WO1989007577A1 - Procede de production de graphite fortement oriente - Google Patents

Procede de production de graphite fortement oriente Download PDF

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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
Application number
PCT/JP1989/000135
Other languages
English (en)
Japanese (ja)
Inventor
Michio Inagaki
Yoshihiro Hishimaya
Yoshihiro Miwa
Osamu Komada
Isanu Natsume
Original Assignee
Toyo Carbon Company Limited
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toyo Carbon Company Limited filed Critical Toyo Carbon Company Limited
Publication of WO1989007577A1 publication Critical patent/WO1989007577A1/fr

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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. .

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  • 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

Procédé de production de graphite fortement orienté, caractérisé en ce qu'une pluralité de films de polymère aromatique sont stratifiés et carbonisés ou qu'une pluralité de films carbonisés sont stratifiés, ces films étant ensuite graphités sous une pression mécanique. Grâce à ce procédé, il est possible d'obtenir aisément du graphite fortement orienté présentant une structure de graphite très développée, ce produit étant équivalent ou supérieur au graphite conventionnel de la meilleure qualité.
PCT/JP1989/000135 1988-02-10 1989-02-10 Procede de production de graphite fortement oriente WO1989007577A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP63/29810 1988-02-10
JP63029810A JPH01203208A (ja) 1988-02-10 1988-02-10 高配向黒鉛の製造方法

Publications (1)

Publication Number Publication Date
WO1989007577A1 true WO1989007577A1 (fr) 1989-08-24

Family

ID=12286378

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP1989/000135 WO1989007577A1 (fr) 1988-02-10 1989-02-10 Procede de production de graphite fortement oriente

Country Status (2)

Country Link
JP (1) JPH01203208A (fr)
WO (1) WO1989007577A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0468524A2 (fr) * 1990-07-27 1992-01-29 Matsushita Electric Industrial Co., Ltd. Procédé pour la fabrication d'un diaphragme acoustique
EP0691699A1 (fr) * 1994-07-06 1996-01-10 Matsushita Electric Industrial Co., Ltd. Matériau couche de graphite

Families Citing this family (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0244020A (ja) * 1988-08-01 1990-02-14 Res Dev Corp Of Japan グラファイトの製造方法
EP0488356B1 (fr) * 1990-11-30 1997-03-05 Matsushita Electric Industrial Co., Ltd. Procédé de fabrication de blocs en graphite à partir de polymères organiques graphitisables et procédé de carbonisation des films en polymère graphitisable
JP2553784B2 (ja) * 1991-07-10 1996-11-13 松下電器産業株式会社 グラファイトの製造方法
TWI478868B (zh) * 2012-09-19 2015-04-01 鐘化股份有限公司 碳質膜之製造方法及石墨膜之製造方法
CN104495795B (zh) * 2014-11-24 2017-03-08 云南云天化股份有限公司 一种石墨片及其制备方法

Citations (2)

* Cited by examiner, † Cited by third party
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

Patent Citations (2)

* Cited by examiner, † Cited by third party
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)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0468524A2 (fr) * 1990-07-27 1992-01-29 Matsushita Electric Industrial Co., Ltd. Procédé pour la fabrication d'un diaphragme acoustique
EP0468524A3 (en) * 1990-07-27 1993-01-27 Matsushita Electric Industrial Co., Ltd Method of manufacturing acoustic diaphragm
EP0691699A1 (fr) * 1994-07-06 1996-01-10 Matsushita Electric Industrial Co., Ltd. Matériau couche de graphite
US5618615A (en) * 1994-07-06 1997-04-08 Matsushita Electric Industrial Co., Ltd. Graphite layer material

Also Published As

Publication number Publication date
JPH01203208A (ja) 1989-08-16

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