WO1989007577A1 - Method of producing highly oriented graphite - Google Patents
Method of producing highly oriented graphite Download PDFInfo
- Publication number
- WO1989007577A1 WO1989007577A1 PCT/JP1989/000135 JP8900135W WO8907577A1 WO 1989007577 A1 WO1989007577 A1 WO 1989007577A1 JP 8900135 W JP8900135 W JP 8900135W WO 8907577 A1 WO8907577 A1 WO 8907577A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- graphite
- highly oriented
- aromatic polymer
- carbonized
- laminated
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/52—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite
- C04B35/524—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbon, e.g. graphite obtained from polymer precursors, e.g. glass-like carbon material
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/20—Graphite
- C01B32/205—Preparation
Definitions
- the present invention relates to vibration elements such as some electrodes, heating elements and structural materials, high-temperature and high-pressure gaskets, heat insulating materials, corrosion-resistant seals, brushes for electric machines, X-ray monochromators, speaker cones, and the like.
- the present invention relates to a method for producing highly oriented graphite used for applications such as a substrate for producing a graphite intercalation compound.
- natural graphite has been used as highly oriented graphite used for applications utilizing the properties of graphite as described above, as well as limited production and low purity.
- it can be used for precipitation from Fe, 1 ⁇ 'i.ZC-based melts, decomposition of carbides such as Si, A £, or precipitation from carbon melts under high temperature and high pressure.
- a highly oriented pyrographite that is produced by pyrolyzing and depositing graphite and hydrocarbons that are produced by hot-working.
- a method of obtaining a graphite phenol film by heat-treating a film of an aromatic polymer There is also known a method of obtaining a graphite phenol film by heat-treating a film of an aromatic polymer.
- an object of the present invention is to produce high-quality highly oriented graphite suitable for industrial use in an industrially advantageous manner.
- the gist of the present invention is characterized in that a plurality of aromatic polymer films are laminated and carbonized, or a plurality of films are laminated after carbonization, and further graphitized under mechanical pressure.
- Graphite ' It depends on the manufacturing method.
- Graphite is formed by regularly assembling and arranging fine crystallites consisting of a graphite layer surface, which is a laminate of carbon net planes.
- the terms carbonization and graphitization are-. The boundaries between each other are not always clear, usually the former is when organic matter decomposes and releases foreign elements, i.e. It. 3 ⁇ 4...., the latter addition-.. te ⁇ elementary plane or product 3 ⁇ 4 'and graphite It means that crystals form and the microcrystals grow and arrange.
- carbonization is used as a term that refers to a state in which carbonization in the above-mentioned normal meaning has been completed and graphitization has not yet been completed but is progressing. .
- X-ray diffraction is often used to evaluate graphite crystals.
- the crystallite size L c in the c-axis direction and the size L a in the a ⁇ direction, which are obtained from the half-widths of the diffraction lines (.0 £) and (hk 0), are often used.
- c. Is equivalent to the interplanar spacing of the graphite layers, and a smaller value means that the graphitization is progressing in the crystallite.
- the residual resistance ratio is the electrical resistivity 0 ⁇ at a temperature near normal temperature and the electrical resistivity P T at an extremely low temperature T 0. And the ratio P ⁇ ⁇ ⁇ ⁇ . It is. The larger the maximum value of the magnetic resistance of one graphite sample and the higher the residual resistance ratio, the more the graphite structure of the graphite sample develops, and the integration of graphite crystallites progresses, and the graphite sample becomes closer to a perfect graphite crystal. It can be said that.
- a plurality of aromatic polymer films are laminated and then carbonized, or carbonized and then laminated, and then graphitized under mechanical pressure. It is a special feature.
- a polymer film containing an aromatic ring in a monomer can be used.
- a graphitizable heat-resistant aromatic polymer specifically, polyimide , Polyamide, Polyimide, Polyoxadiazole, PO:
- Polynaphine Polybis.
- a plurality of aromatic polymer films may be laminated and carbonized, or the films may be carbonized one by one, and other special measures for carbonization are not required.
- the carbonization temperature of the beef that is, the sintering temperature is mainly in the range of 200'C or more depending on the kind of the aromatic polymer of the film material.
- the carbonization temperature of the beef that is, the sintering temperature is mainly in the range of 200'C or more depending on the kind of the aromatic polymer of the film material.
- carbon exceeding 6.90 is hardly graphitized and has poor flexibility, so it is easy to crack when pressurized, and conversely c.
- the graphitization step in the method of the present invention needs to be performed under mechanical pressure to bond the laminated films to each other, particularly under pressure in the film laminating direction.
- a machine called a hot press which simultaneously performs pressurization and heating, is used, and a laminate of the film is about 5 kg / 'cm 2 or more, preferably 100 to Applying a pressure of 500 kg / cm 2 and heating it to a temperature above the graphitization temperature, preferably between 260 and 370,000 in a non-oxidizing atmosphere, will destroy or wear the laminate.
- This makes it possible to produce high-quality, highly-aligned graphite that is firmly integrated without being stiff, and is particularly suitable for aromatic polymer fibers having a repeating unit represented by the above formula (I).
- the film of the aromatic polymer is not limited in principle in the number of layers of the carbonized product, and the films are firmly bound and integrated in the graphitization step. Any number of layers can be used as long as the number of layers is sufficient and uniform and pressurization and heating can be performed.Highly oriented graphite that has a length of about 10 mm even when using a normal electric heating type * press press Can be manufactured. In addition, by taking into account the shrinkage of the aromatic polymer film due to carbonization and graphitization, highly oriented graphite having a desired thickness and size can be produced within the range of hot press capability. .
- Aromatic boron of ⁇ 0 um A stack of 100 pieces of imidfinolene (Dupont's cuff-ton) cut into a rectangle of 60 mm x 30 strokes was stacked, sandwiched between graphite plates from above and below, and passed through a nitrogen flow. In the furnace, the temperature was raised to 160,000 from the room temperature at a rate of 10 minutes per minute, maintained for 1 hour, allowed to cool naturally to room temperature in a furnace, and then graphite tamman passed through a nitrogen stream.
- the bulk specific gravity of the sheet graphite is equal to the theoretical value of ideal graphite, and the lattice constant in the c-axis direction is the same as that of natural graphite of the highest quality. Is comparable to high quality, highly oriented pyrographite.
- a residual resistance ratio ⁇ 3 which is a ratio between the electric resistivity at 300 ° C. and the electric resistivity at the liquid helium temperature. . ⁇ / ⁇ 4. ⁇ ⁇ and liquid nitrogen
- the maximum value of the air resistance when a magnetic field of 1 T is applied at the elementary temperature ( ⁇ P no P) 77 ⁇ , 1 T , max indicates that the platy graphite is a good quality graphite.
- a high-distribution graphite having a graphite structure highly developed and having properties equal to or higher than those of the conventional high quality can be easily obtained, and a great industrial advantage is provided. .
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Ceramic Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Carbon And Carbon Compounds (AREA)
- Pigments, Carbon Blacks, Or Wood Stains (AREA)
Abstract
This invention relates to a method of producing highly oriented graphite characterized in that a plurality of aromatic polymer films are laminated and carbonized or a plurality of carbonized films are laminated, and they are then graphitized under mechanical pressure. According to this method, it is possible to easily obtain highly oriented graphite having a highly developed graphite structure and being equivalent or superior to conventional graphite having the highest quality.
Description
_ ί _ ί
5 明 細 高配向黒鉛の製造方法 5 Akira Fine Manufacturing method of highly oriented graphite
技 術 分 野 Technical field
本発明は一部の電極、 発熱体及び構造材、 高温高圧用 ガスケ ッ ト 、 断熱材、 耐食性シール、 電機用ブラ シ、 X 線モ ノ ク ロメ ータ、 ス ピーカ コー ン等の振動素子並びに 黒鉛層間化合物製造用基材等の用途に用い られる高配向 黒鉛の製造方法に係る ものである。 The present invention relates to vibration elements such as some electrodes, heating elements and structural materials, high-temperature and high-pressure gaskets, heat insulating materials, corrosion-resistant seals, brushes for electric machines, X-ray monochromators, speaker cones, and the like. The present invention relates to a method for producing highly oriented graphite used for applications such as a substrate for producing a graphite intercalation compound.
10 背 景 技 術 10 Background technology
従来、 上記の様な黒鉛の結晶と しての性質を利用する 用途に供する高配向黒鉛と しては、 天然黒鉛が用い られ ているほか、 生産量が限られ、 純度が低い等の問題点が ある天然黒鉛に代わる ものと して、 F e , 1\' i .Z C系融 体からの析出、 S i ， A £等の炭化物の分解又は高温高 圧下での炭素融液からの析出によ つ.て製造される キ ソ ュ黒鉛及び炭化水素を熱分解沈積し、 これに熱間加工を 加えて製造される高配向パイ ログラ フ ァ イ トがある。 又 - ほか 芳香族高分子のフ ィ ルムを熱処理して黒鉛フ ィ ノレ 0 ムを得る方法が知られている„ Conventionally, natural graphite has been used as highly oriented graphite used for applications utilizing the properties of graphite as described above, as well as limited production and low purity. As an alternative to certain natural graphite, it can be used for precipitation from Fe, 1 \ 'i.ZC-based melts, decomposition of carbides such as Si, A £, or precipitation from carbon melts under high temperature and high pressure. There is a highly oriented pyrographite that is produced by pyrolyzing and depositing graphite and hydrocarbons that are produced by hot-working. There is also known a method of obtaining a graphite phenol film by heat-treating a film of an aromatic polymer.
しかし .. キ ッ シ ュ黒鉛は通常は^片状 っ て 、 塊お: 土 ュ黒鉛の製造は多大の労力を要し 高 ffi向パィ コ • 二マ ィ ト は製造方法が複雑である ^ . 芳香族高- - 子 、 マ Λ ルムを熱処理する方 gに て . 材 と して が 方が得 ら る黒^ 向性つ;
なる傾向にある為、 原理的に薄いフ ィ ルムしか得られす 前記のいずれの方法も工業的利用を制約する欠点がある ; 本発明者等はこれらの欠点を解決すベく鋭意検討した 結果、 芳香族高分子のフィル丄を熱処理する方法におい て、 該フ ィ ルム又はその炭化品を複数枚積層して機械加 圧下で熱処理すれば、 材料として用いた複数枚のフ ィ ル ムが互いに強く結着一体化することを見出し、 可久的薄 く て良質な芳香族高分子のフ ィ ルムから該フィ ルム以上 の厚みを有し、 場合によってはリ ジッ ドな高配向黒鉛が 容易に製造できるこ とに想到し、 本発明に到達した。 However .. Kiss graphite is usually flaky, lump: making graphite is very labor intensive, and high efficiencies are difficult to manufacture. Heat-treating aromatic polymers and gums. In principle, only a thin film can be obtained.Either of the above methods has the drawback of restricting industrial use ; the present inventors have conducted intensive studies to solve these drawbacks. In the method of heat-treating an aromatic polymer film, if a plurality of such films or their carbonized products are laminated and heat-treated under mechanical pressure, a plurality of films used as a material are mutually bonded. It was found that it was strongly bound and integrated, and it was possible to easily obtain a rigid thin highly oriented graphite from a thin and high-quality aromatic polymer film to a thicker film than the film. Having arrived at the fact that they can be manufactured, they have reached the present invention.
即ち、 本発明の目的は、 工業的利用に適する良質な高 配向黒鉛を工業的有利に製造することにある。 That is, an object of the present invention is to produce high-quality highly oriented graphite suitable for industrial use in an industrially advantageous manner.
発 明 の 開 示 Disclosure of the invention
本発明の要旨は、 芳香族高分子のフ ィ ルムを、 複数枚 積層して炭化するか又は炭化した後複数枚積層し、 更に 機椟加圧下で黒鉛化する ことを特徵とする高 己 ^黒鉛': 製造方法に存する。 The gist of the present invention is characterized in that a plurality of aromatic polymer films are laminated and carbonized, or a plurality of films are laminated after carbonization, and further graphitized under mechanical pressure. Graphite ': It depends on the manufacturing method.
以下、 本発明を詳細に説明する。 Hereinafter, the present invention will be described in detail.
黒鉛は、 炭素網平面の積層物たる黒鉛層面から成る微 な結晶子が規則的に集合 · 配列して成る ものてあつて 該結晶子の向きのよ く撗つた s鉛を高配 [S1黒鉛という 、 炭化及 黒鉛化なる用語は-. 互いの境 か必ずし 明瞭ではない 、 通常、 前者は有機物が^分解して異種 元素を放出す と iもに ¾素 平面 o生. -: ·る反 it.を ¾ …. 、 後者 加 によ -..て^素 平面か積 ¾'して黒鉛
結晶を成し、 該微結晶が成長 · 配列する こ とをいう。 し かし、 本発明において炭化とは、 上記の通常の意味での 炭化が終了し、 黒鉛化が未だ完了せず進行しつつある状 態をも舍む用語と して使用する こ と とする。 Graphite is formed by regularly assembling and arranging fine crystallites consisting of a graphite layer surface, which is a laminate of carbon net planes. The terms carbonization and graphitization are-. The boundaries between each other are not always clear, usually the former is when organic matter decomposes and releases foreign elements, i.e. It. ¾…., the latter addition-.. te ^ elementary plane or product ¾ 'and graphite It means that crystals form and the microcrystals grow and arrange. However, in the present invention, the term "carbonization" is used as a term that refers to a state in which carbonization in the above-mentioned normal meaning has been completed and graphitization has not yet been completed but is progressing. .
黒鉛の結晶を評価するにはしばしば X線回折法が用い られ、 特に黒鉛の （ 0 0 ） 回折線の位置から計箕され る c軸方向、 即ち黒鉛層面に垂直な方向の格子定数 c 。 . 及び （ 0 0 £ ) 及び （ h k 0 ) 回折線の半価幅から求め られる結晶子の c軸方向の大き さ L c 及び a 铀方向の大 き さ L a がよ く 用いられる。 c 。 は黒鉛層面の層面間隔 に相当 し、 小さい程前記結晶子内で黒鉛化が進んでいる こ とを意味し、 一方 （ 0 0 ) 及び （ h k 0 ) 回折線の 半価幅が小さい程そこから計算される L c 及び L a は大 きい。 黑鉛の結晶子の配向度を評価するに 、 無数の結 晶子の黒鉛層面の法線同士のなす角のばらつきを表すモ ザィ ク スプ レ ；' ドな る量が用い られる。 こ のモザィ ク ス プレ 'ン' ドは、 簡便法と しては通常の結晶 X線回折法にお いて、 黒鉛サ ンプル及び X線検出操置を （ 0 0 2 ) 回折 線が観測される位置にセ ッ ト し .、 黒鉛サ ンつ。ルのみをわ ずかに回転させたとき、 該 （ 0 G 2 ) 回折綿が観測され 得る該黒鉛サ ンプルの回転角の範囲の大き さによ -:.て表 r?される。 即ち、 。 が天然黒鉛の最小使て る ε. マ 0 8 A z jS . L 及 L a か大き ： 、 且つモ 斗 ノ ク スプ i か小さい程黒鉛構造が高 Sに発连 L 良 ¾ '高 向黒 であ δ としえ ：
他に黒鉛を電気的 · 磁気的性質から評価する方法があ り、 その指標として磁気抵抗及び残留抵抗比等が挙げら れる。 磁気抵抗は電気抵抗率を磁場 Bの関数 p ( B ) と 厶 P p ( B ) ~ p ( 0 ) X-ray diffraction is often used to evaluate graphite crystals. In particular, the lattice constant c in the c-axis direction measured from the position of the (00) diffraction line of graphite, ie, the direction perpendicular to the graphite layer surface. The crystallite size L c in the c-axis direction and the size L a in the a 铀 direction, which are obtained from the half-widths of the diffraction lines (.0 £) and (hk 0), are often used. c. Is equivalent to the interplanar spacing of the graphite layers, and a smaller value means that the graphitization is progressing in the crystallite. On the other hand, the smaller the half width of the (00) and (hk0) diffraction lines, The calculated L c and L a are large.黑 In order to evaluate the degree of orientation of the crystallites of lead, a mosaic spread, which represents the variation in the angle between the normals of the graphite layers of innumerable crystallites, is used. In this mosaic plane, as a simple method, in the usual X-ray crystallography method, the (002) diffraction line is observed by the graphite sample and the X-ray detection device. Set it to the position. When only the sample is slightly rotated, the (0 G 2) diffraction cotton is observed according to the magnitude of the rotation angle range of the graphite sample from which the diffraction cotton can be observed. That is,. Is the minimum of natural graphite ε. Ma 08 Az jS. L and La are larger or smaller, and the smaller the diameter is, the higher the graphite structure is. And δ: There are other methods of evaluating graphite from its electrical and magnetic properties, and its indexes include magnetoresistance and residual resistance ratio. Magnetoresistance is a function of magnetic resistance B (p (B) and P p (B) ~ p (0)
して表したとき —— = ： ^ で定義さ When expressed as —— =: defined by ^
P 0 ( 0 ) P 0 (0)
れる量であって、 一方残留抵抗比は常温付近の温度丁に おける電気抵抗率 0 τ と極低温の温度 T 0 における電気 抵抗率 P T。との比 P τ Ζ Ρ τ。である。 ひとつの黒鉛サン プルについて磁気抵抗の最大値が大き く 、 残留抵抗比か 大きい程該黒鉛サ ンプルは黒鉛構造が発達し、 且つ黒鉛 の結晶子同士の一体化が進みより完全な黒鉛結晶に近い といえる。 On the other hand, the residual resistance ratio is the electrical resistivity 0 τ at a temperature near normal temperature and the electrical resistivity P T at an extremely low temperature T 0. And the ratio P τ Ζ τ τ. It is. The larger the maximum value of the magnetic resistance of one graphite sample and the higher the residual resistance ratio, the more the graphite structure of the graphite sample develops, and the integration of graphite crystallites progresses, and the graphite sample becomes closer to a perfect graphite crystal. It can be said that.
本発明方法においては、 かかる良質の高配向黒鉛を製 造すべく芳香族高分子のフ ィルムを複数枚積層した後炭 化するか又は炭化した後複数枚積層し、 更に機械加圧下 で黒鉛化することが特徵である。 材料として用いる前記 フ ィ ルムとしてはモノ マーに芳香環を含む高分子フ ィ ル ムが使用可能であって、 中でも易黒鉛化性の耐熱性芳香 族高分子、 具体的にはボリ イ ミ ド、 ボリ ァ ミ ド、 ボリ マ ミ ドイ ミ ド、 ボリ オキサジァソ一ル、 ポ：| ベンズィ ミ ダ ゾ一ル、 ポ リ フ エ ニ レンビ二 レ ン -. ポ リ ぺ リ ナフク レ ： ポ リ ビス. マ レィ ミ ド ト リ ァ ジ ン及びポ ：| ヒスマ レイ ミ から成る群から選 れた 1 種以上の芳香族高分子 フ - 丄が好ま しい _ 上記の好ま し 芳香族高 子をそ O ^ 返し単位 O構造 で具体的に特定した ^と しては例え
下記の式 （ I ) ~ ( X ) が挙げられる In the method of the present invention, in order to produce such high-quality highly oriented graphite, a plurality of aromatic polymer films are laminated and then carbonized, or carbonized and then laminated, and then graphitized under mechanical pressure. It is a special feature. As the film used as the material, a polymer film containing an aromatic ring in a monomer can be used. Among them, a graphitizable heat-resistant aromatic polymer, specifically, polyimide , Polyamide, Polyimide, Polyoxadiazole, PO: | Benzimidazole, Polyphenylenevinylene-. Polynaphine: Polybis. Maleid triazine and po: | At least one aromatic polymer selected from the group consisting of Hisima Reimi is preferred _ The preferred aromatic polymer is O ^ For example, if ^ is specifically specified by the return unit O structure The following formulas (I) to (X)
T" T "
— N N— )〉一 0—— '： ( ) /— — N N—)〉 1 0—— ': () / —
上1' 1丄— ί ( ITop 1 ' 1丄 — ί (I
.,ィ- 、、ノ ,- h o ., ィ-,, no, -ho
0 0 0 0
10 C 0 - 广ヽ广 C 0 N H一、し） ,一 N H ( I ) 10 C 0-广 ヽ 广 C 0 N H, I), I N H (I)
..z -、、 ..z-,,
■CO C0NH X·厂 NH ■ CO C0NH X · Factory NH
、 〇. ( IV ) , 〇. (IV)
) )
6 )) 6
/
/、、 . 〇 / / ,,.
./.. ./ ..
( Κ ) (Κ)
— : ハ、丫' ,—— 0 —: Ha, 丫 ', —— 0
人 ·> ( X ) Person ·> (X)
- 人. - Man.
0 0 0 0
本発明方法においては、 芳香族高分子のフ イ ルムを複 数枚積層して炭化しても、 該フ ィ ルムを 1 枚ずつ炭化し てもよ く 、 その他炭化に特段の工夫を要しないが、 炭化 後、 黒鉛化の工程に供するフ ィ ルムの c軸方向の格子定 数 c。 が e. 7 5 6. 9 0 Aとなる様に炭化条 ΐ牛、 即ち主 として焼成温度をフ ィ ルムの材料の芳香族高分子の種類 に応じて 2 0 0 0 'C以上の範囲で調節する のが好ま しい, なぜなら、 c。 が 6. 9 0 人を越える炭素は殆んど黒鉛化 が進んでお らず可撓性に乏しい為加圧する と割れ易く 、 逆に c。 が 6. 7 5 Α未浩だと各マ „· ルムの黒鉛化が進み すぎており、 該っ ィ ルムの積層体を改 て加圧下で加熱 しても各フ ル ム同士の結着一体化 ぅ '： 亍ゎれず— ニ G)積層面：ニ剝離亀裂を生しる ¾ か δか で フ' 炭化 工程 加 で ί*τ r; て い . あま
り強 く 加圧する と炭化に際して放出される異種元素含有 ガスが逃げ場を失い気泡となって残る惧れがあり、 又炭 化により硬化したフ ィ ルムが割れるのを防 ぐ意味からも、 加圧は炭化すべきフ ィ ルム の位置がずれない程度の弱い 加圧で十分である。 In the method of the present invention, a plurality of aromatic polymer films may be laminated and carbonized, or the films may be carbonized one by one, and other special measures for carbonization are not required. Is the lattice constant c in the c-axis direction of the film to be subjected to the graphitization process after carbonization. In order to obtain e.75.690 A, the carbonization temperature of the beef, that is, the sintering temperature is mainly in the range of 200'C or more depending on the kind of the aromatic polymer of the film material. Prefer to adjust, because c. However, carbon exceeding 6.90 is hardly graphitized and has poor flexibility, so it is easy to crack when pressurized, and conversely c. However, in the case of 6.75 Α, the graphitization of each film was progressing too much, and even if the film laminate was heated under pressure again, the bonding of the films was unified. Chemical composition: 亍 ゎ — G G) Laminated surface: ί * τ r ; in the carbonization process, depending on whether 剝 or δ causes a separation crack. When pressurized too strongly, the gas containing different elements released during carbonization may lose its escape space and remain as bubbles, and pressurization is also used to prevent the film hardened by carbonization from cracking. It is sufficient to apply a weak pressure that does not displace the position of the film to be carbonized.
本発明方法中の黒鉛化の工程は、 積層されたフ ィ ルム 同士を互いに結着せしめるベ く 機械加圧下、 特にフ ィ ル ムの積層方向への加圧下で行う必要があり、 その為には ホ ッ ト プレス と呼ばれる加圧及び加熱を同時に行う機被 を用いるのが普通であって、 該フ ィ ルム の積層物に 5 kg /' cm 2 程度以上、 好ま し く は 1 0 0 〜 5 0 0 kg / cm 2 の 圧力をかけ、 非酸化性雰囲気下、 黒鉛化温度以上、 好ま し く は 2 6 0 0 〜 3 7 0 0 て程度に加熱すれば、 該積層 物を破壞又は消耗せしめる惧れな く 強固に一体化した良 質な高配向黒鉛を製造でき る こ と となり適当であって、 特に前記式 （ I ) で表される繰り返し単位を舍む芳香族 高分子のフ ィ ルム の場合には 3 ί 0 0 〜 3 7 0 0 て程度 に加熱するのが好ま しい。 The graphitization step in the method of the present invention needs to be performed under mechanical pressure to bond the laminated films to each other, particularly under pressure in the film laminating direction. Usually, a machine called a hot press, which simultaneously performs pressurization and heating, is used, and a laminate of the film is about 5 kg / 'cm 2 or more, preferably 100 to Applying a pressure of 500 kg / cm 2 and heating it to a temperature above the graphitization temperature, preferably between 260 and 370,000 in a non-oxidizing atmosphere, will destroy or wear the laminate. This makes it possible to produce high-quality, highly-aligned graphite that is firmly integrated without being stiff, and is particularly suitable for aromatic polymer fibers having a repeating unit represented by the above formula (I). In the case of rum, it is preferable to heat the mixture to about 300 to 3700.
その他、 例えば誘導加熱型ホ ッ ト プレスを用いる場合 の様に被加熱物に直接通電しないで加熱し加圧する方法 を採る場合には、 初めから複数枚積層 した高分子 フ -ί ル丄を連続し 1 回の工程だけで黒鉛化し 、 一体化する 二 こができ る。 - 、 機械加圧の際に 芳香斿高分子の -. 一の積層物又 その 化品を ¾型と ¾型〇 抶 加圧: 5; 加熱すれ： . 従 得^ 1： . -, ：こ異 Ο高 向 IP.
鉛が容易に製造できる。 更に、 前記炭化及び/又は黒鉛 化の工程において被炭化物又は被黒鉛化物をフイ ルム面 上に働く互いに約り合う力で周囲から引っ張りつつ加熱 すれば、 より高配向の黒鉛が得られる。 In addition, when a method of heating and pressurizing without directly energizing the object to be heated, such as when using an induction heating type hot press, is used, a plurality of polymer layers are continuously stacked from the beginning. However, it can be graphitized and integrated in only one process. -When the mechanical pressure is applied, the aromatic or high molecular compound is used.-One laminate or its compound is pressed into a mold and a mold. Pressing: 5; Heating:. Differential IP. Lead can be easily manufactured. Furthermore, in the carbonization and / or graphitization step, if the material to be carbonized or the material to be graphitized is heated while being pulled from the surroundings by a force approximately equal to each other acting on the film surface, graphite with higher orientation can be obtained.
筒、 本究明方法において、 芳香族高分子のフ ィ ルムは その炭化品の積層枚数には原理的には制約がなく、 前記 黒鉛化の工程において各フィ ルム同士を強固に結着一体 化せしめるのに充分で且つ均一な加圧及び加熱を行える 程度の積層枚数なら何枚でもよ く、 通常の通電加熱型 * ッ ト プレスを用いた場合でも 1 0 mm程度の 1Ϊみを有する 高配向黒鉛の製造が可能である。 又、 炭化及び黒鉛化に 伴う芳香族高分子フィルムの収縮率を考慮することによ り、 ホ ッ トプレスの能力の範囲内で所望の厚み及び大き さを有する高配向黒鉛を製造することもできる。 In the present investigation method, the film of the aromatic polymer is not limited in principle in the number of layers of the carbonized product, and the films are firmly bound and integrated in the graphitization step. Any number of layers can be used as long as the number of layers is sufficient and uniform and pressurization and heating can be performed.Highly oriented graphite that has a length of about 10 mm even when using a normal electric heating type * press press Can be manufactured. In addition, by taking into account the shrinkage of the aromatic polymer film due to carbonization and graphitization, highly oriented graphite having a desired thickness and size can be produced within the range of hot press capability. .
発明を実施するための最良の形態 以下、 本発明を実施例により更に詳細に説明する力;、 本発明はその要旨を超えない限り、 下記実施例により限 定されるものではない。 BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in more detail with reference to examples; however, the present invention is not limited to the following examples unless it exceeds the gist thereof.
実施例 Example
下記の式 （ I ) The following equation (I)
0 0 0 0
'へ、 z、- —— 'To z,---
一 One
0 C 0 C
で表される操返し単位を含む 5：さ δ 0 u mの芳香族ボリ
ィ ミ ド フ イ ノレム （デュポン社製カ フ' ト ン） を 6 0 mm X 3 0 画の長方形に切断したものを 1 0 0枚積み重ね、 上下 から黒鉛板で挟み、 窒素気流を通した炉内で室温から毎 分 1 0 ての昇温速度で 1 6 0 0 てまで昇温して 1 時間保 持し、 炉中にて室温まで自然放冷し、 次いで窒素気流を 通した黒鉛タ ンマン炉に入れ、 毎分 2 0 ての昇温速度で 2 5 0 0 てまで异温して 1 時間保持し、 室温まで自然放 冷したとこ ろ、 X線回折像から計算した c紬方向の格子 定数が 6. 7 6 Aである炭素焼成体が得られた。 該炭素焼 成体を黒鉛ダイ ス中にセ ッ 卜 し、 上下から 2 0 0 kg / cm 2 の圧力で加圧しながら 2 0 k Wで 3 0分間通電加熱し、 室温まで放冷して 4 5 腿 X 2 5 腿 X 3 mmの扳状黒鉛を得 た。 該板状黒鉛の諸特性を表一 1 に示す。 Including the repeat unit represented by 5: Aromatic boron of δ 0 um A stack of 100 pieces of imidfinolene (Dupont's cuff-ton) cut into a rectangle of 60 mm x 30 strokes was stacked, sandwiched between graphite plates from above and below, and passed through a nitrogen flow. In the furnace, the temperature was raised to 160,000 from the room temperature at a rate of 10 minutes per minute, maintained for 1 hour, allowed to cool naturally to room temperature in a furnace, and then graphite tamman passed through a nitrogen stream. Placed in a furnace, heated to 250 ° C at a heating rate of 20 ° C per minute, held for 1 hour, allowed to cool naturally to room temperature, and latticed in the c-pong direction calculated from X-ray diffraction images A carbon fired body having a constant of 6.76 A was obtained. The carbon sintered body was set in a graphite die, heated by applying electricity at 20 kW for 30 minutes while applying a pressure of 200 kg / cm 2 from above and below, and allowed to cool to room temperature, and then cooled. Graphite having thigh X 25 thigh X 3 mm was obtained. Table 11 shows various properties of the sheet graphite.
表 ― 1 table 1
産業上の利用分野 Industrial applications
本発明方法によれば、 黒鉛構造が高度に発達した、 従 来の最高品質のものと同等以上の性質を有する高配商黒 鉛が容易に得られ、 多大の工業的利益を提供するもので ある。
According to the method of the present invention, a high-distribution graphite having a graphite structure highly developed and having properties equal to or higher than those of the conventional high quality can be easily obtained, and a great industrial advantage is provided. .
Claims
(1) 芳香族高分子のフ ィ ルムを、 複数枚積層して炭化 するか又は炭化した後複数枚積層し、 更に機械加圧下で 黒鉛化する こ とを特徴とする高配向黒鉛の製造方法。 (1) A method for producing highly oriented graphite, characterized in that a plurality of aromatic polymer films are laminated and carbonized or a plurality of carbonized films are laminated and then graphitized under mechanical pressure. .
(2) 前記芳香族高分子がポ リ イ ミ ド、 ボリ ア ミ ド、 ボ リ ア ミ ドイ ミ ド、 ポ リ オキサジァゾ一ル、 ボ リ ベンズィ ミ ダゾ一ル、 ボ リ フ エ 二 レ ンビニ レ ン、 ボ リ ペ リ ナフタ レ ン、 ポ リ ビスマ レイ ミ ド ト リ ア ジ ン及びポ リ ビスマ レ ィ ミ ドから成る群から選ばれた 1 種以上の芳香族高分子 である こ とを特徴とする請求の範囲第 1 項記載の高配向 黒鉛の製造方法。
(2) The aromatic polymer is polyimid, polyamido, polyamidoimid, polyoxadiazole, polybenzimidazole, polyphenylenevinylene. Characterized in that it is at least one aromatic polymer selected from the group consisting of polyolefin, polynapinaphthalene, polyvisma leimido triazine, and polyvisma imide. 2. The method for producing highly oriented graphite according to claim 1, wherein:
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63029810A JPH01203208A (en) | 1988-02-10 | 1988-02-10 | Production of highly oriented graphite |
| JP63/29810 | 1988-02-10 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO1989007577A1 true WO1989007577A1 (en) | 1989-08-24 |
Family
ID=12286378
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/JP1989/000135 WO1989007577A1 (en) | 1988-02-10 | 1989-02-10 | Method of producing highly oriented graphite |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JPH01203208A (en) |
| WO (1) | WO1989007577A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0468524A2 (en) * | 1990-07-27 | 1992-01-29 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing acoustic diaphragm |
| EP0691699A1 (en) * | 1994-07-06 | 1996-01-10 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0244020A (en) * | 1988-08-01 | 1990-02-14 | Res Dev Corp Of Japan | Production of graphite |
| EP0488356B1 (en) * | 1990-11-30 | 1997-03-05 | Matsushita Electric Industrial Co., Ltd. | Processes for producing graphite blocks from graphitizable organic polymers and process for carbonizing graphitizable polymer films |
| JP2553784B2 (en) * | 1991-07-10 | 1996-11-13 | 松下電器産業株式会社 | Graphite manufacturing method |
| TWI478868B (en) * | 2012-09-19 | 2015-04-01 | 鐘化股份有限公司 | Method for producing carbonaceous film, and method for producing graphite film |
| CN104495795B (en) * | 2014-11-24 | 2017-03-08 | 云南云天化股份有限公司 | A kind of graphite flake and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS645634A (en) * | 1987-06-30 | 1989-01-10 | Aisin Aw Co | Die for warm punching and shaving |
| JPS6456365A (en) * | 1987-08-26 | 1989-03-03 | Japan Res Dev Corp | Production of graphite |
-
1988
- 1988-02-10 JP JP63029810A patent/JPH01203208A/en active Pending
-
1989
- 1989-02-10 WO PCT/JP1989/000135 patent/WO1989007577A1/en unknown
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS645634A (en) * | 1987-06-30 | 1989-01-10 | Aisin Aw Co | Die for warm punching and shaving |
| JPS6456365A (en) * | 1987-08-26 | 1989-03-03 | Japan Res Dev Corp | Production of graphite |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0468524A2 (en) * | 1990-07-27 | 1992-01-29 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing acoustic diaphragm |
| EP0468524A3 (en) * | 1990-07-27 | 1993-01-27 | Matsushita Electric Industrial Co., Ltd | Method of manufacturing acoustic diaphragm |
| EP0691699A1 (en) * | 1994-07-06 | 1996-01-10 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
| US5618615A (en) * | 1994-07-06 | 1997-04-08 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01203208A (en) | 1989-08-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Hishiyama et al. | Graphite films prepared from carbonized polyimide films | |
| EP3257811B1 (en) | Smooth-surfaced graphite membrane and method for producing same | |
| WO2017148105A1 (en) | Carbonized membrane prepared from flexible polyimide and preparation method therefor | |
| EP0205970A2 (en) | Process for producing graphite films | |
| Sharma et al. | Edge controlled growth of hexagonal boron nitride crystals on copper foil by atmospheric pressure chemical vapor deposition | |
| WO1989007577A1 (en) | Method of producing highly oriented graphite | |
| US4954193A (en) | Method for making a graphite film or sheet | |
| EP0360217B1 (en) | Process for producing graphite blocks | |
| CN110451964A (en) | A kind of preparation method of high orientation Graphite block material | |
| JP3065896B2 (en) | Manufacturing method of highly oriented graphite | |
| KR101473432B1 (en) | Method for fabricating graphite | |
| KR101471397B1 (en) | Method for fabricating graphite | |
| JP4419337B2 (en) | Highly oriented graphite layered sheet and method for producing the same | |
| EP0449312A2 (en) | Process for preparing a graphite film or block from polyamido acid films | |
| JP2553784B2 (en) | Graphite manufacturing method | |
| JPH0742095B2 (en) | Graphite manufacturing method | |
| EP0803487B1 (en) | Process for producing carbonaceous preform | |
| JP4691721B2 (en) | Composite film made of cloth and clay | |
| JP3036039B2 (en) | Graphite block and method of manufacturing the same | |
| JP2013216552A (en) | Film composed of carbon atom and method for producing the film | |
| JPH04202052A (en) | Production of graphite | |
| JP3749286B2 (en) | Method for producing carbonized aromatic polyimide film laminate | |
| JPS60239358A (en) | Carbonaceous thin plate and manufacture | |
| JPH0283208A (en) | Production of graphite | |
| JPH0517117A (en) | Production of graphite |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| AK | Designated states |
Kind code of ref document: A1 Designated state(s): US |
|
| AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH DE FR GB IT LU NL SE |