JP4565155B2 - Clay composition for porous metal or porous ceramics, and method for producing porous metal or porous ceramics using the same - Google Patents
Clay composition for porous metal or porous ceramics, and method for producing porous metal or porous ceramics using the same Download PDFInfo
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- JP4565155B2 JP4565155B2 JP2005132405A JP2005132405A JP4565155B2 JP 4565155 B2 JP4565155 B2 JP 4565155B2 JP 2005132405 A JP2005132405 A JP 2005132405A JP 2005132405 A JP2005132405 A JP 2005132405A JP 4565155 B2 JP4565155 B2 JP 4565155B2
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- 239000004927 clay Substances 0.000 title claims description 85
- 229910052751 metal Inorganic materials 0.000 title claims description 60
- 239000002184 metal Substances 0.000 title claims description 60
- 239000000203 mixture Substances 0.000 title claims description 60
- 239000000919 ceramic Substances 0.000 title claims description 34
- 238000004519 manufacturing process Methods 0.000 title claims description 27
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- 239000011148 porous material Substances 0.000 claims description 65
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- 239000011230 binding agent Substances 0.000 claims description 22
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
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- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Powder Metallurgy (AREA)
Description
本発明は、多孔質金属又は多孔質セラミックス用粘土組成物、それを用いた多孔質金属又は多孔質セラミックスの製造方法に関するものである。 The present invention relates to a clay composition for porous metal or porous ceramics, and a method for producing porous metal or porous ceramics using the same.
所要形状の金属製品の製造法として、粘土状の素材を所要形状に成型した後、それを乾燥するか、あるいは脱脂後焼結する方法が知られているが（特許文献１ないし３参照）、この方法は得られる金属製品を高密度とするのを課題とするものであって、多孔質とするものではない。
また、多孔質体としては、気孔率を変化させる製法も知られているが（特許文献４ないし７参照）、これらの方法では気孔率を任意に調整・設計して変化させるのは困難である。
また、方向性のある気孔をもつ多孔質材料の製造方法も提案されてはいるが（特許文献８、９参照）、この方法も多孔質材料に高い気孔率をもたせるのは技術的に難しく、また気孔径の制御も困難である。
As a method for producing a metal product of a required shape, a method is known in which a clay-like material is molded into a required shape and then dried or degreased and sintered (see Patent Documents 1 to 3). This method is intended to increase the density of the resulting metal product, and is not porous.
In addition, as a porous body, manufacturing methods for changing the porosity are known (see Patent Documents 4 to 7), but it is difficult to arbitrarily adjust and design the porosity by these methods. .
In addition, although a method for producing a porous material having directional pores has been proposed (see Patent Documents 8 and 9), it is technically difficult for this method to give the porous material a high porosity, It is also difficult to control the pore diameter.
本発明の課題は、このような事情の下、多孔質金属又は多孔質セラミックス用粘土組成物やそれを用いて容易に多孔質材料、中でも気孔径や気孔率に分布、例えば傾斜性分布等をもたせ、また、気孔に方向性をもたせた多孔質材料を製造する方法を提供することにある。 Under such circumstances, the object of the present invention is to provide a clay composition for a porous metal or a porous ceramics or a porous material, and easily distribute a porous material, particularly a pore diameter and a porosity, such as a gradient distribution. It is another object of the present invention to provide a method for producing a porous material in which pores are oriented.
本発明者は、多孔質金属や多孔質セラミックスを製造するのに適した粘土組成物を開発すべく鋭意研究を重ねた結果、所定気孔形成材を用い、これと所定無機粉と所定バインダーを含むスラリーにゲル化剤を加えることが、課題解決に資することを見出し、この知見に基づいて本発明をなすに至った。 As a result of intensive studies to develop a clay composition suitable for producing porous metals and porous ceramics, the present inventor has used a predetermined pore forming material and includes a predetermined inorganic powder and a predetermined binder. It has been found that adding a gelling agent to the slurry contributes to solving the problem, and the present invention has been made based on this finding.
すなわち、本発明は、以下のとおりのものである。
（１）ポリビニルアルコールを主成分として含む粘性のある水溶性高分子からなるバインダーの水溶液と、金属粉又はセラミックス粉と、粒径５〜５０００μｍの発泡樹脂、中空樹脂及び中実樹脂の中から選ばれた少なくとも１種の樹脂からなる気孔形成材とを含んでなるスラリーに、ゲル化剤を加えて粘土状の粘土組成物とする際に、気孔形成材の含有割合を異にする２種以上の粘土組成物とし、それら２種以上の粘土組成物を組み合わせて成形し、乾燥したのち、焼成するとともに気孔形成材を焼失させることを特徴とする多孔質材料の製造方法。
（２）組み合わせて成形するのを、２種以上の粘土組成物を、気孔形成材の含有割合が積層方向に傾斜分布を呈するように積層することによって行い、厚さ方向に気孔率が傾斜分布を呈する多孔質材料を製造する前記（１）記載の製造方法。
（３）（Ａ）ポリビニルアルコールを主成分として含む粘性のある水溶性高分子からなるバインダーの水溶液と、金属粉又はセラミックス粉と、粒径５〜５０００μｍの発泡樹脂、中空樹脂及び中実樹脂の中から選ばれた少なくとも１種の樹脂からなる気孔形成材とを含んでなるスラリーに、ゲル化剤を加えて粘土状としてなる粘土組成物と、（Ｂ）ポリビニルアルコールを主成分として含む粘性のある水溶性高分子からなるバインダーの水溶液と混合させた金属粉又はセラミックス粉を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物及び（Ｃ）ポリビニルアルコールを主成分として含む粘性のある水溶性高分子からなるバインダーの水溶液と混合させた気孔形成材を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物の一方又は両方とを組み合わせて成形し、乾燥したのち、焼成するとともに気孔形成材を焼失させることを特徴とする多孔質材料の製造方法。
（４）（Ｃ）ポリビニルアルコールを主成分として含む粘性のある水溶性高分子からなるバインダーの水溶液と混合させた気孔形成材を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物を棒状に成形して第一の芯材とし、これを包むように（Ｂ）ポリビニルアルコールを主成分として含む粘性のある水溶性高分子からなるバインダーの水溶液と混合させた金属粉又はセラミックス粉を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物を包着したものを引き伸ばし、これを数等分し、これらをまとめて棒状に成形して第二の芯材とし、これを包むように粘土組成物（Ｂ）を包着したものを引き伸ばす操作を繰り返すことにより、引き伸ばし方向に繊維状の気孔形成材が列設された多孔質体前駆体を作成し、該前駆体を乾燥し、これを包むように粘土組成物（Ｂ）を包着したのち、乾燥し、さらにこれを包むように（Ａ）ポリビニルアルコールを主成分として含む粘性のある水溶性高分子からなるバインダーの水溶液と、金属粉又はセラミックス粉と、粒径５〜５０００μｍの発泡樹脂、中空樹脂及び中実樹脂の中から選ばれた少なくとも１種の樹脂からなる気孔形成材とを含んでなるスラリーに、ゲル化剤を加えて粘土状としてなる粘土組成物を包着したのち、乾燥し、焼成するとともに気孔形成材を焼失させることを特徴とする多孔質材料の製造方法。
（５）気孔形成材が発泡ポリスチレンからなる前記（１）ないし（４）のいずれかに記載の多孔質材料の製造方法。
（６）ゲル化剤が含ホウ素化合物、コンゴーレッド、又は、フェノールである前記（１）ないし（５）のいずれかに記載の多孔質材料の製造方法。
（７）含ホウ素化合物が硼砂又は硼酸である前記（６）記載の多孔質材料の製造方法。
（８）スラリーがさらに界面活性剤を含むものである前記（１）ないし（７）のいずれかに記載の多孔質材料の製造方法。
（９）金属粉が、貴金属、貴金属合金、銅、ニッケル、チタン、モリブデン、タングステン、アルミニウム系合金、銅系合金、チタン系合金、モリブデン系合金、タングステン系合金、ニッケル系合金、鉄系合金、コバルト系合金、磁性合金、超硬合金、耐食合金、耐熱合金、導電用合金、超電導合金、摺動用合金、軸受用合金、防振合金、水素貯蔵用合金、形状記憶合金、電極用合金、金属間化合物、ステンレス鋼、炭素鋼、合金鋼、磁石鋼、工具鋼及び高速度鋼の中から選ばれた少なくとも１種である前記（１）ないし（８）のいずれかに記載の多孔質材料の製造方法。
（１０）セラミックス粉が、シリカ、シリカ‐アルミナ、シリカ‐マグネシア、シリカ‐チタニア、シリカ‐ジルコニア、アルミナ、アルミナ‐マグネシア、アルミナ‐チタニア、アルミナ‐ボリア、アルミナ‐ジルコニア、アルミナ‐ホスファ、チタニア、ジルコニア、ボリア、ケイ石、ケイ砂、カオリン、ベントナイト、マグネサイト、ドロマイト、長石、陶石、ゼオライト、シリコンカーバイド、ＰＺＴ及び磁性セラミックスの中から選ばれた少なくとも１種である前記（１）ないし（８）のいずれかに記載の多孔質材料の製造方法。
That is, the present invention is as follows.
(1) An aqueous solution of a binder composed of a viscous water-soluble polymer containing polyvinyl alcohol as a main component, a metal powder or a ceramic powder, a foamed resin having a particle size of 5 to 5000 μm, a hollow resin, and a solid resin. Two or more kinds having different content ratios of the pore-forming material when adding a gelling agent to the slurry comprising the pore-forming material composed of at least one kind of resin to obtain a clay-like clay composition the clay composition, and molding a combination of these two or more clay compositions, after drying, a manufacturing method of a porous material, characterized in that burning off the pore-forming material with firing.
(2) Molding in combination is performed by laminating two or more clay compositions so that the content ratio of the pore-forming material exhibits a gradient distribution in the lamination direction, and the porosity has a gradient distribution in the thickness direction. The manufacturing method of said (1) description which manufactures the porous material which exhibits this.
(3) (A) An aqueous solution of a binder comprising a viscous water-soluble polymer containing polyvinyl alcohol as a main component, a metal powder or a ceramic powder, a foamed resin having a particle size of 5 to 5000 μm, a hollow resin, and a solid resin. A clay composition which is made into a clay by adding a gelling agent to a slurry comprising a pore-forming material comprising at least one resin selected from the above; and (B) a viscous composition containing polyvinyl alcohol as a main component . A clay composition obtained by adding a gelling agent to a slurry containing a metal powder or a ceramic powder mixed with an aqueous solution of a binder made of a water-soluble polymer, and a viscosity containing (C) polyvinyl alcohol as a main component. A gelling agent is added to a slurry containing a pore-forming material mixed with an aqueous binder solution composed of a water-soluble polymer to form a clay. Comprising one or a combination of the both molding clay composition, after drying, a manufacturing method of a porous material, characterized in that burning off the pore-forming material with firing.
(4) (C) Clay composition obtained by adding a gelling agent to a slurry containing a pore-forming material mixed with an aqueous solution of a binder made of a viscous water-soluble polymer containing polyvinyl alcohol as a main component to form a clay. A metal powder or ceramic powder mixed with an aqueous solution of a binder made of a viscous water-soluble polymer containing polyvinyl alcohol as a main component so as to wrap the product into a rod shape to be a first core material. A slurry obtained by adding a gelling agent and encapsulating a clay composition in a clay form is stretched, divided into several equal parts, and these are collectively formed into a rod shape to form a second core material. A porous body precursor in which fibrous pore-forming materials are arranged in the stretching direction is prepared by repeating the operation of stretching the clay composition (B) wrapped so as to wrap The precursor is dried, after Tsutsumigi clay composition (B) so as to wrap it, dried, comprising a water-soluble polymer with a viscous comprising as further main components (A) polyvinyl alcohol so as to wrap them A slurry comprising an aqueous solution of a binder, metal powder or ceramic powder, and a pore forming material comprising at least one resin selected from a foamed resin having a particle size of 5 to 5000 μm, a hollow resin and a solid resin. A method for producing a porous material, comprising: encapsulating a clay composition that is made into a clay by adding a gelling agent ; drying and firing; and burning the pore-forming material.
(5) The method for producing a porous material according to any one of (1) to (4), wherein the pore forming material is made of expanded polystyrene.
(6) The method for producing a porous material according to any one of (1) to (5), wherein the gelling agent is a boron-containing compound, Congo red, or phenol.
(7) The method for producing a porous material according to (6), wherein the boron-containing compound is borax or boric acid.
(8) The method for producing a porous material according to any one of (1) to (7), wherein the slurry further contains a surfactant.
(9) Metal powder is noble metal, noble metal alloy, copper, nickel, titanium, molybdenum, tungsten, aluminum alloy, copper alloy, titanium alloy, molybdenum alloy, tungsten alloy, nickel alloy, iron alloy, Cobalt alloys, magnetic alloys, cemented carbides, corrosion resistant alloys, heat resistant alloys, conductive alloys, superconducting alloys, sliding alloys, bearing alloys, anti-vibration alloys, hydrogen storage alloys, shape memory alloys, electrode alloys, metals The porous material according to any one of (1) to (8), which is at least one selected from an intermetallic compound, stainless steel, carbon steel, alloy steel, magnet steel, tool steel, and high-speed steel Production method.
(10) Ceramic powder is silica, silica-alumina, silica-magnesia, silica-titania, silica-zirconia, alumina, alumina-magnesia, alumina-titania, alumina-boria, alumina-zirconia, alumina-phospha, titania, zirconia (1) to (8) which is at least one selected from boria, quartzite, quartz sand, kaolin, bentonite, magnesite, dolomite, feldspar, porcelain stone, zeolite, silicon carbide, PZT and magnetic ceramics. The method for producing a porous material according to any one of the above.
本発明の粘土組成物は、粘性のある水溶性高分子からなるバインダーの水溶液、金属粉又はセラミックス粉（以下、金属・セラミックス粉ともいう）及び気孔形成材を含んでなるスラリー（以下、粉体等含有スラリーともいう）に、ゲル化剤を加えて粘土状としてなるものである。 The clay composition of the present invention comprises a binder aqueous solution composed of a viscous water-soluble polymer, a metal powder or ceramic powder (hereinafter also referred to as metal / ceramic powder) and a slurry comprising a pore-forming material (hereinafter referred to as powder). It is also referred to as an equal-containing slurry) and a gelling agent is added to form a clay.
この金属粉としては、水と接触させても急激に酸化することのないものが好ましく、このようなものの金属種としては、例えば金、銀、白金、パラジウム等の貴金属やその合金、銅、ニッケル、チタン、モリブデン、タングステン、アルミニウム系合金、銅系合金、チタン系合金、モリブデン系合金、タングステン系合金、ニッケル系合金、鉄系合金、コバルト系合金、磁性合金（例えばＳｍ−Ｃｏ系磁性体、Ｎｄ−Ｆｅ−Ｂ系磁性体等）、超硬合金、耐食合金、耐熱合金、導電用合金、超電導合金、摺動用合金、軸受用合金、防振合金、水素貯蔵用合金、形状記憶合金、電極用合金、金属間化合物、ステンレス鋼、炭素鋼、合金鋼、磁石鋼、工具鋼、高速度鋼等が挙げられる。これらは１種用いてもよいし、また、２種以上を組み合わせて用いてもよい。
また、セラミックス粉としては、例えばシリカ、シリカ‐アルミナ、シリカ‐マグネシア、シリカ‐チタニア、シリカ‐ジルコニア、アルミナ、アルミナ‐マグネシア、アルミナ‐チタニア、アルミナ‐ボリア、アルミナ‐ジルコニア、アルミナ‐ホスファ、チタニア、ジルコニア、ボリア、ケイ石、ケイ砂、カオリン、ベントナイト、マグネサイト、ドロマイト、長石、陶石、ゼオライト、シリコンカーバイド、ＰＺＴ、磁性セラミックス等が挙げられる。これらは１種用いてもよいし、また、２種以上を組み合わせて用いてもよい。
金属粉やセラミックス粉の粒径については特に制限されないが、通常１００μｍ以下、好ましくは２０〜０．１μｍの範囲で、目標とする気孔径、気孔率等を考慮しつつ選ばれる。
This metal powder is preferably one that does not oxidize rapidly even when brought into contact with water. Examples of such metal species include noble metals such as gold, silver, platinum, and palladium, and alloys thereof, copper, nickel. , Titanium, molybdenum, tungsten, aluminum alloy, copper alloy, titanium alloy, molybdenum alloy, tungsten alloy, nickel alloy, iron alloy, cobalt alloy, magnetic alloy (for example, Sm-Co magnet, Nd-Fe-B magnetic materials), cemented carbide, corrosion resistant alloy, heat resistant alloy, conductive alloy, superconducting alloy, sliding alloy, bearing alloy, anti-vibration alloy, hydrogen storage alloy, shape memory alloy, electrode Alloy, intermetallic compound, stainless steel, carbon steel, alloy steel, magnet steel, tool steel, high speed steel and the like. These may be used alone or in combination of two or more.
Examples of the ceramic powder include silica, silica-alumina, silica-magnesia, silica-titania, silica-zirconia, alumina, alumina-magnesia, alumina-titania, alumina-boria, alumina-zirconia, alumina-phospha, titania, Examples include zirconia, boria, quartzite, quartz sand, kaolin, bentonite, magnesite, dolomite, feldspar, porcelain stone, zeolite, silicon carbide, PZT, and magnetic ceramics. These may be used alone or in combination of two or more.
The particle size of the metal powder or ceramic powder is not particularly limited, but is usually 100 μm or less, preferably in the range of 20 to 0.1 μm, taking into account the target pore diameter, porosity and the like.
上記バインダーは、水溶液とすると粘性を示す水溶性高分子であればよく、このようなものとしては、例えばポリビニルアルコール、メチルセルロース、エチルセルロース等のアルキルセルロース、ポリエチレングリコール、ポリビニールピロリドン、その他、天然増粘材としてのキサンタンガム、アガロース、マンノース、アルギン酸ナトリウム、デキストラン、グアガム、カラギーナン、ペクチン、ジュランガムなどが取り扱いが容易であり、これらの水溶性高分子は１種用いてもよいし、また、２種以上を組み合わせて用いてもよい。中でもポリビニールアルコールが目的粘土組成物に容易に薄く、あるいは細く引き延ばせるなど優れた成形加工性をもたらし、例えば粘土組成物をそのまま圧延・乾燥・焼成することによって、例えば厚さ０．１〜０．５ｍｍ、気孔率８０〜９５％のシート状の多孔質体等を容易に製造するのを可能にするので、本発明では、ポリビニルアルコールを主成分として含む粘性のある水溶性高分子を用いる。 The binder may be a water-soluble polymer that exhibits viscosity when used as an aqueous solution. Examples of such a binder include alkyl celluloses such as polyvinyl alcohol, methyl cellulose, and ethyl cellulose, polyethylene glycol, polyvinyl pyrrolidone, and other natural thickening agents. Xanthan gum, agarose, mannose, sodium alginate, dextran, guar gum, carrageenan, pectin, duran gum and the like as materials are easy to handle, and these water-soluble polymers may be used alone or in combination of two or more. You may use it in combination. Among them, polyvinyl alcohol brings excellent molding processability such as being easily thinned or thinly stretched to the target clay composition. For example, by rolling, drying and firing the clay composition as it is, for example, a thickness of 0.1 to 0 The sheet-like porous body having a thickness of 0.5 mm and a porosity of 80 to 95% can be easily produced. In the present invention, a viscous water-soluble polymer containing polyvinyl alcohol as a main component is used.
上記気孔形成材は、粒径５〜５０００μｍ、好ましくは２０〜１０００μｍの発泡樹脂、中空樹脂及び中実樹脂の中から選ばれた少なくとも１種の樹脂からなるものであって、樹脂の材質については加熱あるいはその他の手法による分解が可能であれば限定されないが、好ましくは発泡ポリスチレンが用いられる。気孔形成材は、それを含まない粘土をそのまま乾燥させると収縮してしまうのに対し、目的粘土組成物について乾燥による収縮を起こさせないようにするのに有用である。 The pore forming material is composed of at least one resin selected from a foamed resin, a hollow resin and a solid resin having a particle size of 5 to 5000 μm, preferably 20 to 1000 μm. Although it will not be limited if decomposition | disassembly by a heating or another method is possible, Preferably a polystyrene foam is used. The pore-forming material is useful for preventing shrinkage due to drying of the target clay composition, whereas the pore-forming material shrinks when the clay containing it is dried as it is.
粉体等含有スラリーにおいて、金属・セラミックス粉の含有割合は体積基準で５〜７０％、好ましくは１０〜６０％の範囲で、また気孔形成材の含有割合は金属・セラミックス粉と水溶性高分子水溶液の合計体積に対し、嵩体積基準で５〜４０００％、好ましくは１０〜２０００％の範囲で選ばれ、水溶性高分子水溶液は水溶性高分子濃度が該水溶液に対して０．５〜３０質量％、好ましくは１〜１５質量％の範囲になるように調整されたものがよい。
さらに、気孔形成材は望む気孔率に応じて上記含有割合を変動させるが、高気孔率の場合には粉体等含有スラリーに対し５〜２０倍のタップ体積となるようにすることも可能である。また、高気孔率の気孔形成には気孔形成材の形状を真球形、あるいはそれに近い形状とすることが望ましい。
In the slurry containing powder and the like, the content ratio of the metal / ceramic powder is 5 to 70%, preferably 10 to 60% by volume, and the content ratio of the pore forming material is the metal / ceramic powder and the water-soluble polymer. It is selected in the range of 5 to 4000%, preferably 10 to 2000%, based on the bulk volume with respect to the total volume of the aqueous solution. The water-soluble polymer aqueous solution has a water-soluble polymer concentration of 0.5 to 30 with respect to the aqueous solution. What was adjusted so that it might become the range of 1 mass%, preferably 1-15 mass% is good.
Furthermore, the pore forming material varies the content ratio according to the desired porosity, but in the case of a high porosity, the tap volume may be 5 to 20 times that of the slurry containing powder or the like. is there. For the formation of pores with a high porosity, the shape of the pore-forming material is preferably a true sphere or a shape close thereto.
また、粉体等含有スラリーには、必要に応じ、適宜任意成分添加することもできる。
このような添加成分としては、例えば界面活性剤、成形性向上材、可塑剤、溶媒などが挙げられる。
界面活性剤は粉体等含有スラリーにおいてその表面張力を低下させたり、気孔形成材のなじみを向上させたりするのに有用であり、好ましくはアルキル硫酸エステル塩、アルキルエーテル硫酸エステル塩、α−オレフィンスルホン酸塩、アルカンスルホン酸塩、アルキルベンゼンスルホン酸塩などのアニオン界面活性剤や、ポリオキシエチルアルキルエーテル等のポリエチレングリコール誘導体、多価アルコール誘導体などのノニオン界面活性剤、市販の汎用中性洗剤が挙げられる。
界面活性剤の添加量は気孔形成材やその粉体等含有スラリーに対する含有割合等に応じて適宜調節される。
また、成形性向上材は、目的粘土組成物について成形性、中でも延性を向上させるのに有用であり、好ましくはでんぷん、多糖類等が挙げられ、さらにでんぷん類としては、小麦粉、コーンスターチ、馬鈴薯でんぷんなどが入手容易で取り扱いやすいので有利である。
また、可塑剤としては、金属粉又はセラミックス粉の分散効果を高めるもの、好ましくはグリセリン、エチレングリコールが挙げられる。
また、溶媒としては、乾燥性を高めるもの、好ましくはエタノールのようなアルコール類が挙げられる。
Moreover, arbitrary components can also be suitably added to slurry containing powder etc. as needed.
Examples of such additive components include surfactants, moldability improvers, plasticizers, solvents, and the like.
The surfactant is useful for reducing the surface tension of the slurry containing powder or the like, or improving the familiarity of the pore-forming material, preferably alkyl sulfate ester salt, alkyl ether sulfate ester salt, α-olefin. Anionic surfactants such as sulfonates, alkane sulfonates, and alkylbenzene sulfonates, nonionic surfactants such as polyethylene glycol derivatives such as polyoxyethyl alkyl ether, polyhydric alcohol derivatives, and commercially available general-purpose neutral detergents Can be mentioned.
The addition amount of the surfactant is appropriately adjusted according to the content ratio of the pore-forming material and its powder-containing slurry.
Further, the moldability improving material is useful for improving the moldability, particularly ductility, of the target clay composition, preferably starch, polysaccharides, etc., and starches include flour, corn starch, potato starch Are easy to obtain and easy to handle.
Examples of the plasticizer include those that enhance the dispersion effect of metal powder or ceramic powder, preferably glycerin and ethylene glycol.
Moreover, as a solvent, what improves drying property, Preferably alcohols like ethanol are mentioned.
本発明において用いられるゲル化剤は、前記諸成分を混合して調製されるスラリーに混合することにより、これを粘土状とするものであればよく、例えば水溶性高分子がポリビニルアルコールの場合、このようなものとしては、含ホウ素化合物、コンゴーレッド、フェノールなどが挙げられ、中でも硼砂、硼酸等の含ホウ素化合物が好ましい。 The gelling agent used in the present invention is not particularly limited as long as it is made into a clay by mixing with the slurry prepared by mixing the various components. For example, when the water-soluble polymer is polyvinyl alcohol, Examples of such compounds include boron-containing compounds, Congo red, and phenol. Among them, boron-containing compounds such as borax and boric acid are preferable.
前記した本発明の粘土組成物を用いて多孔質材料を製造することができる。
その簡単な方法としては、前記粘土組成物を成形し、乾燥したのち、焼成するとともに気孔形成材を焼失させる方法が挙げられる。
また、この方法において、成形を、本発明の粘土組成物として気孔形成材の含有割合を異にする２種以上のものを用い、これを組み合わせて行うこと、例えば２種以上の粘土組成物を、気孔形成材の含有割合が積層方向に傾斜分布を呈するように積層することなども可能である。
また、（Ａ）本発明の粘土組成物と、（Ｂ）粘性のある水溶性高分子からなるバインダーの水溶液と混合させた金属粉又はセラミックス粉を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物及び（Ｃ）粘性のある水溶性高分子からなるバインダーの水溶液と混合させた気孔形成材を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物の一方又は両方とを組み合わせて成形し、乾燥したのち、焼成するとともに気孔形成材を焼失させる方法も挙げられる。
このような方法により、任意に気孔率の分布を変化させた材料の成形も可能となり、特に、気孔形成材の含有量を変えた粘土組成物を層状に積み上げ圧延することによって、例えば０．５〜２ｍｍの厚さの間で気孔率を８０〜９５％と変化させた多孔質体の製造も可能である。
さらには、（Ｃ）粘性のある水溶性高分子からなるバインダーの水溶液と混合させた気孔形成材を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物を棒状に成形して第一の芯材とし、これを包むように（Ｂ）粘性のある水溶性高分子からなるバインダーの水溶液と混合させた金属粉又はセラミックス粉を含んでなるスラリーにゲル化剤を加えて粘土状としてなる粘土組成物を包着したものを引き伸ばし、これを数等分し、これらをまとめて棒状に成形して第二の芯材とし、これを包むように粘土組成物（Ｂ）を包着したものを引き伸ばす操作を繰り返すことにより、引き伸ばし方向に繊維状の気孔形成材が列設された多孔質体前駆体を作成し、該前駆体を乾燥し、これを包むように粘土組成物（Ｂ）を包着したのち、乾燥し、さらにこれを包むように（Ａ）本発明の粘土組成物を包着したのち、乾燥し、焼成するとともに気孔形成材を焼失させる方法も挙げられる。
このような方法により、気孔形成材を含まない金属粘土に金属を含まない粘土の芯をとおし、引き延ばしながら畳み込む操作を何度も繰り返すことによって、材料の縦方向に繊維状に通気孔が通る構造の多孔質材料の製造も可能である。この場合、乾燥時の収縮を避けるため、成形した素材を一旦凍結し凍結乾燥法により乾燥することもできる。
さらにまた、このような方法を組み合わせて繊維状に走った多孔質構造や、気孔率の高い構造を組み合わせ複雑な気孔構造を持つ多孔質体を製造することも可能である。
A porous material can be produced using the above-described clay composition of the present invention.
As a simple method thereof, there is a method in which the clay composition is molded and dried, and then fired and the pore forming material is burned off.
Further, in this method, the molding is carried out by using two or more types having different pore-forming material content ratios as the clay composition of the present invention, and combining them, for example, two or more types of clay compositions. It is also possible to laminate the pore forming material so that the content ratio of the pore forming material exhibits a gradient distribution in the lamination direction.
Also, a clay is obtained by adding a gelling agent to a slurry comprising (A) the clay composition of the present invention and (B) a metal powder or ceramic powder mixed with an aqueous solution of a binder comprising a viscous water-soluble polymer. One of the clay composition formed into a clay form by adding a gelling agent to a slurry comprising a pore-forming material mixed with an aqueous solution of a binder composed of a viscous water-soluble polymer and (C) a viscous water composition Alternatively, a method may be mentioned in which both are molded, dried and then fired and the pore-forming material is burned off.
By such a method, it is possible to mold a material with arbitrarily changed porosity distribution, and in particular, by laminating and rolling a clay composition having a changed content of the pore forming material in layers, for example, 0.5 It is also possible to produce a porous body having a porosity of 80 to 95% with a thickness of ˜2 mm.
Further, (C) a clay composition obtained by adding a gelling agent to a slurry containing a pore-forming material mixed with an aqueous solution of a binder made of a viscous water-soluble polymer to form a clay is formed into a rod shape. As a first core material, a gelling agent is added to a slurry containing metal powder or ceramic powder mixed with an aqueous solution of a binder made of a viscous water-soluble polymer so as to wrap it as a clay. A clay composition (B) encased in a clay composition (B) is stretched, divided into several equal parts, and these are collectively formed into a rod shape to form a second core material. The porous body precursor in which fibrous pore forming materials are arranged in the stretching direction is prepared by repeating the operation of stretching the clay, the precursor is dried, and the clay composition (B) is wrapped so as to wrap it. Dry after wearing , After further has Tsutsumigi clay composition as (A) the present invention wrap it, dried, how to burn the pore-forming material can be cited as well as sintering.
By such a method, through a metal clay not containing pore-forming material through a clay core containing no metal, and by repeatedly repeating the operation of stretching, a structure in which ventilation holes pass in the form of fibers in the longitudinal direction of the material It is also possible to produce a porous material. In this case, in order to avoid shrinkage at the time of drying, the formed material can be once frozen and dried by a freeze-drying method.
Furthermore, it is also possible to manufacture a porous body having a complicated pore structure by combining a porous structure running in a fibrous form by combining such methods and a structure having a high porosity.
本発明の多孔質金属又は多孔質セラミックス用粘土組成物は、容易に引き伸ばしたり、圧延したり、薄くしたりするなど成形加工性に優れている。
本発明方法によれば、気孔率、気孔径、気孔の方向等の制御された多孔質金属又は多孔質セラミックスを製造することができ、例えば超硬合金のような難加工性材料から貴金属等までの広範な金属やセラミックスを含む幅広い材料の微細なセル構造をもつ高気孔率の多孔質体等を例えばバルク素材等として製造することが可能となる。
本発明方法により得られる多孔質材料の応用範囲は極めて広く、種々の技術分野、例えば、航空宇宙材料、スポーツ用品素材等の軽量かつ高比強度が要求される分野、断熱特性、耐熱性、吸振性の要求される分野、緩衝材料、梱包材料などの衝撃エネルギーの吸収が要求される分野、軽量化の要求される分野、フィルター材料、触媒担体材料、電極材料など広い表面積が要求される分野、生体適合性の要求される分野における素材として利用することが可能である。
本発明方法は、特に安価に供給される鉄系素材やセラミックスについてその多孔質化を実現した効果が大きく、様々の分野における多孔質材料を供するのに資するものである。
The clay composition for porous metal or porous ceramics of the present invention is excellent in moldability such as being easily stretched, rolled, or thinned.
According to the method of the present invention, it is possible to produce a porous metal or porous ceramic with controlled porosity, pore diameter, pore direction, etc., for example, from difficult-to-work materials such as cemented carbide to precious metals, etc. It is possible to manufacture a porous material having a high porosity having a fine cell structure of a wide range of materials including a wide range of metals and ceramics, for example, as a bulk material.
The application range of the porous material obtained by the method of the present invention is very wide, and various technical fields such as aerospace materials and sports equipment materials that require lightweight and high specific strength, heat insulation properties, heat resistance, vibration absorption, etc. Fields that require safety, fields that require absorption of impact energy such as buffer materials and packaging materials, fields that require weight reduction, fields that require a large surface area such as filter materials, catalyst carrier materials, and electrode materials, It can be used as a material in a field requiring biocompatibility.
The method of the present invention is particularly effective in realizing the porosity of iron-based materials and ceramics supplied at low cost, and contributes to providing porous materials in various fields.
次に、実施例により本発明を実施するための最良の形態を説明する。 Next, the best mode for carrying out the present invention will be described by way of examples.
＜多孔質板＞
金属粉として、平均粒径３μｍのＳＵＳ３１６Ｌステンレス鋼粉（アトミックス社製、ＰＦ−３）（以下、ステンレス鋼粉ＰＦという）を、また、高分子水溶液として、平均分子量１１５０００、ポリビニルアルコールの６質量％水溶液（日本合成化学工業社製、ゴーセノール）（以下、６％ＰＶＡ液という）を、また、ゲル化剤として硼砂の８質量％水溶液（以下、８％硼砂液という）を、また、気孔形成材として、平均粒径０．１ｍｍの発泡スチロール球（積水化成品工業社製、膨張率２０倍）をそれぞれ用いた。
６％ＰＶＡ液８０容量％（２５ｍｌ）とステンレス鋼粉ＰＦ２０容量％（５０ｇ）を混合してスラリーを調製し、このスラリーに対し、それぞれ４、６、８及び１２ｇと用量を種々変えて気孔形成用樹脂材を混入し、それぞれにさらに８％硼砂液５ｍｌを加えてゲル化させ粘土状として各金属粘土組成物（それぞれ金属粘土組成物Ａ、金属粘土組成物Ｂ、金属粘土組成物Ｃ、金属粘土組成物Ｄという）を得た。
これらの各金属粘土組成物を０．５ｍｍ厚の薄板状にローラーで圧延成型し６０℃で２時間乾燥したのち、真空雰囲気下１０５０℃で１時間焼成したところ、厚さ０．４ｍｍの軽量の各種多孔質金属板が得られた。これらの多孔質金属板の各気孔率は、気孔形成用樹脂材の混入量の増える順に、８１％、８６％、８８％、９３％と増大した。
このような金属板は、電極、フィルター、触媒担体、軽量構造物外装用など広範囲の用途に利用しうる。
<Porous plate>
As a metal powder, SUS316L stainless steel powder (PF-3, manufactured by Atomix Co., Ltd., hereinafter referred to as stainless steel powder PF) having an average particle diameter of 3 μm, and as an aqueous polymer solution, an average molecular weight of 115000 and 6 masses of polyvinyl alcohol. % Aqueous solution (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., Gohsenol) (hereinafter referred to as 6% PVA solution), 8% by weight aqueous solution of borax (hereinafter referred to as 8% borax solution) as a gelling agent, and pore formation As materials, polystyrene foam balls having an average particle diameter of 0.1 mm (manufactured by Sekisui Plastics Co., Ltd., expansion rate 20 times) were used.
A slurry was prepared by mixing 80% by volume (25ml) of 6% PVA liquid and 20% by volume (50g) of stainless steel powder PF, and pores were formed by varying the doses to 4, 6, 8 and 12g, respectively. Each resin clay composition (metal clay composition A, metal clay composition B, metal clay composition C, metal Clay composition D) was obtained.
Each of these metal clay compositions was rolled and formed into a 0.5 mm thick sheet with a roller, dried at 60 ° C. for 2 hours, and then baked at 1050 ° C. for 1 hour in a vacuum atmosphere. Various porous metal plates were obtained. The porosity of these porous metal plates increased to 81%, 86%, 88%, and 93% in order of increasing amount of the pore forming resin material.
Such a metal plate can be used for a wide range of applications such as electrodes, filters, catalyst carriers, and exteriors for lightweight structures.
＜傾斜構造多孔質板＞
実施例１と同様にして得られた金属粘土組成物Ａ、金属粘土組成物Ｃ及び金属粘土組成物Ｄを使用し、厚さ方向に気孔率が変化する多孔質板を以下のようにして作製した。
すなわち、これらの各金属粘土組成物を０．５ｍｍ厚の薄板状にローラーで圧延成型し、重ねあわせ、６０℃で２時間乾燥したのち、真空雰囲気下１０５０℃で１時間焼成したところ、気孔率が厚さ方向へ徐々に変化する厚さ１．２ｍｍの多孔質金属板が得られた。気孔率は高気孔率部分で９３％、低気孔率部分で８０％であった。
このような金属板は、気化装置、燃焼装置等の気化部材用などの用途に利用しうる。
<Inclined porous plate>
Using the metal clay composition A, the metal clay composition C, and the metal clay composition D obtained in the same manner as in Example 1, a porous plate whose porosity varies in the thickness direction is prepared as follows. did.
That is, each of these metal clay compositions was rolled into a 0.5 mm thick sheet with a roller, overlapped, dried at 60 ° C. for 2 hours, and then fired at 1050 ° C. for 1 hour in a vacuum atmosphere. A porous metal plate having a thickness of 1.2 mm in which the thickness gradually changes in the thickness direction was obtained. The porosity was 93% at the high porosity portion and 80% at the low porosity portion.
Such a metal plate can be used for applications such as a vaporizing device and a vaporizing member such as a combustion device.
＜縦貫通気孔を有する材料＞
実施例１と同様に、高分子水溶液としての６％ＰＶＡ液、金属粉としてのステンレス鋼粉ＰＦ、ゲル化剤としての８％硼砂液、気孔形成材としての発泡スチロール球を使用した。
気孔形成材を含まない金属粘土及び気孔形成材粘土はそれぞれ以下のようにして作製した。
すなわち、６％ＰＶＡ液２５ｍｌに対しステンレス鋼粉ＰＦ１５０ｇを混合してスラリーを調製し、このスラリーに８％硼砂液５ｍｌを加えてゲル化させ粘土状として該金属粘土を得た。
また、６％ＰＶＡ液２５ｍｌに対し発泡スチロール球１０ｇを混合してスラリーを調製し、このスラリーに８％硼砂液５ｍｌを加えてゲル化させ粘土状として気孔形成材粘土を得た。
気孔形成材粘土を長尺で直径１０ｍｍの丸棒に成型し、その丸棒を包むように厚さ１ｍｍの金属粘土を巻き付けたのち、直径が１／３程度になるまで引き伸ばし、短尺に７等分し、これらをまとめてまた１つの丸棒にするという操作を３回程度繰り返して軸方向に繊維状の気孔形成材が揃った多孔質体前駆体を作製し、この前駆体を６０℃で２４時間乾燥し、水素雰囲気下で１０５０℃で１時間焼成して軸方向に気孔が揃った多孔質ステンレス鋼を多孔質金属として作製した。この多孔質金属の気孔率は８０％、気孔径は０．４ｍｍ程度であった。
このように引き伸ばしてはまとめる操作を繰り返せば、金属粉と気孔形成材の粒径により制約されるものの、気孔径をさらに小さくしていくことが可能である。
<Material with vertical through-holes>
As in Example 1, a 6% PVA liquid as a polymer aqueous solution, stainless steel powder PF as a metal powder, 8% borax liquid as a gelling agent, and a polystyrene foam as a pore forming material were used.
The metal clay not containing pore forming material and the pore forming material clay were prepared as follows.
That is, 150 g of stainless steel powder PF was mixed with 25 ml of 6% PVA liquid to prepare a slurry, and 5 ml of 8% borax liquid was added to the slurry to gel, thereby obtaining the metal clay as a clay.
Further, 10 g of polystyrene foam spheres were mixed with 25 ml of 6% PVA liquid to prepare a slurry, and 5 ml of 8% borax liquid was added to the slurry to gel, thereby obtaining a pore forming material clay as clay.
After forming the pore-forming material clay into a long round bar with a diameter of 10 mm, wrapping the metal clay with a thickness of 1 mm so as to wrap the round bar, stretch it until the diameter becomes about 1/3, and divide it into seven equal parts. Then, the operation of putting these together into one round bar is repeated about three times to produce a porous body precursor in which fibrous pore-forming materials are aligned in the axial direction. Porous stainless steel with pores aligned in the axial direction was produced as a porous metal by drying for a period of time and firing for 1 hour at 1050 ° C. in a hydrogen atmosphere. This porous metal had a porosity of 80% and a pore diameter of about 0.4 mm.
If the operations of stretching and grouping are repeated in this manner, the pore diameter can be further reduced, although it is limited by the particle size of the metal powder and the pore-forming material.
＜生体用構造材＞
実施例３と同様にして得た多孔質体前駆体を乾燥後、所望の形状に整えたのち、その上に、実施例３と同様にして得た、気孔形成材を含まない金属粘土を薄く引き延ばして貼り付け、乾燥させた。
このようにして得られた成型体の表面にさらに実施例１と同様にして得た金属粘土組成物Ｃを薄く引きのばしたものを貼り付けて乾燥させて前駆体を作成し、この前駆体を十分な時間をかけて脱脂し焼成することにより、図１に示す構造をもつ製品を作製した。
このようにして得られた製品は、内部が方向性を持つ多孔質状態で、気孔の軸方向に対する強度にすぐれると同時に軽量であり、全体が緻密な層で包まれ、表面が多孔質状態の層でさらに包まれているので、生体との適合性を向上させうる生体用構造材として有用である。
<Biological structural material>
After the porous body precursor obtained in the same manner as in Example 3 was dried and adjusted to a desired shape, a metal clay containing no pore forming material obtained in the same manner as in Example 3 was thinly formed thereon. It was stretched and pasted and dried.
A precursor obtained by applying a thin stretch of the metal clay composition C obtained in the same manner as in Example 1 to the surface of the molded body thus obtained and drying it. The product having the structure shown in FIG. 1 was produced by degreasing and baking the material for a sufficient time.
The product obtained in this way is porous with a directional orientation, is excellent in strength in the axial direction of the pores, and is lightweight at the same time. The whole is wrapped in a dense layer, and the surface is in a porous state. It is useful as a structural material for living body that can improve compatibility with a living body.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Families Citing this family (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2069087A2 (en) * | 2006-07-19 | 2009-06-17 | Tower Technology Holdings (Pty) Limited | A method of agglomeration |
| JP2008260655A (en) * | 2007-04-12 | 2008-10-30 | Matsushita Electric Ind Co Ltd | Porous ceramic, and filter for sensor using the same |
| JP5202869B2 (en) * | 2007-05-10 | 2013-06-05 | 一般財団法人川村理化学研究所 | Porous material |
| JP2009120446A (en) * | 2007-11-15 | 2009-06-04 | Shinei Sangyo Kk | Heat insulating material |
| KR101116192B1 (en) | 2008-07-04 | 2012-02-22 | 비에스월드시스템 주식회사 | Method for manufacturing high strength alloy open cell of hollow sphere |
| EP2489749B1 (en) * | 2009-10-14 | 2019-08-07 | Japan Science and Technology Agency | Processes for producing precursor for functionally gradient material and producing functionally gradient material, precursor for functionally gradient material, and functionally gradient material |
| KR101355802B1 (en) | 2013-01-08 | 2014-01-27 | 한국기계연구원 | Composition used for manufacturing porous sodium borate-bonded sic ceramics, method for manufacturing porous sodium borate-bonded sic ceramics using the same, porous sodium borate-bonded sic ceramics manufactured thereby, and catalyst substrate, preform for fabricating composite material and particulate filter containing the same |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001335806A (en) * | 2000-05-23 | 2001-12-04 | Natl Inst Of Advanced Industrial Science & Technology Meti | Clay composition and method for producing molding consisting of metal or ceramics using the composition |
| JP2003129109A (en) * | 2001-10-26 | 2003-05-08 | Hitachi Metals Ltd | Method for manufacturing porous sintered compact |
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2005
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2001335806A (en) * | 2000-05-23 | 2001-12-04 | Natl Inst Of Advanced Industrial Science & Technology Meti | Clay composition and method for producing molding consisting of metal or ceramics using the composition |
| JP2003129109A (en) * | 2001-10-26 | 2003-05-08 | Hitachi Metals Ltd | Method for manufacturing porous sintered compact |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20200054656A (en) * | 2018-11-12 | 2020-05-20 | 구본주 | Method for making porosity ceramic |
| WO2020101200A1 (en) * | 2018-11-12 | 2020-05-22 | 구본주 | Method for manufacturing porous ceramic article |
| KR102127713B1 (en) | 2018-11-12 | 2020-06-29 | 구본주 | Method for making porosity ceramic |
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