JP2010228934A - Method for heat-treating thin plate-like molding - Google Patents

Method for heat-treating thin plate-like molding Download PDF

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JP2010228934A
JP2010228934A JP2009075513A JP2009075513A JP2010228934A JP 2010228934 A JP2010228934 A JP 2010228934A JP 2009075513 A JP2009075513 A JP 2009075513A JP 2009075513 A JP2009075513 A JP 2009075513A JP 2010228934 A JP2010228934 A JP 2010228934A
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thin plate
molded body
graphite powder
shaped
heat
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Makoto Aoki
信 青木
Shigeru Murakami
繁 村上
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Fuji Electric Co Ltd
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Fuji Electric Systems Co Ltd
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for heat-treating a thin plate-like molding where a laminated thin plate-like molding is heat-treated, the occurrence of the warping and cracks of carbon thin plates obtained by heat-treating the thin plate-like molding is prevented and a technique for mass-production by increasing the quantity of the carbon thin plates produced by one performance of heat treatment is provided. <P>SOLUTION: Problems are solved by heat-treating the thin plate-like molding after a coating film containing graphite powders is formed on both surfaces or one surface of the thin plate-like molding or by heat-treating the thin plate-like molding where a sheet containing graphite powders is intercalated between the thin plate-like moldings and laminated. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

本発明は、燃料電池の構成部材として用いられるセパレータ板や多孔質カーボン板などの炭素薄板を製造する工程のうち、薄板状成形体を加熱処理して炭素薄板を得る工程に係る技術に関する。   The present invention relates to a technique related to a process of obtaining a carbon thin plate by heat-treating a thin plate-shaped formed body among steps of manufacturing a carbon thin plate such as a separator plate or a porous carbon plate used as a constituent member of a fuel cell.

燃料電池を構成する部材として炭素薄板が使用される。ガス不透過性のセパレータ板やガス流路付き基材としての多孔質カーボン板などである。これらの炭素薄板は、木材、紙、セルロース繊維、熱硬化性樹脂などの有機物や黒鉛粉末、炭素繊維などのカーボン材料を原料として成形された薄板状成形体を加熱して、炭化する、あるいは黒鉛化することにより製造される。特許文献１には、薄板状成形体をアルゴンガス中などの無酸素雰囲気下、１０００℃ほどの温度で加熱して炭化することにより、炭素薄板が得られることが記載されている。また、この得られた炭素薄板をさらに高温の２０００℃以上に加熱し、黒鉛化することにより、炭素薄板は電気伝導性、熱伝導性、耐食性などがより優れたものとなる。ここで、薄板状成形体は、たとえば特許文献２に示されている方法により、炭素繊維、パルプ、熱硬化性樹脂を含む混合物を原料として、抄紙したものを成形して得ることができる。   A carbon thin plate is used as a member constituting the fuel cell. Examples thereof include a gas-impermeable separator plate and a porous carbon plate as a substrate with a gas flow path. These carbon thin plates are carbonized by heating a thin plate-like molded body formed from a carbon material such as wood, paper, cellulose fiber, thermosetting resin, or other organic matter, graphite powder, or carbon fiber, or graphite. Is manufactured. Patent Document 1 describes that a carbon thin plate can be obtained by heating and carbonizing a thin plate-shaped molded body at a temperature of about 1000 ° C. in an oxygen-free atmosphere such as argon gas. Further, by heating the obtained carbon thin plate to a higher temperature of 2000 ° C. or more and graphitizing, the carbon thin plate becomes more excellent in electrical conductivity, thermal conductivity, corrosion resistance and the like. Here, the thin plate-like molded body can be obtained by molding a paper-made material using, as a raw material, a mixture containing carbon fiber, pulp, and thermosetting resin, for example, by the method disclosed in Patent Document 2.

薄板状成形体を炭化する、あるいは黒鉛化する加熱処理方法として、特許文献３には、３０枚積層した薄板状成形体を均熱板（黒鉛板、厚さ３０ｍｍ）で挟んでから、パッキング材（黒鉛粒子、コークス粉末）の充填層に埋め込んだ状態で、加熱する方法が記載されている。ここで、薄板状成形体は５枚積層ごとに均熱部材（厚さ６ｍｍの黒鉛板）が挿入されて、３０枚が積層されている。特許文献３の実施例では、厚さの異なる黒鉛板（厚さ３０ｍｍと６ｍｍ）が使用されているが、薄板状成形体の数枚から数十枚積層ごとに、厚さが１０ｍｍほどの黒鉛板を挿入することもできる。
薄板状成形体を熱伝導性が良い黒鉛板で挟んで加熱処理するのは、加熱昇温時に、薄板状成形体の面内温度分布を均一化し、炭化あるいは黒鉛化により得られる炭素薄板のそり、割れなどの不具合の発生を防止することを目的とする。このように、加熱処理により得られる炭素薄板のそり、割れなどの不具合の発生を防止するため、積層した薄板状成形体に組み合わせて均熱板や均熱部材が使用されるが、均熱板や均熱部材の使用には、次のような問題点がある。 As a heat treatment method for carbonizing or graphitizing a thin plate-shaped molded body, Patent Document 3 discloses that a 30-layer laminated thin plate-shaped molded body is sandwiched between soaking plates (graphite plate, thickness 30 mm), and then a packing material. A method of heating in a state of being embedded in a packed bed of (graphite particles, coke powder) is described. Here, in the thin plate-like molded body, a soaking member (graphite plate having a thickness of 6 mm) is inserted every five sheets, and 30 sheets are laminated. In the example of Patent Document 3, graphite plates having different thicknesses (thickness of 30 mm and 6 mm) are used. However, graphite having a thickness of about 10 mm is laminated every several to several tens of thin plate-like molded bodies. A board can also be inserted.
The thin plate-shaped compact is heat-treated by sandwiching it with a graphite plate with good thermal conductivity, and the in-plane temperature distribution of the thin-plate-shaped compact is made uniform during heating and the carbon thin plate obtained by carbonization or graphitization is warped. The purpose is to prevent the occurrence of defects such as cracks. Thus, in order to prevent the occurrence of problems such as warping and cracking of the carbon thin plate obtained by the heat treatment, a soaking plate or a soaking member is used in combination with the laminated thin plate-shaped molded body. In addition, the use of a soaking member has the following problems.

厚さ１０ｍｍほどの均熱板を、薄板状成形体の数枚から数十枚積層ごとに挿入する場合、挿入した均熱板の厚さは無視できないものとなる。たとえば、薄板状成形体（厚さ２ｍｍ）を１００枚積層するとき（その総厚さは２００ｍｍ、積層全体を挟持する上下の黒鉛板の厚さは除く。）、薄板状成形体の１０枚積層ごとに、均熱板（厚さ１０ｍｍ）を挿入するとすれば、挿入する均熱板９枚の厚さは合計９０ｍｍとなり、薄板状成形体の総厚さ（２００ｍｍ）の約１／２に相当する。９０ｍｍは薄板状成形体（厚さ２ｍｍ）の４５枚分に相当し、挿入する均熱板が不要であれば、さらに薄板状成形体４５枚の加熱処理が可能となる。
このように、挿入する均熱板の総厚さが厚いものとなるため、限られたスペース（内容積）の加熱炉や加熱容器を用いて製作する炭素薄板の数量は限定されることとなる。 When a soaking plate having a thickness of about 10 mm is inserted every several to several tens of thin plate-like molded bodies, the thickness of the inserted soaking plate cannot be ignored. For example, when laminating 100 sheets (thickness: 2 mm) (total thickness is 200 mm, excluding the thickness of the upper and lower graphite plates sandwiching the entire lamination), 10 sheets of sheet-like shaped bodies are laminated. If a soaking plate (thickness 10 mm) is inserted every time, the thickness of the nine soaking plates to be inserted is 90 mm in total, which is equivalent to about 1/2 of the total thickness (200 mm) of the thin plate-like molded body. To do. 90 mm corresponds to 45 sheets of a thin plate-shaped body (thickness 2 mm), and if a soaking plate to be inserted is not required, 45 sheets of the thin plate-shaped body can be further heat-treated.
Thus, since the total thickness of the soaking plate to be inserted becomes thick, the number of carbon thin plates to be manufactured using a heating furnace or heating container with a limited space (internal volume) will be limited. .

以上のように、均熱板や均熱部材の使用は、炭素薄板のそり、割れなどの不具合の発生を防止するために有効であるが、一回の加熱処理で製作できる炭素薄板の数量が制限されるため、炭素薄板の量産には適さない問題点がある。そこで、本発明は、炭素薄板のそり、割れの発生を防止するとともに、一回の加熱処理で製作できる炭素薄板の数量を増して、量産を可能とする技術を提供することを課題とする。
特開昭６０−１５５５１６号公報 特開２００９−４１３６号公報 特開昭６２−１４３８０７号公報 As described above, the use of soaking plates and soaking members is effective in preventing the occurrence of defects such as warping and cracking of the carbon thin plate, but the number of carbon thin plates that can be produced by a single heat treatment is small. Due to limitations, there is a problem that is not suitable for mass production of carbon thin plates. Accordingly, an object of the present invention is to provide a technology that enables mass production by preventing the occurrence of warping and cracking of the carbon thin plate and increasing the number of carbon thin plates that can be manufactured by a single heat treatment.
JP 60-155516 A JP 2009-4136 A Japanese Patent Laid-Open No. 62-143807

上記課題は、薄板状成形体の両面または片面上に、黒鉛粉を含む被膜を形成したのち、薄板状成形体を加熱処理すること、あるいは黒鉛粉を含むシートを、薄板状成形体の間に挿入して積層した薄板状成形体を加熱処理することにより解決される。
請求項１に記載の発明は、積層した薄板状成形体を加熱処理する薄板状成形体の加熱処理方法において、前記薄板状成形体の両面または片面上に、黒鉛粉を含む被膜を形成したのち、前記薄板状成形体を積層し、加熱処理することを特徴とする薄板状成形体の加熱処理方法に係るものである。請求項１に記載の発明によれば、薄板状成形体の両面または片面上に、黒鉛粉を含む被膜が形成される。熱伝導性が良好な黒鉛粉を含む被膜が薄板状成形体の表面に形成されているため、加熱昇温時に、薄板状成形体の面内温度分布は容易に均一となり、そり、割れの発生が防止されることとなる。 The above-mentioned problem is that after a film containing graphite powder is formed on both surfaces or one side of the thin plate-shaped molded body, the thin plate-shaped molded body is heat-treated, or a sheet containing graphite powder is placed between the thin plate-shaped molded bodies. The problem is solved by heat-treating the thin plate-like molded body inserted and laminated.
The invention according to claim 1 is a heat treatment method for a thin plate-shaped molded body in which a laminated thin plate-shaped molded body is heat-treated, and after a film containing graphite powder is formed on both surfaces or one surface of the thin plate-shaped molded body. The present invention relates to a method for heat-treating a thin plate-shaped product, wherein the thin plate-shaped product is laminated and heat-treated. According to invention of Claim 1, the film containing graphite powder is formed on both surfaces or one side of a thin plate-shaped molded object. Since the coating containing graphite powder with good thermal conductivity is formed on the surface of the thin plate-shaped molded product, the in-plane temperature distribution of the thin plate-shaped molded product becomes easily uniform during heating and heating, and warpage and cracking occur. Will be prevented.

熱伝導性の良好な黒鉛粉として、結晶性の高い黒鉛粉が望ましく、天然黒鉛では鱗状黒鉛、ＳｉＣ（炭化ケイ素）の製造時に得られる分解黒鉛、製鋼工程で熔鋼中に溶解していた炭素が析出して得られるキッシュ黒鉛、黒鉛化度の高い人造黒鉛など、結晶面間隔（ｄ００２）が３．４Å以下の黒鉛の粉末が適する。また、黒鉛粉を酸処理後、１０００℃程度にて膨張させた膨張黒鉛粉や、炭素繊維のうち黒鉛構造が発達した黒鉛短繊維も用いることができる。
黒鉛粉の粒度は、１００μｍを超えると、被膜の形成やシート化が困難となるため、１００μｍ以下が望ましい。ただし、多孔質カーボン板など多孔質の炭素薄板を製造する場合には、その表面の細孔が黒鉛粉により目詰まりを生じるほど黒鉛粉が微粒子でないことを要する。黒鉛粉を含む被膜は、黒鉛粉と粘度を混合し、混練したものを、薄板状成形体の表面に塗布することにより形成できる。また、黒鉛粉を薄板状成形体の表面に擦り付けることによっても被膜を形成することができる。 Graphite powder with high crystallinity is desirable as graphite powder with good thermal conductivity. For natural graphite, scaly graphite, cracked graphite obtained during the manufacture of SiC (silicon carbide), carbon dissolved in molten steel in the steelmaking process A graphite powder having a crystal plane spacing (d002) of 3.4 mm or less is suitable, such as quiche graphite obtained by precipitation of graphite and artificial graphite having a high degree of graphitization. Moreover, the expanded graphite powder which expanded graphite powder at about 1000 degreeC after acid treatment, and the graphite short fiber in which the graphite structure was developed among carbon fibers can also be used.
If the particle size of the graphite powder exceeds 100 μm, it becomes difficult to form a film or form a sheet. However, when producing a porous carbon thin plate such as a porous carbon plate, it is necessary that the graphite powder is not fine enough that the pores on the surface are clogged by the graphite powder. The film containing graphite powder can be formed by mixing and kneading graphite powder and viscosity on the surface of a thin plate-shaped molded body. The film can also be formed by rubbing the graphite powder against the surface of the thin plate-shaped molded body.

薄板状成形体（厚さ２ｍｍ）を１００枚積層して、加熱処理する場合、薄板状成形体の片面に、黒鉛粉を含む被膜（厚さ０．２ｍｍ）を形成するときは、黒鉛粉を含む被膜の総厚さは２０ｍｍとなる。２０ｍｍは、薄板状成形体の総厚さ（２００ｍｍ）の１／１０であり、薄板状成形体１０枚分に相当するにすぎない。黒鉛粉を含む被膜（厚さ０．２ｍｍ）を形成することにより、上述した均熱板（厚さ１０ｍｍ）９枚を挿入する場合（総厚さ９０ｍｍ、薄板状成形体４５枚分）より、薄板状成形体を３５枚多く加熱処理できることとなる。
請求項２に記載の発明は、前記黒鉛粉を含む被膜が、黒鉛粉、バインダーを含む塗布液を前記薄板状成形体の表面に塗布して形成したものであることを特徴とする請求項１に記載の薄板状成形体の加熱処理方法に係るものである。請求項２に記載の発明によれば、薄板状成形体の表面には、黒鉛粉、バインダーを含む塗布液が塗布されることにより被膜が形成される。熱伝導性が良好な黒鉛粉を含む被膜が薄板状成形体の表面に形成されているため、加熱昇温時に、薄板状成形体の面内温度分布は容易に均一となる。 When laminating 100 sheets of thin plate-shaped bodies (thickness 2 mm) and heat-treating them, when forming a film containing graphite powder (thickness 0.2 mm) on one side of the thin plate-shaped molded body, The total thickness of the coating film is 20 mm. 20 mm is 1/10 of the total thickness (200 mm) of the thin plate-shaped molded body, and only corresponds to 10 thin plate-shaped molded bodies. By forming a film containing graphite powder (thickness 0.2 mm), when inserting the above-mentioned nine soaking plates (thickness 10 mm) (total thickness 90 mm, thin plate-like molded body 45 pieces), It is possible to heat-treat a large number of thin plate-shaped molded bodies.
The invention according to claim 2 is characterized in that the coating film containing graphite powder is formed by applying a coating liquid containing graphite powder and a binder to the surface of the thin plate-like molded body. This relates to the heat treatment method for a thin plate-like molded product described in 1. According to the second aspect of the present invention, a coating film is formed on the surface of the thin plate-shaped body by applying a coating liquid containing graphite powder and a binder. Since the coating containing graphite powder having good thermal conductivity is formed on the surface of the thin plate-shaped molded body, the in-plane temperature distribution of the thin plate-shaped molded body easily becomes uniform when the temperature is raised by heating.

黒鉛粉を含む被膜は、薄板状成形体の両面または片面に形成することができる。塗布液は、黒鉛粉とバインダーを混合し、有機溶剤、水などの希釈液を用いて粘度を調整し作製する。バインダーとして、炭化率が高い樹脂であるフェノール樹脂、ポリアクリロニトリル樹脂、塩化ビニール樹脂などを用いることができる。他に、炭化率の低い樹脂であるポリエチレン樹脂、ポリスチレン樹脂、ポリビニルアルコール樹脂（ＰＶＡ）、エポキシ樹脂、ウレタン樹脂のほかセルロースも使用できる。バインダーの配合量（ｗｔ％）は、黒鉛粉の重量（ａ）、バインダーの重量（ｂ）の合計（ａ＋ｂ）に対し、３０ｗｔ％以下であることが望ましい。バインダーの配合量が多い場合、黒鉛粉を含む被膜の熱伝導性が低下し、また被膜が接着層となって、隣接する薄板状成形体が接着し、分離が困難となることがあることによる。   The coating film containing graphite powder can be formed on both surfaces or one surface of the thin plate-shaped molded body. The coating solution is prepared by mixing graphite powder and a binder and adjusting the viscosity using a diluent such as an organic solvent or water. As the binder, a phenol resin, a polyacrylonitrile resin, a vinyl chloride resin, or the like, which is a resin having a high carbonization rate, can be used. In addition, a polyethylene resin, a polystyrene resin, a polyvinyl alcohol resin (PVA), an epoxy resin, and a urethane resin, which are resins having a low carbonization rate, can also be used. The blending amount (wt%) of the binder is desirably 30 wt% or less with respect to the total (a + b) of the weight (a) of the graphite powder and the weight (b) of the binder. When the amount of the binder is large, the thermal conductivity of the coating containing graphite powder is lowered, and the coating becomes an adhesive layer, and the adjacent thin plate-shaped molded product may adhere and may be difficult to separate. .

後述する実施例の記載で述べるように、黒鉛粉とバインダーを混合した塗布液を薄板状成形体の表面に塗布して、黒鉛粉を含む被膜を形成する実験を行った。薄板状成形体（厚さ２ｍｍ）１００枚の各片面に黒鉛粉を含む被膜（厚さ０．２ｍｍ）を形成して積層し、加熱処理した場合、全数良好であった。黒鉛粉を含む被膜の総厚さ２０ｍｍは、積層した薄板状成形体の総厚さ（２００ｍｍ）の１／１０にすぎない。
請求項３に記載の発明は、積層した薄板状成形体を加熱処理する薄板状成形体の加熱処理方法において、黒鉛粉を含むシートを、前記薄板状成形体の間に挿入して、前記薄板状成形体を加熱処理することを特徴する薄板状成形体の加熱処理方法に係るものである。請求項３に記載の発明によれば、黒鉛粉を含むシートが、薄板状成形体の間に挿入されて、薄板状成形体が積層され、加熱処理される。熱伝導性が良好な黒鉛粉を含むシートが薄板状成形体の間に挿入されているため、加熱昇温時に、薄板状成形体の面内温度分布は容易に均一となる。 As will be described in the description of examples described later, an experiment was performed in which a coating liquid containing graphite powder and a binder was applied to the surface of a thin plate-shaped body to form a film containing graphite powder. When 100 sheets of thin plate-shaped compacts (thickness 2 mm) were coated with a film (graph thickness 0.2 mm) containing graphite powder on each side, the total number was good. The total thickness of 20 mm of the film containing graphite powder is only 1/10 of the total thickness (200 mm) of the laminated thin plate-like molded bodies.
According to a third aspect of the present invention, in the heat treatment method for a thin plate-shaped formed body, in which the laminated thin plate-shaped formed body is heat-treated, a sheet containing graphite powder is inserted between the thin plate-shaped formed bodies, and the thin plate The present invention relates to a heat treatment method for a thin plate-shaped molded body, characterized by heat-treating the shaped molded body. According to invention of Claim 3, the sheet | seat containing graphite powder is inserted between thin plate-shaped molded objects, a thin plate-shaped molded object is laminated | stacked, and it heat-processes. Since the sheet containing the graphite powder having good thermal conductivity is inserted between the thin plate-like molded bodies, the in-plane temperature distribution of the thin plate-like molded body is easily uniform at the time of heating and heating.

請求項４に記載の発明は、積層した前記薄板状成形体を、積層方向０．００３ＭＰａ以上で加圧して、加熱処理することを特徴とする請求項１ないし請求項３に記載の薄板状成形体の加熱処理方法に係るものである。請求項４に記載の発明によれば、積層された薄板状成形体は、積層方向０．００３ＭＰａ以上で加圧され、加熱処理される。積層された薄板状成形体の最上層に、黒鉛のブロック材などを載せて、積層方向０．００３ＭＰａ以上で加圧することにより、薄板状成形体のそりの発生が防止される。請求項１ないし請求項３に記載の発明と併せて実施することで、薄板状成形体を加熱処理して得られる炭素薄板のそりの発生を防止する効果が増すこととなる。
請求項５に記載の発明は、前記加熱処理が、前記薄板状成形体を炭化すること、または黒鉛化することであることを特徴とする請求項１ないし請求項４に記載の薄板状成形体の加熱処理方法に係るものである。請求項５に記載の発明によれば、加熱処理により、薄板状成形体を炭化する工程、または黒鉛化する工程において、薄板状成形体の両面または片面上に、黒鉛粉を含む被膜が形成される。薄板状成形体の表面に、黒鉛粉、バインダーを含む塗布液が塗布されることにより被膜が形成されてもよい。あるいは、黒鉛粉を含むシートが、薄板状成形体の間に挿入されて、薄板状成形体が積層されてもよい。熱伝導性が良好な黒鉛粉を含む被膜が薄板状成形体の表面に形成されている、または黒鉛粉を含むシートが、薄板状成形体の間に挿入されているため、加熱昇温時に、薄板状成形体の面内温度分布は容易に均一となる。さらに薄板状成形体を炭化する工程、または黒鉛化する工程において、積層した前記薄板状成形体を、積層方向０．００３ＭＰａ以上で加圧することにより、薄板状成形体を加熱処理して得られる炭素薄板のそりの発生を防止する効果が増すこととなる。 The invention according to claim 4 is characterized in that the laminated sheet-like molded body is subjected to heat treatment by pressurizing in a lamination direction of 0.003 MPa or more. This relates to a body heat treatment method. According to invention of Claim 4, the laminated | stacked thin plate-shaped molded object is pressurized by the lamination direction 0.003 Mpa or more, and is heat-processed. By placing a graphite block material or the like on the uppermost layer of the laminated sheet-like molded bodies and pressurizing them in the lamination direction of 0.003 MPa or more, the occurrence of warping of the sheet-like molded bodies is prevented. By carrying out the present invention together with the inventions according to claims 1 to 3, the effect of preventing warpage of the carbon thin plate obtained by heat-treating the thin plate-like molded body is increased.
The invention according to claim 5 is characterized in that the heat treatment is carbonization or graphitization of the thin plate-shaped molded body. This relates to the heat treatment method. According to the invention described in claim 5, in the step of carbonizing the thin plate-shaped body or the step of graphitizing by heat treatment, a film containing graphite powder is formed on both surfaces or one surface of the thin plate-shaped body. The A coating film may be formed by applying a coating liquid containing graphite powder and a binder to the surface of the thin plate-shaped molded body. Or the sheet | seat containing graphite powder may be inserted between thin plate-shaped molded objects, and a thin plate-shaped molded object may be laminated | stacked. Since a film containing graphite powder having good thermal conductivity is formed on the surface of the thin plate-shaped molded body, or a sheet containing graphite powder is inserted between the thin plate-shaped molded bodies, The in-plane temperature distribution of the thin plate-like molded body is easily uniform. Furthermore, carbon obtained by heat-treating the thin plate-shaped molded body by pressurizing the laminated thin plate-shaped molded body in a laminating direction of 0.003 MPa or more in the step of carbonizing the thin plate-shaped molded body or the step of graphitizing. The effect of preventing the occurrence of warping of the thin plate will increase.

以上の請求項１ないし請求項５に記載の発明によれば、薄板状成形体の加熱処理方法において、薄板状成形体の両面または片面上に、黒鉛粉を含む被膜が形成される。または、薄板状成形体の表面に、黒鉛粉、バインダーを含む塗布液が塗布されることにより被膜が形成される。あるいは黒鉛粉を含むシートが、薄板状成形体の間に挿入されて、薄板状成形体が積層される。熱伝導性が良好な黒鉛粉を含む被膜が薄板状成形体の表面に形成されている、または黒鉛粉を含むシートが、薄板状成形体の間に挿入されているため、加熱昇温時に、薄板状成形体の面内温度分布は容易に均一となる。このため、薄板状成形体を加熱処理して得られる炭素薄板にそり、割れなどの不具合が発生することを防止できる効果が得られる。さらに、積層した前記薄板状成形体を積層方向０．００３ＭＰａ以上で加圧することにより、炭素薄板のそりの発生を防止する効果が増すこととなる。   According to the first to fifth aspects of the present invention, in the heat treatment method for a thin plate-shaped body, a film containing graphite powder is formed on both surfaces or one surface of the thin plate-shaped body. Or a coating film is formed by apply | coating the coating liquid containing graphite powder and a binder to the surface of a thin plate-shaped molded object. Or the sheet | seat containing graphite powder is inserted between thin plate-shaped molded objects, and a thin plate-shaped molded object is laminated | stacked. Since a film containing graphite powder having good thermal conductivity is formed on the surface of the thin plate-shaped molded body, or a sheet containing graphite powder is inserted between the thin plate-shaped molded bodies, The in-plane temperature distribution of the thin plate-like molded body is easily uniform. For this reason, the effect which can prevent that troubles, such as a curvature and a crack, generate | occur | produce in a carbon thin plate obtained by heat-processing a thin plate-shaped molded object is acquired. Furthermore, the effect of preventing warpage of the carbon thin plate is increased by pressurizing the laminated sheet-like formed body at a lamination direction of 0.003 MPa or more.

後述する実施例の記載で述べるように、黒鉛粉とバインダーを混合した塗布液を薄板状成形体の表面に塗布して、黒鉛粉を含む被膜を形成する実験を行った。薄板状成形体（厚さ２ｍｍ）１００枚の各片面に黒鉛粉を含む被膜（厚さ０．２ｍｍ）を形成して積層し、加熱処理した場合、そり、割れなどの不具合はなく、全数良好であった。黒鉛粉を含む被膜の総厚さ２０ｍｍは、薄板状成形体の総厚さ（２００ｍｍ）の１／１０にすぎず、一回の加熱処理で製作できる炭素薄板の数量を増すことができ、量産を可能とするものである。
以上のように、一回の加熱処理で製作できる炭素薄板の数量が制限され、炭素薄板の量産には適さないという従来技術が有する問題点を、本発明は解消するものである。 As will be described in the description of examples described later, an experiment was performed in which a coating liquid containing graphite powder and a binder was applied to the surface of a thin plate-shaped body to form a film containing graphite powder. When a thin sheet-like molded body (thickness 2 mm) is coated with a film containing graphite powder (thickness 0.2 mm) on each side of 100 sheets, heat treatment is performed, and there are no problems such as warping and cracking, and the number is all good Met. The total thickness of the coating film containing graphite powder is only 1/10 of the total thickness (200 mm) of the thin plate-like molded body, and the number of carbon thin plates that can be manufactured by one heat treatment can be increased, so that mass production is possible. Is possible.
As described above, the present invention solves the problems of the prior art that the number of carbon thin plates that can be manufactured by a single heat treatment is limited and is not suitable for mass production of carbon thin plates.

本発明の実施例として、薄板状成形体の表面に黒鉛粉を含む被膜を形成した実施例１について述べる。   As an example of the present invention, Example 1 in which a film containing graphite powder is formed on the surface of a thin plate-like molded body will be described.

１）薄板状成形体の製作
炭素繊維（ドナック社製ドナカーボ・Ｓチョップ）２０ｗｔ％、パルプ（針葉樹晒クラフトパルプ）２５ｗｔ％、フェノール樹脂（旭有機材製ＳＰ２６０）５５ｗｔ％を混合して得られたスラリーを原料とし、抄紙機により抄紙して、薄板状成形体（厚さ２ｍｍ、５００ｍｍ角）を製作した。さらに、この薄板状成形体にフェノール樹脂を含浸したのち、１２０℃で乾燥した。
２）黒鉛を含む被膜の形成
黒鉛粉として、人造黒鉛粉（日本黒鉛工業製ＰＡＧ、粒度５０μｍ、結晶面間隔（ｄ００２）３．３５Å）と鱗状黒鉛粉（日本黒鉛工業製ＣＰ、粒度１０μｍ、結晶面間隔（ｄ００２）３．３５Å）を用いた。バインダーとして、フェノール樹脂（昭和高分子製ＢＲＬ―１２０Ｚ）、ポリビニルアルコール樹脂（ＰＶＡ、クラレ製ポバール）を用いた。 1) Manufacture of a thin plate-like molded body Obtained by mixing 20 wt% of carbon fiber (Donac Donakabo S-chop), 25 wt% of pulp (coniferous bleached kraft pulp), and 55 wt% of phenol resin (Asahi Organic Products SP260). Slurry was used as a raw material, and paper was made with a paper machine to produce a thin plate-shaped body (thickness 2 mm, 500 mm square). Furthermore, this thin plate-like molded body was impregnated with a phenol resin and then dried at 120 ° C.
2) Formation of a film containing graphite As graphite powder, artificial graphite powder (PAG manufactured by Nippon Graphite Industry, particle size 50 μm, crystal plane spacing (d002) 3.35 mm) and scaly graphite powder (CP manufactured by Nippon Graphite Industry, particle size 10 μm, crystal) A surface interval (d002) of 3.35 mm) was used. As the binder, a phenol resin (BRL-120Z manufactured by Showa Polymer Co., Ltd.) and a polyvinyl alcohol resin (PVA, manufactured by Kuraray Co., Ltd.) were used.

黒鉛粉とバインダーを８５：１５の重量比で混合したのち、エタノールまたは水で希釈して塗布液とした。薄板状成形体の片面または両面に、塗布液を塗布したのち、１５０℃で１時間乾燥して、黒鉛粉を含む被膜を形成した。塗布前後の薄板状成形体の厚さをマイクロメーターで測定し、被膜の厚さを求めた。
以上の被膜の形成とは別に、黒鉛粉を含むシートとして、黒鉛シート（東洋炭素製パーマフォイル、厚さ０．４ｍｍ、黒鉛の結晶面間隔（ｄ００２）３．３５Å）を用いた。
３）加熱処理
片面または両面に黒鉛粉を含む被膜を形成した薄板状成形体（１００枚）を黒鉛製の加熱容器内に積み重ねた（(表１)
の試料Ｎｏ．１〜２５）。また、薄板状成形体（黒鉛粉を含む被膜なし）の間に、黒鉛シートを挿入して、１００枚を積み重ねた（(表１)
の試料Ｎｏ．２６〜２８）。積層した薄板状成形体（１００枚、黒鉛粉を含む被膜なし）の２箇所のみに、黒鉛板（厚さ１０ｍｍ）を挿入したものを、従来技術による比較例とした（(表１)
の比較例１〜３）。 Graphite powder and binder were mixed at a weight ratio of 85:15, and then diluted with ethanol or water to obtain a coating solution. A coating solution was applied to one side or both sides of the thin plate-like molded body, and then dried at 150 ° C. for 1 hour to form a film containing graphite powder. The thickness of the thin plate-shaped molded body before and after coating was measured with a micrometer to determine the thickness of the coating.
Apart from the formation of the above-mentioned film, a graphite sheet (Peryofoil made by Toyo Tanso Co., Ltd., thickness 0.4 mm, crystal plane spacing (d002) 3.35 mm) was used as a sheet containing graphite powder.
3) Heat treatment Thin plate-like molded bodies (100 sheets) having a film containing graphite powder formed on one side or both sides were stacked in a graphite heating vessel ((Table 1)
Sample No. 1-25). In addition, 100 sheets were stacked by inserting a graphite sheet between thin plate-shaped molded bodies (without a film containing graphite powder) ((Table 1)
Sample No. 26-28). A comparative example according to the prior art was obtained by inserting a graphite plate (thickness 10 mm) into only two places of the laminated sheet-like molded bodies (100 sheets, no coating containing graphite powder) ((Table 1)
Comparative Examples 1 to 3).

以上の積層した薄板状成形体の上下両端に、黒鉛板（厚さ１０ｍｍ）を置いて、薄板状成形体を挟持した。さらに、積層した薄板状成形体の一部について、最上層の黒鉛板の上に黒鉛ブロックを載せて、積層方向に加圧した（０．００１ＭＰａ、０．００３ＭＰａ）。加熱容器内の空間部分に、パッキング材（詰め粉コークス）を充填したのち、アチソン炉を用いて加熱容器を加熱した。加熱温度を１５００℃、２６００℃とし、加熱時間を２０時間とした。
加熱処理により得られた炭素薄板について、波打ちの有無、そりの状態を検査した。(表１)
は検査結果を示すもので、良否判定として、１００枚全数に波打ちがなく、そりが８ｍｍ以内のものを○、波打ちがあるもの、または、そりが８ｍｍを超えるものは×とした。 A graphite plate (thickness 10 mm) was placed on the upper and lower ends of the laminated thin plate-shaped molded body, and the thin plate-shaped molded body was sandwiched. Further, a part of the laminated sheet-shaped molded body was placed on the uppermost graphite plate and pressed in the stacking direction (0.001 MPa, 0.003 MPa). After filling the space in the heating container with a packing material (stuffed coke), the heating container was heated using an Atchison furnace. The heating temperature was 1500 ° C., 2600 ° C., and the heating time was 20 hours.
The carbon thin plate obtained by the heat treatment was inspected for the presence of waviness and the state of warpage. (Table 1)
Indicates the inspection result, and as a pass / fail judgment, all 100 sheets had no undulations, and those with a warpage within 8 mm were marked with ◯, those with undulations, or those with a warpage exceeding 8 mm were marked with ×.

黒鉛粉が人造黒鉛粉（日本黒鉛工業製ＰＡＧ）である場合（試料Ｎｏ．１〜１５）、黒鉛粉を含む被膜の厚さが０．１ｍｍのもの（試料Ｎｏ．１、４、１１、１４）に、全数波打ちが生じた。被膜の厚さが０．２ｍｍ、０．４ｍｍのものは、全数に波打ちがなく、そりも少なかった。なお、以上の結果は、バインダーのフェノール樹脂とポリビニルアルコール樹脂（ＰＶＡ）について同様であった。
被膜の厚さが０．２ｍｍの場合、片面のみの被膜形成であっても、全数良好であり、片面に０．２ｍｍ厚さの被膜を形成すれば、加熱された薄板状成形体の温度分布の均一化に効果があることが示された。一方、被膜の厚さが０．１ｍｍでは、両面の被膜形成であっても、全数波打ちが生じた。被膜の厚さが０．１ｍｍの場合、薄板状成形体の温度分布を均一化するほど、薄板状成形体表面の熱伝導性がないことが示された。 When the graphite powder is artificial graphite powder (Nippon Graphite Industries PAG) (Sample Nos. 1 to 15), the thickness of the film containing the graphite powder is 0.1 mm (Sample Nos. 1, 4, 11, and 14). ) Was completely waved. When the thickness of the coating was 0.2 mm or 0.4 mm, the total number was not wavy and the warpage was small. In addition, the above result was the same about the phenol resin and polyvinyl alcohol resin (PVA) of a binder.
When the thickness of the coating is 0.2 mm, even if the coating is formed on only one side, the total number is good. If a coating having a thickness of 0.2 mm is formed on one side, the temperature distribution of the heated thin plate-like molded body It has been shown that there is an effect on homogenization of. On the other hand, when the thickness of the coating film was 0.1 mm, even when the coating film was formed on both sides, the entire wave was generated. When the thickness of the coating was 0.1 mm, it was shown that the thermal conductivity of the surface of the thin plate-shaped molded body was not so great that the temperature distribution of the thin plate-shaped molded body was made uniform.

黒鉛粉が鱗状黒鉛粉（日本黒鉛工業製ＣＰ）である場合（試料Ｎｏ．１６〜２５）につても、上述の人造黒鉛粉と同様、黒鉛粉を含む被膜の厚さが０．１ｍｍのもの（試料Ｎｏ．１６、１９）に、全数波打ちが生じた。被膜の厚さが０．２ｍｍ、０．４ｍｍのものは、全数に波打ちがなく、そりも少なかった。
以上の結果において、そりは、加圧力が０．００３ＭＰａの場合（試料Ｎｏ．７、１０、２２、２５）、減少し（１ｍｍ、１ｍｍ以下）、積層方向の加圧により、そりの発生を防止する効果が増す結果が得られた。
黒鉛シートを薄板状成形体の間に挿入した場合（試料Ｎｏ．２６〜２８）、すべてが全数良好であった。
積層した薄板状成形体の２箇所に黒鉛板（厚さ１０ｍｍ）を挿入した場合（比較例１〜３）、波打ちを生じた。０．００３ＭＰａの加圧をした場合でも（比較例２、３）、半数に波打ちを生じ、上述の黒鉛粉を含む被膜を形成した場合に明らかであった加圧による効果はみられなかった。 Even when the graphite powder is scaly graphite powder (CP made by Nippon Graphite Industry) (sample Nos. 16 to 25), the thickness of the coating film containing the graphite powder is 0.1 mm as in the case of the artificial graphite powder described above. (Sample Nos. 16 and 19) were entirely waved. When the thickness of the coating was 0.2 mm or 0.4 mm, the total number was not wavy and the warpage was small.
In the above results, warpage is reduced when the applied pressure is 0.003 MPa (sample No. 7, 10, 22, 25) (1 mm, 1 mm or less), and warpage is prevented by pressurization in the stacking direction. The result of increasing the effect was obtained.
When the graphite sheet was inserted between the thin plate-like molded bodies (Sample Nos. 26 to 28), all the samples were good.
When a graphite plate (thickness 10 mm) was inserted into two places of the laminated thin plate-like molded bodies (Comparative Examples 1 to 3), undulation was generated. Even when a pressure of 0.003 MPa was applied (Comparative Examples 2 and 3), half of the undulations occurred, and the effect of the pressurization that was apparent when the coating film containing the graphite powder was formed was not observed.

挿入した黒鉛板２枚の厚さは２０ｍｍであり、黒鉛粉を含む被膜（厚さ０．２ｍｍ）を薄板状成形体１００枚の片面に形成した場合の被膜の総厚さ（２０ｍｍ）と同じである。同じ２０ｍｍであるが、黒鉛粉を含む被膜の場合は全数良好であるのに対し、黒鉛板挿入の場合は波打ちを生じる結果であった。黒鉛粉を含む被膜を形成する本発明の技術は、炭素薄板の波打ち、そりなどの発生を防止する効果において、従来技術より優れる。
以上の実施例１では、加熱処理温度を１５００℃、２６００℃としたが、本発明は他の温度での加熱処理についても実施できる。たとえば、薄板状成形体の加熱処理として、８００〜１２００℃での炭化処理、１２００〜３０００℃での黒鉛化処理について、本発明を実施することができる。

Figure 2010228934
The thickness of the two inserted graphite plates is 20 mm, and is the same as the total thickness (20 mm) of the coating when a coating containing graphite powder (thickness 0.2 mm) is formed on one surface of 100 sheets of the thin plate-like molded body. It is. In the case of a coating containing graphite powder, the total number was 20 mm, but in the case of inserting a graphite plate, it was a result of waviness. The technique of the present invention for forming a film containing graphite powder is superior to the prior art in the effect of preventing the occurrence of waviness and warpage of the carbon thin plate.
In the above Example 1, the heat treatment temperature is set to 1500 ° C. and 2600 ° C., but the present invention can also be applied to heat treatment at other temperatures. For example, the present invention can be carried out with respect to a carbonization treatment at 800 to 1200 ° C. and a graphitization treatment at 1200 to 3000 ° C. as the heat treatment of the thin plate-shaped molded body.
Figure 2010228934

Claims (5)

積層した薄板状成形体を加熱処理する薄板状成形体の加熱処理方法において、前記薄板状成形体の両面上または片面上に、黒鉛粉を含む被膜を形成したのち、前記薄板状成形体を積層し、加熱処理することを特徴とする薄板状成形体の加熱処理方法。   In the heat treatment method for a thin plate-shaped molded body, in which the laminated thin-plate molded body is heat-treated, a film containing graphite powder is formed on both surfaces or one surface of the thin plate-shaped molded body, and then the thin plate-shaped molded body is laminated. And a heat treatment method for the thin plate-shaped molded body. 前記黒鉛粉を含む被膜が、前記黒鉛粉、バインダーを含む塗布液を前記薄板状成形体の表面に塗布して形成したものであることを特徴とする請求項１に記載の薄板状成形体の加熱処理方法。   2. The thin plate-shaped molded body according to claim 1, wherein the film containing the graphite powder is formed by applying a coating liquid containing the graphite powder and a binder to the surface of the thin plate-shaped molded body. Heat treatment method. 積層した薄板状成形体を加熱処理する薄板状成形体の加熱処理方法において、黒鉛粉を含むシートを、前記薄板状成形体の間に挿入して、前記薄板状成形体を加熱処理することを特徴する薄板状成形体の加熱処理方法。   In the heat treatment method for a thin plate-shaped molded body in which the laminated thin-plate molded body is heat-treated, a sheet containing graphite powder is inserted between the thin plate-shaped molded bodies, and the thin plate-shaped molded body is heat-treated. A heat treatment method for a thin sheet-shaped molded article. 積層した前記薄板状成形体を、積層方向０．００３ＭＰａ以上で加圧して、加熱処理することを特徴とする請求項１ないし請求項３に記載の薄板状成形体の加熱処理方法。   The heat treatment method for a thin plate-shaped body according to any one of claims 1 to 3, wherein the laminated thin plate-shaped body is subjected to a heat treatment by pressurizing in a lamination direction of 0.003 MPa or more. 前記加熱処理が、前記薄板状成形体を炭化すること、または黒鉛化することであることを特徴とする請求項１ないし請求項４に記載の薄板状成形体の加熱処理方法。   The heat treatment method for a thin plate-shaped body according to any one of claims 1 to 4, wherein the heat treatment is carbonization or graphitization of the thin plate-shaped body.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015180598A (en) * 2015-06-17 2015-10-15 イビデン株式会社 Method for producing graphite material, and graphite material
JP2020087826A (en) * 2018-11-29 2020-06-04 アイシン化工株式会社 Gas diffusion layer substrate and manufacturing method thereof

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* Cited by examiner, † Cited by third party
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JPH0211322A (en) * 1988-06-30 1990-01-16 Nippon Carbon Co Ltd Sheetlike carbon composite material and its manufacture
JPH03197309A (en) * 1989-12-25 1991-08-28 Kawasaki Steel Corp Baking method for sheet resin form
JPH0517116A (en) * 1991-07-10 1993-01-26 Matsushita Electric Ind Co Ltd Production of graphite

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH0211322A (en) * 1988-06-30 1990-01-16 Nippon Carbon Co Ltd Sheetlike carbon composite material and its manufacture
JPH03197309A (en) * 1989-12-25 1991-08-28 Kawasaki Steel Corp Baking method for sheet resin form
JPH0517116A (en) * 1991-07-10 1993-01-26 Matsushita Electric Ind Co Ltd Production of graphite

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2015180598A (en) * 2015-06-17 2015-10-15 イビデン株式会社 Method for producing graphite material, and graphite material
JP2020087826A (en) * 2018-11-29 2020-06-04 アイシン化工株式会社 Gas diffusion layer substrate and manufacturing method thereof

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