to 3000°C under normal pressure in an inert gas atmosphere, if necessary.
複合材料における炭素繊維の体積含有率（Ｖｆ）は、目
的によって任意に決定されるが、通常は５〜７０％であ
る。The volume content (Vf) of carbon fibers in the composite material is arbitrarily determined depending on the purpose, but is usually 5 to 70%.
実施例
以下に実施例をあげ、本発明を具体的に説明するが、本
発明はこれらに限定されるものではない。EXAMPLES The present invention will be specifically explained with reference to Examples below, but the present invention is not limited thereto.
（実施例１）
軟化点２８０℃の光学的異方性相１００ ｖｏｔ％の石
油系ピッチを石英製開放型容器に入れ、その上部にアル
ミナ５０重量％、シリカ５０重８％よりなるセラミック
の短繊維をピッチ１００重量部にたいして１００重量部
充填して、ＨＩＰ装置においてアルゴンガスによ’）
１０００ ｋ？／ｃｒｎ２に加圧し、８００℃において
加圧炭化処理した。得られた炭化物は、密閉型容器中で
ＨＩＦ処理したものと比ぺなんら遜色なかった。また炉
内の汚れは非常圧軽微であった。(Example 1) Petroleum-based pitch with a softening point of 280° C. and an optically anisotropic phase of 100 vot% is placed in an open quartz container, and a ceramic strip made of 50 wt. % alumina and 50 wt. % silica is placed on top of the container. Fill 100 parts by weight of fibers into 100 parts by weight of pitch, and heat with argon gas in a HIP machine.
1000k? /crn2 and subjected to pressure carbonization treatment at 800°C. The obtained carbide was comparable to that obtained by HIF treatment in a closed container. Also, there was very little dirt inside the furnace.
（実施例２）
実施例１で用いた石油系ピッチをステンレス製フォイル
で包含し、さらにその外側にピッチ１００重量部にたい
して１０００！量部の純度９９％、粒径５μの鉄粉を充
填し、アルゴンガスによす１０００ ｋｙ／ｉｙ２に加
圧し、８００℃において加圧炭化処理した。得られた炭
化物は、亀裂が非常に少なかった。また炉内の汚れは非
常に軽微であった。(Example 2) The petroleum-based pitch used in Example 1 was wrapped in a stainless steel foil, and 1000! It was filled with iron powder having a purity of 99% and a particle size of 5 μm, and was pressurized to 1000 ky/iy2 using argon gas, and subjected to pressure carbonization at 800°C. The resulting carbide had very few cracks. Also, there was very little dirt inside the furnace.
（比較例１）
実施例１で用いた石油系ピッチをステンレス製コンテナ
に真空封入し、ＨＩＰ装置において、アルゴンガスによ
り１０００ ’ｔｙｌ（７）２に加圧し、１０００℃に
おいて加圧炭化処理したところ、炉内の汚れは軽微であ
ったが、得られた炭化物には亀裂が多く見られた。(Comparative Example 1) The petroleum pitch used in Example 1 was vacuum sealed in a stainless steel container, pressurized to 1000'tyl(7)2 with argon gas in a HIP device, and subjected to pressure carbonization at 1000°C. Although there was only slight contamination inside the furnace, many cracks were observed in the obtained carbide.
（比較例２）
実施例１で用いた石油系ピッチを開放型ステンレス製コ
ンテナに入れ、ＨＩＰ装置において、アルゴンガスによ
り１０００ ｋｙ／ｃｎｔ”に加圧し、１０００℃にお
いて加圧炭化処理したところ、得られた炭化物には亀裂
が少なかったが、炉内の汚れがみられた。(Comparative Example 2) The petroleum pitch used in Example 1 was placed in an open stainless steel container, pressurized to 1000 ky/cnt'' with argon gas in a HIP device, and subjected to pressure carbonization treatment at 1000°C. There were few cracks in the carbide, but dirt inside the furnace was visible.
（実施例３）
軟化点２８０℃の光学的異方性相９０ ｖｏｔ％の石油
系ピッチをアルミニウム製フォイルで包含し、さらにそ
の外側にアルミナ５０重量％、シリカ５０重量％よりな
るセラミックファイバーのフェルトを、ピッチ１００重
を部にたいして２００００重量填し、アルゴンガスによ
！１１０００にν論２に加圧し、５５０℃において加圧
炭化処理した。(Example 3) A petroleum pitch containing 90 vot% of an optically anisotropic phase with a softening point of 280° C. is enclosed in an aluminum foil, and a ceramic fiber felt made of 50 wt. % alumina and 50 wt. % silica is further placed on the outside of the aluminum foil. Fill 20,000 weights of 100 weights of pitch into each section and use argon gas! The material was pressurized to 11,000 kW theory 2 and subjected to pressure carbonization treatment at 550°C.
得られた炭化物は、亀裂が非常に少なかった。また炉内
の汚れは非常に軽微であった。The resulting carbide had very few cracks. Also, there was very little dirt inside the furnace.
（実施例４）
実施例１で用いた石油系ピッチをアルミナ容器に入れ、
その上部にアルミナ５０重量％、シリカ５０重量％上り
なるセラミックファイバーのフェルト、低炭素鋼のスチ
ールウール、さらに前記セラミックファイバーのフェル
トをそれぞれピッチ１００Ｍ量部にたいして１００重量
部、３００重量部および２５重量部ずつ３層に充填し、
排気機構付ＨＩＰ装置においてアルゴンガスにより１０
００ ｋｙ／ｃｒｎ”に加圧し、８００℃において加圧
炭化処理した。得られた炭化物は、亀裂が非常に少なか
った。また炉内の汚れは非常に軽微であった。(Example 4) The petroleum pitch used in Example 1 was placed in an alumina container,
On top of that, ceramic fiber felt containing 50% by weight of alumina and 50% by weight of silica, steel wool made of low carbon steel, and 100 parts by weight, 300 parts by weight, and 25 parts by weight of the ceramic fiber felt, respectively, based on 100 M parts of pitch. Fill each layer in 3 layers,
10 minutes using argon gas in a HIP device with an exhaust mechanism.
00 ky/crn'' and pressure carbonization treatment at 800°C.The obtained carbide had very few cracks.Furthermore, there was very little contamination in the furnace.
（実施例５）
直径１０μ（ミクロン）のピッチ系炭素繊維の３０００
本束の２次元織物（平織）を積層し、これに実施例１で
用いたピッチを含浸した。含浸物をアルミニウム製フォ
イルで包含し、さらにその外側にアルミナ５０重量％、
シリカ５０重景チよりなるセラミックファイノく−のフ
ェルトをピッチ１００重量部にたいして１００００重量
填し、Ｈ工Ｐ装置において窒素ガスにより１０００ ｋ
ｙ／ｃｍ”に加圧し、２層ｍ’／ｈｒで排気しながら、
５５０℃において加圧炭化処理した。加圧炭化に続き、
常圧下、不活性ガス雰囲気下で２５００℃において黒鉛
化処理した。得られた炭素／炭素複合材料を走査型電子
顕微鏡、および偏光顕微鏡で観察したところ、繊維束内
および繊維束間にもマトリックスがよく充填されており
、炭素繊維の織物の変形も見られなかった。また炉内の
汚れは非常に軽微であった。(Example 5) 3000 pitch-based carbon fibers with a diameter of 10μ (microns)
This bundle of two-dimensional fabrics (plain weave) was laminated and impregnated with the pitch used in Example 1. The impregnated material is wrapped in an aluminum foil, and 50% by weight of alumina is added to the outside of the aluminum foil.
10,000 weight parts of ceramic fin felt made of silica 50 heavy weight was added to 100 parts by weight of pitch, and heated to 1000 kg using nitrogen gas in a H-P apparatus.
While pressurizing to y/cm" and exhausting at two layers m'/hr,
Pressure carbonization treatment was performed at 550°C. Following pressure carbonization,
Graphitization treatment was performed at 2500° C. under normal pressure and an inert gas atmosphere. When the obtained carbon/carbon composite material was observed using a scanning electron microscope and a polarizing microscope, it was found that the matrix was well filled within and between the fiber bundles, and no deformation of the carbon fiber fabric was observed. . Also, there was very little dirt inside the furnace.
（比較例３）
実施例５と同じ含浸物をステンレス製コンテナに真空封
入し、ＨＩＰ装置において実施例５と同じ条件で処理し
た。(Comparative Example 3) The same impregnated material as in Example 5 was vacuum sealed in a stainless steel container and treated in a HIP apparatus under the same conditions as in Example 5.
得られたものは、コンテナの圧力により炭素繊維の織物
が変形していた。The resulting carbon fiber fabric was deformed by the pressure of the container.
（実施例６）
直径１０μ（ミクロン）のピッチ系炭素繊維の３０００
本束の３次元直交織物に実施例１で用いた石油系ピッチ
を含浸した。含浸物をステンレス製フォイルで包含し、
その上部にアルミナ５０重ｉ％、シリカ５０重量％より
なるセラミックファイバーのフェルトをピッチ１００重
量部にたいして３００重量部充填して、排気機構付ＨＩ
Ｐ装置において窒素ガスによ、り １０００ ｋｙ／ｃ
ｒｎ”に加圧し、８００℃において加圧炭化処理した。(Example 6) 3000 pitch-based carbon fibers with a diameter of 10μ (microns)
The three-dimensional orthogonal fabric of this bundle was impregnated with the petroleum pitch used in Example 1. enclosing the impregnated material in stainless steel foil;
The upper part is filled with 300 parts by weight of ceramic fiber felt made of 50% by weight alumina and 50% by weight silica for a pitch of 100 parts by weight.
1000 ky/c by nitrogen gas in P equipment
rn'' and subjected to pressure carbonization treatment at 800°C.
加圧炭化に続き、常圧下、不活性ガス雰囲気下で２５０
０℃において黒鉛化処理した。Following pressure carbonization, 250°C under normal pressure and inert gas atmosphere.
Graphitization treatment was carried out at 0°C.
得られた炭素／炭素複合材料を走査型電子顕微鏡、およ
び偏光顕微鏡で観察したところ、繊維束内および繊維束
間にもマトリックスがよく充填されており、炭素繊維の
織物の変形も見られなかった。また炉内の汚れは非常に
軽微であった。When the obtained carbon/carbon composite material was observed using a scanning electron microscope and a polarizing microscope, it was found that the matrix was well filled within and between the fiber bundles, and no deformation of the carbon fiber fabric was observed. . Also, there was very little dirt inside the furnace.
（比較例４）
実施例６と同じ含浸物をステンレス製コンテナに真空封
入し、ＨＩＰ装置において実施例６と同じ条件で処理し
た。(Comparative Example 4) The same impregnated material as in Example 6 was vacuum sealed in a stainless steel container and treated in a HIP apparatus under the same conditions as in Example 6.
得られたものは、コンテナの圧力により炭素繊維の織物
が変形していた。The resulting carbon fiber fabric was deformed by the pressure of the container.
（実施例７）
直径１０μ（ミクロン）のピッチ系炭素繊維の２０００
本束の３次元織物に実施例１で用いた石油系ピッチを含
浸した。含浸物の外側に純度９９％、粒径５μの鉄粉を
充填し、排気機構付ＨＩＰ装置において窒素ガスにより
１０００ｋｙ／ｃｍ２に加圧し、１０００℃において加
圧炭化処理した。(Example 7) 2000 pitch-based carbon fibers with a diameter of 10μ (microns)
The three-dimensional fabric of this bundle was impregnated with the petroleum pitch used in Example 1. The outside of the impregnated product was filled with iron powder having a purity of 99% and a particle size of 5 μm, and was pressurized to 1000 ky/cm 2 with nitrogen gas in a HIP device equipped with an exhaust mechanism, and subjected to pressure carbonization treatment at 1000°C.
加圧炭化に続き、常圧下、不活性ガス雰囲気下で１７０
０℃において炭化処理した。これに再び軟化点２８０℃
の光学的異方性ピッチを含浸し、排気機構付ＨＩＰ装置
において前記条件で加圧炭化処理した。このサイクルを
５回くりかえした。得られた炭素／炭素複合材料は、が
さ密度１７４、曲げ強度は３５ ｋ、／朋２であった。Following pressure carbonization, 170% carbonization under normal pressure and inert gas atmosphere
Carbonization treatment was carried out at 0°C. This again has a softening point of 280°C.
was impregnated with optically anisotropic pitch, and subjected to pressure carbonization treatment under the above conditions in a HIP device with an exhaust mechanism. This cycle was repeated five times. The obtained carbon/carbon composite material had a bulk density of 174 and a bending strength of 35 K/2.
Claims (2)
、鉄および鉄系合金よりなる群より選ばれる少なくとも
一種の物質の共存下において熱間静水圧加圧下で熱処理
し、必要に応じてさらに炭化あるいは黒鉛化することを
特徴とする炭素材料の製造法。(1) Carbonaceous pitch is placed in an open container and heat-treated under hot isostatic pressure in the coexistence of at least one substance selected from the group consisting of refractory fibers, iron, and iron-based alloys. A method for producing a carbon material characterized by further carbonization or graphitization.
含浸物を開放型容器に入れ、耐火物繊維、鉄および鉄系
合金よりなる群より選ばれる少なくとも一種の物質の共
存下において熱間静水圧加圧下で熱処理し、必要に応じ
てさらに炭化あるいは黒鉛化することを特徴とする炭素
／炭素複合材料の製造法。(2) Carbon fiber tow is impregnated with carbonaceous pitch, this impregnated material is placed in an open container, and heated in the coexistence of at least one substance selected from the group consisting of refractory fibers, iron, and iron-based alloys. A method for producing a carbon/carbon composite material, which is characterized by heat treatment under isostatic pressure and further carbonization or graphitization as necessary.
Priority Applications (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063172A JPH075367B2 (en) | 1988-03-18 | 1988-03-18 | Method for producing carbon material and carbon / carbon composite material |
| EP88312352A EP0323750B1 (en) | 1987-12-28 | 1988-12-28 | Process for producing carbon material and carbon/carbon composites |
| DE3855100T DE3855100T2 (en) | 1987-12-28 | 1988-12-28 | Process for the production of carbon material and carbon-carbon composites |
| US07/291,007 US5114635A (en) | 1987-12-28 | 1988-12-28 | Process for producing carbon material and carbon/carbon composites |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63063172A JPH075367B2 (en) | 1988-03-18 | 1988-03-18 | Method for producing carbon material and carbon / carbon composite material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01239064A true JPH01239064A (en) | 1989-09-25 |
| JPH075367B2 JPH075367B2 (en) | 1995-01-25 |
Family
ID=13221575
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63063172A Expired - Lifetime JPH075367B2 (en) | 1987-12-28 | 1988-03-18 | Method for producing carbon material and carbon / carbon composite material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH075367B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013086999A (en) * | 2011-10-14 | 2013-05-13 | Ihi Aerospace Co Ltd | Method for densifying porous structure and densifying apparatus |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01264966A (en) * | 1987-12-28 | 1989-10-23 | Kawasaki Heavy Ind Ltd | Production of carbon material and carbon/carbon composite material |
-
1988
- 1988-03-18 JP JP63063172A patent/JPH075367B2/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01264966A (en) * | 1987-12-28 | 1989-10-23 | Kawasaki Heavy Ind Ltd | Production of carbon material and carbon/carbon composite material |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2013086999A (en) * | 2011-10-14 | 2013-05-13 | Ihi Aerospace Co Ltd | Method for densifying porous structure and densifying apparatus |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH075367B2 (en) | 1995-01-25 |
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