JP5764506B2 - Ceramic porous body-metal heat insulating material and manufacturing method thereof - Google Patents
Ceramic porous body-metal heat insulating material and manufacturing method thereof Download PDFInfo
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- Porous Artificial Stone Or Porous Ceramic Products (AREA)
- Ceramic Products (AREA)
Description
本発明は、セラミックス多孔体の表面の一部に金属層が強固に結合してなる断熱材を提供する技術に関し、より詳しくは、強固に結合している金属層の存在により、簡便にかつ耐久性に優れる状態で金属部品などに組み込むことを可能にした、例えば、エンジンやタービンの断熱効率を高め、省エネ効果を得るための有用な断熱材として利用できるセラミックス多孔体−金属断熱材、及びその製造方法に関する。 The present invention relates to a technique for providing a heat insulating material in which a metal layer is firmly bonded to a part of the surface of a ceramic porous body. More specifically, the present invention is simple and durable due to the presence of a strongly bonded metal layer. The ceramic porous body-metal heat insulating material that can be used as a useful heat insulating material for improving the heat insulating efficiency of an engine or turbine and obtaining an energy saving effect, and the like It relates to a manufacturing method.
セラミックス多孔体は、セラミックス材料本来が有する高い耐熱性に加えて、多くの気孔が存在することによって実現される高い気孔率から、高温断熱性を有する優れた機能性材料として、広範囲の産業分野での利用が期待されている。しかし、一般的にセラミックスは金属材料と比較して熱膨張係数が小さいことから、金属を主とする機械部品へセラミックスを組み込んだ場合に、急昇温及び急降温を繰り返す使用環境下では、これら異種材料を複合化させたことに起因するクラック等が生じて耐久性に劣り、セラミックスの組み込みは困難であるという課題があった。このため、従来より、金属とセラミックス多孔体とを種々の方法によって複合化させることで、セラミックスの特徴である高温断熱性を有しながら、金属部品に組み込むことを可能にした複合体についての提案がある。 In addition to the high heat resistance inherent in ceramic materials, ceramic porous bodies are used in a wide range of industrial fields as an excellent functional material having high-temperature thermal insulation properties due to the high porosity achieved by the presence of many pores. Is expected to be used. However, in general, ceramics have a smaller coefficient of thermal expansion than metal materials. Therefore, when ceramics are incorporated into mechanical parts mainly made of metal, these are used in environments where rapid temperature rise and fall are repeated. There was a problem that cracks and the like due to the composite of different materials were generated and the durability was inferior, making it difficult to incorporate ceramics. For this reason, by combining various metal and ceramic porous bodies using various methods, proposals have been made for composites that can be incorporated into metal parts while maintaining the high-temperature thermal insulation characteristic of ceramics. There is.
ここで、セラミックス多孔体に限らず、セラミックスと金属との異種材料同士を複合化させる方法としては、溶射や蒸着、メタライズなどによって、セラミックス或いは金属からなる材料表面に皮膜を形成する方法、溶融金属とセラミックスとを、含浸や鋳ぐるみによって互いに溶着する方法、その他、原料組成の制御により構造体の片面から反対面にかけて組成の傾斜をつけることによる複合化や、接着剤や結合剤（材）を用いての結合などの方法が知られている。下記に述べるように、これらの技術を利用し、有用な複合体を得ることを目的として、例えば、金属基材表面にセラミックス多孔体からなる層を設けたり、セラミックス多孔体表面に金属膜を形成する等、より良好な機能性が付与された複合化材料を得る方法が種々提案されている。 Here, not only the porous ceramic body but also a method of compounding different materials of ceramic and metal include a method of forming a film on the surface of a material made of ceramic or metal by spraying, vapor deposition, metallization, etc., molten metal A method of welding ceramics and ceramics together by impregnation or cast-in, other methods such as compounding by controlling the composition of the raw material to incline the composition from one side to the other side, and adhesives and binders (materials) Methods such as bonding using them are known. As described below, for the purpose of obtaining a useful composite using these technologies, for example, a layer made of a ceramic porous body is provided on the surface of a metal substrate, or a metal film is formed on the surface of the ceramic porous body. Various methods have been proposed for obtaining composite materials with better functionalities such as the above.
例えば、金属基材を熱から保護するために、金属基材表面に、気孔を有するセラミックス断熱層と封孔層とを積層してなる遮熱コーティング構造を形成することについての提案がある（特許文献１参照）。また、耐食性や耐摩耗性を向上させる目的で形成されている耐食性合金皮膜層を有する可動部品表面を保護するために、可動部品の表面に、無機系封孔剤で封孔処理されたアルミナを主成分とする溶射皮膜を形成することについての提案がある（特許文献２参照）。また、逆に、セラミックス基板表面に、無電解めっきして金属膜を形成する方法（特許文献３参照）や、セラミックス多孔体にアルミニウムを主成分とする金属を含浸する工程を有する、表面状態、物性面共に良好なアルミニウム合金−セラミックス質複合体を得る方法（特許文献４参照）についての提案がある。また、セラミックス製多孔体を溶融金属によって鋳ぐるみ一体化させたセラミックス・金属複合材料についての提案もある（特許文献５参照）。その他、傾斜複合化や（特許文献６参照）、結合性の向上のために、金属とセラミックスの結合体の、セラミックス側にろう付を目的として、予めメタライズ処理を施すことについての提案もある（特許文献７、８参照）。 For example, in order to protect a metal substrate from heat, there is a proposal for forming a thermal barrier coating structure in which a ceramic heat insulating layer having pores and a sealing layer are laminated on the surface of a metal substrate (patent) Reference 1). In addition, in order to protect the surface of the movable part having a corrosion-resistant alloy film layer formed for the purpose of improving the corrosion resistance and wear resistance, the surface of the movable part is coated with alumina sealed with an inorganic sealing agent. There is a proposal for forming a thermal spray coating as a main component (see Patent Document 2). Inversely, a method of forming a metal film by electroless plating on the surface of a ceramic substrate (see Patent Document 3), a surface state having a step of impregnating a ceramic porous body with a metal mainly composed of aluminum, There is a proposal for a method (see Patent Document 4) for obtaining an aluminum alloy-ceramic composite having good physical properties. There is also a proposal for a ceramic / metal composite material in which a porous ceramic body is integrated with a molten metal by casting (see Patent Document 5). In addition, there is also a proposal for performing metallization in advance for the purpose of brazing the composite of a metal and a ceramic to the ceramic side in order to make a slant composite (see Patent Document 6) and to improve the bondability (see FIG. (See Patent Documents 7 and 8).
一方、従来より、断熱特性を向上させる目的で、様々なセラミックス多孔体についての検討がなされている。出願人らは、原料の種類を問わず、すべてのセラミックス材料に応用が可能である技術として、断熱材に求められる十分な強度を有し、しかも断熱特性が向上した断熱材として極めて有用な新規な微構造の気孔の形成を簡便に実現する方法を提案している。該方法によれば、ゲル化凍結法を用い、特殊な添加物を加えることで、セラミックスに高い気孔率を維持させながら、ガスの流れを抑制する構造を容易に形成することができる(特許文献９参照)。 On the other hand, various ceramic porous bodies have been studied for the purpose of improving heat insulation properties. Applicants are new technology that is extremely useful as a heat-insulating material that has sufficient strength required for heat-insulating materials and improved heat-insulating properties as a technology that can be applied to all ceramic materials regardless of the type of raw materials. Has proposed a method for easily realizing the formation of fine pores. According to this method, by using a gelation freezing method and adding a special additive, it is possible to easily form a structure that suppresses gas flow while maintaining high porosity in ceramics (Patent Document). 9).
しかしながら、下記に述べるように、これらの従来技術によっても金属を主とする機械部品へセラミックスを組み込んで複合化させることは難しく、より簡便に耐久性に優れる複合体の開発が望まれている。まず、上記した特許文献１や特許文献２に記載の技術では、金属基材表面に形成される、気孔を有するセラミックス断熱層における気孔径や気孔径分布を制御することが困難であり、高気孔率のセラミックス多孔質断熱材に比べて気孔率に劣るものになるため、十分な断熱性が達成されないという課題がある。また、上記した特許文献３に記載の技術は、皮膜形成工程が多く、煩雑であり、セラミックス多孔体と金属とを複合化した材料を簡便に提供し得るものではなかった。さらに、上記した特許文献４や特許文献５に記載の技術では、金属を溶融させるための設備が必要であることに加えて、金属の融点以上に熱せられている溶融金属とセラミックス多孔体を接触させる際の熱衝撃を緩和させるため、セラミックス多孔体をあらかじめ上記と同等の温度にまで加熱しなければならないという実用上の課題もある。また、上記した特許文献７及び特許文献８に記載の技術は、多くの工程を含み、煩雑であり、セラミックス多孔体と金属とを複合化した材料を簡便に提供し得るものではなかった。
However, as described below, it is difficult to incorporate ceramics into a mechanical part mainly composed of metal by these conventional techniques, and it is desired to develop a composite that is simple and excellent in durability. First, with the techniques described in
また、上記した特許文献９に記載の技術は、様々な材料において、高い気孔率を有する断熱性と強度の両方において優れるセラミックス断熱材を提供することを目的としたものであるため、セラミックス多孔体と金属の複合化は全く考慮されていない。これに対し、この技術によって得られる多孔質セラミックスは、最大９９％の超高気孔率を有しており、熱容量も小さく、同時に気孔壁の薄壁化のため固体間の熱伝導を抑制でき、気孔内部に多数の節状の膜が掛け渡され隔壁構造が存在するため、気体の伝熱や対流が高度に抑制されて、優れた断熱特性を示す。特に、この技術によって得られる多孔質セラミックスは、上記構造に加え、表面に緻密層が配置されたものとなるため、さらに高温での輻射をも抑制でき、上記した固体伝熱・気体伝熱（対流）に加えて、輻射の熱伝導までの三要素を全て抑制した優れた断熱性能を実現した従来にないものである。このように、特許文献９に記載の技術によって提供される多孔質セラミックスは、上記した特徴的な構造を有することで、繊維状断熱材に匹敵する低熱伝導率を有しつつ、ブロック状断熱材と同等以上の強度を実現できる新しい断熱材であり、その広範な利用が期待される。しかし、セラミックスであることに変わりはなく、金属を主とする金属部品や装置等に良好な状態に組み込むことができなければ、その用途は限定されたものになり、その優れた機能の利用は大きく制限される。 In addition, the technique described in Patent Document 9 described above is intended to provide a ceramic heat insulating material that is excellent in both heat insulating properties and strength having a high porosity in various materials. There is no consideration of metal complexation. On the other hand, the porous ceramics obtained by this technology have an ultra-high porosity of 99% at the maximum, a small heat capacity, and at the same time, the heat conduction between solids can be suppressed due to the thin wall of the pores. Since a large number of nodular membranes are spanned inside the pores and a partition wall structure exists, heat transfer and convection of the gas are highly suppressed, and excellent heat insulating properties are exhibited. In particular, since the porous ceramic obtained by this technique has a dense layer on the surface in addition to the above structure, it can further suppress radiation at high temperatures, and the above-described solid heat transfer / gas heat transfer ( In addition to convection), it has never been possible to achieve excellent heat insulation performance that suppresses all three elements up to the heat conduction of radiation. As described above, the porous ceramic provided by the technique described in Patent Document 9 has the above-described characteristic structure, and thus has a low thermal conductivity comparable to the fibrous heat insulating material, and a block-shaped heat insulating material. It is a new heat insulating material that can achieve strength equal to or better than that, and is expected to be widely used. However, there is no change to ceramics, and if it cannot be incorporated in a good state in metal parts and equipment mainly made of metal, its use will be limited, and the use of its superior functions will be limited. Greatly limited.
従って、本発明の目的は、高温断熱性が期待されるセラミックス多孔体に金属を、金属溶融炉等の特別の設備を必要とせずに、より簡便な方法で強固に結合させることができる技術を見出し、ひいては、当該技術によって提供される、表面の少なくとも一部に金属層が強固に結合されたセラミックス多孔体を用いることで、金属を主とするエンジンやタービンなどの機械部品や装置等へ、セラミックス多孔体を簡便に、耐久性に優れる状態で組み込むことを可能にできる、セラミックス多孔体−金属断熱材を提供することにある。さらに、本発明の目的は、断熱材として極めて優れた有用な、例えば、先に挙げた特許文献９で提案されているような強度向上と断熱特性の向上を同時に高いレベルで実現した多孔質セラミックス等を、金属を主とした機械部品や装置等へ、簡便に、耐久性に優れる状態で組み入れることを可能にすることで、高気孔率のセラミックス多孔質断熱材と比べて遜色のない高い気孔率を有し、これによって、例えば、エンジンやタービンの断熱効率をより高め、より高い省エネ効果を実現できるセラミックス多孔体と金属との簡便な複合化技術を提供することにある。 Accordingly, an object of the present invention is to provide a technology that can firmly bond a metal to a ceramic porous body that is expected to have high-temperature heat insulation properties by a simpler method without requiring special equipment such as a metal melting furnace. By using a ceramic porous body in which the metal layer is firmly bonded to at least a part of the surface, which is provided by the technique, and provided by the technology, to mechanical parts and devices such as engines and turbines mainly using metal, An object of the present invention is to provide a ceramic porous body-metal heat insulating material that can easily incorporate a ceramic porous body in a state of excellent durability. Furthermore, the object of the present invention is a porous ceramic that is extremely useful as a heat insulating material, for example, at the same time realizing high strength and high heat insulating properties as proposed in Patent Document 9 mentioned above. Can be incorporated into mechanical parts and devices mainly made of metal in a state of excellent durability, and high porosity that is comparable to ceramic porous insulation with high porosity. Thus, for example, it is to provide a simple composite technology of a ceramic porous body and a metal that can increase the heat insulation efficiency of an engine or a turbine and realize a higher energy saving effect.
上記の目的は、下記の本発明によって達成される。すなわち、本発明は、セラミックス多孔体の表面の少なくとも一部に金属層が強固に結合してなる、金属を主とする機械部品などとの接合などによる複合化が容易にできるセラミックス多孔体−金属断熱材であって、セラミックス多孔体と金属層とが結合しているセラミックス多孔体と金属との界面に、該セラミックスと該金属と、必要に応じて接着させた該金属とは別の金属が含有されてなる中間層が形成されており、かつ、該中間層のセラミックス多孔体側において、結合させたいずれかの金属がセラミックス多孔体の細孔内部まで侵入していることを特徴とするセラミックス多孔体−金属断熱材を提供する。 The above object is achieved by the present invention described below. That is, the present invention relates to a ceramic porous body-metal that can be easily combined by joining with a mechanical component mainly composed of metal, in which a metal layer is firmly bonded to at least a part of the surface of the ceramic porous body. A heat insulating material, which is different from the metal bonded to the ceramic and the metal, if necessary, at the interface between the ceramic porous body and the metal where the ceramic porous body and the metal layer are bonded. A porous ceramic material, characterized in that an intermediate layer is formed, and on the ceramic porous body side of the intermediate layer, any bonded metal penetrates into the pores of the ceramic porous material. Body-metal insulation is provided.
上記セラミックス多孔体−金属断熱材の好ましい形態としては、下記のことが挙げられる。すなわち、前記形成された中間層の厚みが２０〜５００μｍの範囲内にあり、かつ、前記結合させた金属がセラミックス多孔体の細孔内部に存在している範囲が、セラミックス多孔体の表面から１０〜３００μｍであること；前記セラミックス多孔体が、気孔率が５０〜９９％で、かつ、気孔径が１０〜３００μｍの円筒形状のマクロ細孔を有し、その細孔の内壁に多数の節状の膜が掛け渡され隔壁を形成した、不連通の細孔を有する隔壁構造を主とするものであること；前記セラミックス多孔体の２つ以上の面にそれぞれ金属層が強固に結合してなる、金属層−セラミックス多孔体−金属層構造を有すること；前記セラミックス多孔体が、アルミナ、シリカ、ジルコニア、炭化硼素、窒化珪素、コーディエライト、グラファイトからなる群から選ばれる少なくとも１種を含有する材質からなることである。 The following is mentioned as a preferable form of the said ceramic porous body-metal heat insulating material. That is, the thickness of the formed intermediate layer is in the range of 20 to 500 μm, and the range in which the bonded metal is present in the pores of the ceramic porous body is 10 from the surface of the ceramic porous body. The porous ceramic body has cylindrical macropores having a porosity of 50 to 99% and a pore diameter of 10 to 300 μm, and a large number of nodal shapes on the inner wall of the pores The main structure is a partition wall structure having discontinuous pores in which a film of the above is stretched to form a partition wall; and a metal layer is firmly bonded to each of two or more surfaces of the ceramic porous body. Metal layer-ceramic porous body-having a metal layer structure; whether the ceramic porous body is made of alumina, silica, zirconia, boron carbide, silicon nitride, cordierite, or graphite Is that made of a material containing at least one selected.
本発明は、別の実施形態として、上記いずれかのセラミックス多孔体−金属断熱材の製造方法であって、セラミックス多孔体表面に金属層を結合させる部分に、電子ビーム面加工装置を用い、カソードに対する加速印加電圧を１０ｋＶ〜３０ｋＶ、電子銃ハウジング内の希ガスのガス圧を０．０３ＭＰａ〜０．０９ＭＰａの範囲で制御して、電子ビームの照射エネルギー密度が０．１〜１０Ｊ／ｃｍ2の範囲に制御した電子ビームを照射し、照射した部分を表面改質した後、その表面改質部分に、結合させる厚み１００〜５，０００μｍの金属を接触させた状態で積層させ、セラミックス多孔体と金属が接触した状態を保持できるように冶具にて上記積層状態を固定し、真空条件下或いは不活性雰囲気下、５００℃以上の温度で加熱してセラミックス多孔体と金属とを結合させて金属層を形成することを特徴とするセラミックス多孔体−金属断熱材の製造方法を提供する。 As another embodiment, the present invention provides a method for producing any one of the above ceramic porous body-metal heat insulating materials, wherein an electron beam surface processing apparatus is used in a portion where a metal layer is bonded to the surface of the ceramic porous body, and a cathode Accelerating applied voltage is controlled in the range of 10 kV to 30 kV, the gas pressure of the rare gas in the electron gun housing is controlled in the range of 0.03 MPa to 0.09 MPa, and the irradiation energy density of the electron beam is 0.1 to 10 J / cm 2 . The surface of the irradiated portion is irradiated with a controlled electron beam, and the irradiated portion is laminated with a metal having a thickness of 100 to 5,000 μm in contact with the surface-modified portion. The above laminated state is fixed with a jig so that the metal can be kept in contact, and heated at a temperature of 500 ° C. or higher under vacuum or in an inert atmosphere. A method for producing a ceramic porous body-metal heat insulating material is provided, wherein a metal layer is formed by bonding a porous metal body and a metal.
上記セラミックス多孔体−金属断熱材の製造方法の好ましい形態としては、電子ビームを照射して前記表面改質をした後、セラミックス多孔体の改質した面に、さらに、結合させる金属以外の１０〜１００μｍの厚みの金属箔又は粒径１０〜３００μｍの金属粉末を、接着および含浸させ、その後にセラミックス多孔体と金属との結合を行うこと；前記セラミックス多孔体が、気孔率が５０〜９９％で、かつ、気孔径が１０〜３００μｍの円筒形状のマクロ細孔を有し、その細孔の内壁に多数の節状の膜が掛け渡され隔壁を形成した、不連通の細孔を有する隔壁構造を主とするものであることが挙げられる。 As a preferable embodiment of the method for producing the ceramic porous body-metal heat insulating material, after the surface modification is performed by irradiating an electron beam, the surface of the ceramic porous body is further modified to 10 to 10 other than the metal to be bonded. Adhering and impregnating a metal foil having a thickness of 100 μm or a metal powder having a particle diameter of 10 to 300 μm and then bonding the ceramic porous body to the metal; the ceramic porous body has a porosity of 50 to 99% A partition wall structure having discontinuous pores having cylindrical macropores with a pore diameter of 10 to 300 μm, and having a plurality of nodular membranes formed on the inner walls of the pores to form partition walls Is the main thing.
本発明によれば、金属とセラミックス多孔体とを、直接或いは必要に応じて金属箔又は金属粉末を利用することで、強固に結合させた、セラミックス多孔体の表面の少なくとも一部に金属層が結合してなるセラミックス多孔体−金属断熱材が提供される。特に、該断熱材は、本発明の特有の方法によって、金属層がセラミックス多孔体に、直接或いは必要に応じて金属箔又は金属粉末を利用して結合したものであるため、その境界面に前駆層（表面改質層とも呼ぶ）を経て形成される中間層は、厚みが薄く、かつ結合させた金属がセラミックス多孔体の細孔内部まで侵入したものになっており、その結合状態は、このアンカー効果によってもたらされたと考えられる極めて強固なものになる。さらに、このセラミックス多孔体の表面に強固に結合している金属層を利用して、金属を主たる材料とした装置や部品等への組み込みに用いることで、従来、様々な産業分野で用いられている高気孔率のセラミックス多孔質断熱材と比べても遜色のない、高い高温断熱性を実現したセラミックス多孔体を、金属を主たる材料とした装置等の断熱材として有効に利用できるようになる。より具体的には、本発明によれば、高温断熱性が期待される優れた特性を有するセラミックス多孔体の表面に、セラミックス多孔体表面を改質させるための簡便な工程を経ることで、従来技術のように、金属溶融炉等といった特別の設備や複雑な処理工程を必要とすることなく、金属層を強固に結合することができ、これによって、断熱材としての機能性に優れたセラミックス多孔体を、金属を主たる材料とした部品や装置等に簡便に組み入れる技術の提供が可能になる。本発明の技術では、金属層を形成させる際の処理によって、結合させたセラミックス多孔体の本来の特性が損なわれることが殆どないので、セラミックス多孔体に、先に説明した、断熱特性の期待される高気孔率及び気孔形状が制御された、遮熱性・ガス遮断性に優れたものを用いれば、提供されるセラミックス多孔体−金属断熱材は、高温断熱性を有し、しかも極めて簡便に金属部品などに組み込むことが可能な優れたものになる。したがって、本発明の技術を用いることで、例えば、エンジンやタービンに適用した場合に、セラミックス多孔体が優れた断熱材として機能し、これらの効率をより高めることができる。 According to the present invention, the metal layer is formed on at least a part of the surface of the ceramic porous body in which the metal and the ceramic porous body are bonded directly or as necessary using a metal foil or a metal powder. A bonded ceramic porous body-metal heat insulating material is provided. In particular, the heat insulating material is obtained by bonding the metal layer to the ceramic porous body directly or using a metal foil or a metal powder as required by the method specific to the present invention. The intermediate layer formed through the layer (also referred to as the surface modification layer) is thin, and the bonded metal has penetrated into the pores of the ceramic porous body. It becomes extremely strong that is thought to have been brought about by the anchor effect. Furthermore, by using the metal layer that is firmly bonded to the surface of the ceramic porous body, it can be used for incorporation into devices and parts made of metal as the main material, and has been used in various industrial fields. The ceramic porous body that realizes high-temperature heat insulation, which is inferior to that of high-porosity ceramic porous heat insulating materials, can be effectively used as a heat insulating material for devices using metal as a main material. More specifically, according to the present invention, by passing through a simple process for modifying the surface of the ceramic porous body, the surface of the ceramic porous body having excellent properties expected to have high-temperature heat insulation properties, Like technology, the metal layer can be firmly bonded without the need for special equipment such as a metal melting furnace or complicated processing steps. It is possible to provide a technique for easily incorporating the body into a component or device made mainly of metal. In the technology of the present invention, the original characteristics of the bonded ceramic porous body are hardly impaired by the treatment in forming the metal layer. Therefore, the ceramic porous body is expected to have the heat insulating characteristics described above. The ceramic porous body-metal heat insulating material to be provided has high temperature heat insulating properties and is extremely easy to use if a material having a high porosity and controlled pore shape and excellent heat and gas barrier properties is used. It becomes an excellent one that can be incorporated into parts. Therefore, by using the technique of the present invention, for example, when applied to an engine or a turbine, the ceramic porous body functions as an excellent heat insulating material, and these efficiencies can be further increased.
以下、発明を実施するための好ましい形態を挙げて、本発明をより詳細に説明する。以下の説明は、発明の趣旨をよりよく理解可能とするためのものであり、本発明を限定するものではない。
本発明のセラミックス多孔体−金属断熱材は、セラミックス多孔体と金属とが結合している境界面に、該セラミックスと該金属と、必要に応じて該金属とは別の金属が含有されてなる中間層が形成されており、かつ、該中間層のセラミックス多孔体側の境界において、結合させた金属がセラミックス多孔体の細孔内部まで侵入していることを特徴とする。このような、結合により形成される中間層の厚みは２０〜５００μｍ程度と薄く、しかも、いわゆるアンカー効果が得られる結合させた金属がセラミックス多孔体の細孔に表面から１０から３００μmの内部まで侵入した従来にない特徴的なセラミックス多孔体と金属との結合状態によって、本発明の断熱材は、高温断熱性を有し、かつ容易に金属部品に組み込むことが可能である優れた機能性を発揮し得るものとなる。
Hereinafter, the present invention will be described in more detail with reference to preferred embodiments for carrying out the invention. The following description is for making the gist of the invention better understood and is not intended to limit the present invention.
The ceramic porous body-metal heat insulating material of the present invention contains the ceramic, the metal, and, if necessary, a metal different from the metal at the interface where the ceramic porous body and the metal are bonded. An intermediate layer is formed, and the bonded metal penetrates into the pores of the ceramic porous body at the boundary of the intermediate layer on the ceramic porous body side. The thickness of such an intermediate layer formed by bonding is as thin as about 20 to 500 μm, and the bonded metal that provides a so-called anchor effect penetrates into the pores of the ceramic porous body from the surface to the inside of 10 to 300 μm. Due to the unprecedented characteristic ceramic porous body and metal bonding state, the heat insulating material of the present invention has high-temperature heat insulating properties and excellent functionality that can be easily incorporated into metal parts. It will be possible.
そして、この特徴的な結合状態は、従来にない簡便な本発明の製造方法によって容易に得られる。具体的には、セラミックス多孔体表面の金属を結合させる部分に、制御された電子ビームを照射させるという極めて簡便な方法で、まず、層厚の制御された表面改質層（結合した界面の中間層となる前駆層）を形成し、その後に形成した前駆層に結合させる厚みが１００〜５，０００μｍ程度の金属を積層させ、この積層し、接触した状態を保持して、真空下或いは不活性雰囲気下、加熱することで結合させるという、簡単で少ない工程数で、上記したように、厚みが薄く、しかも、セラミックス多孔体の細孔内部まで金属が侵入した状態の中間層が形成され、その結果、優れた機能性を実現した本発明の断熱材が得られる。 And this characteristic coupling | bonding state is easily obtained by the simple manufacturing method of this invention which is not in the past. Specifically, a surface modified layer with a controlled layer thickness (in the middle of the bonded interface) is applied by a very simple method of irradiating a portion of the ceramic porous body where the metal is bonded with a controlled electron beam. A precursor layer to be a layer) is formed, and a metal having a thickness of about 100 to 5,000 μm to be bonded to the formed precursor layer is laminated, and this laminated layer is kept in contact and kept under vacuum or inactive. As described above, an intermediate layer in which a metal is infiltrated into the pores of the ceramic porous body is formed as described above with a simple and small number of steps of bonding by heating in an atmosphere. As a result, the heat insulating material of the present invention that achieves excellent functionality can be obtained.
本発明のセラミックス多孔体−金属断熱材の積層構造は、金属部品に組み込むためにどちらか一方の面が金属であればよいが、金属−セラミックス多孔体−金属というように、例えば、セラミックス多孔体の対峙する２面を金属が積層してなる３層構造としてもよい。該３層構造の場合は、これを金属部品等に組み入れると、どちらか一方の金属層が金属部品等との接着や接合など、組み込みの役割をなし、もう一方の金属層がエンジンやタービンなど作動時に衝撃を受ける環境下においてセラミックス多孔体の皮膜層として、セラミックス多孔体層による断熱層の破損を防ぐことができる。 In the laminated structure of the ceramic porous body-metal heat insulating material of the present invention, either one of the surfaces may be a metal so as to be incorporated into a metal part. It is good also as a 3 layer structure formed by laminating | stacking a metal on the 2 surfaces which oppose. In the case of the three-layer structure, when this is incorporated into a metal part or the like, one of the metal layers plays a role of incorporation, such as adhesion or bonding to the metal part or the like, and the other metal layer serves as an engine or turbine. It is possible to prevent the heat insulating layer from being damaged by the ceramic porous body layer as a coating layer of the ceramic porous body under an environment that receives an impact during operation.
本発明のセラミックス多孔体−金属断熱材の製造方法は、（１）セラミックス多孔体の表面を電子ビーム照射により表面改質をする工程と、（２）セラミックス多孔体の表面改質層（前駆層）と金属とを積層し、接触した状態を保持しながら、真空条件下、特定の温度範囲で加熱し、上記表面改質層と金属とを結合する工程とを有する。 The method for producing a ceramic porous body-metal heat insulating material of the present invention includes (1) a step of surface modification of the surface of the ceramic porous body by electron beam irradiation, and (2) a surface modified layer (precursor layer) of the ceramic porous body. ) And a metal, and heating in a specific temperature range under a vacuum condition while maintaining a contact state, and bonding the surface modified layer and the metal.
より具体的には、上記した（１）の工程において、セラミックス多孔体における、金属と複合化させる面部分に、電子ビーム面加工装置を用い、カソードに対する加速印加電圧を１０ｋＶ〜３０ｋＶ、電子銃ハウジング内の希ガスのガス圧を０．０３ＭＰａ〜０．０９ＭＰａの範囲で制御して、電子ビームの照射エネルギー密度が０．１〜１０Ｊ／ｃｍ2の範囲に制御した電子ビーム（以下単に電子ビームとも言う）を照射して、層厚を制御した表面改質層（前駆層）を形成する。そして、この前駆層に、複合化させる金属を積層し、接触した状態を保持しながら、真空条件下或いは不活性雰囲気下、５００℃以上の温度で加熱する（２）の工程を経ることで、強固に異種材料である金属が結合された、高温断熱性を有し、かつ容易に金属部品に組み込むことが可能な本発明のセラミックス多孔体−金属断熱材が得られる。 More specifically, in the above-described step (1), an electron beam surface processing apparatus is used for the surface portion of the ceramic porous body to be combined with the metal, the acceleration applied voltage to the cathode is 10 kV to 30 kV, and the electron gun housing An electron beam (hereinafter simply referred to as an electron beam) in which the gas pressure of the rare gas is controlled in the range of 0.03 MPa to 0.09 MPa and the irradiation energy density of the electron beam is controlled in the range of 0.1 to 10 J / cm 2. To form a surface modified layer (precursor layer) having a controlled layer thickness. Then, by laminating the metal to be composited on this precursor layer and maintaining the contacted state, it is heated under a vacuum condition or in an inert atmosphere at a temperature of 500 ° C. or higher (2), The ceramic porous body-metal heat insulating material of the present invention, which has a high-temperature heat insulating property and can be easily incorporated into metal parts, is obtained by firmly bonding metals, which are different materials.
本発明に用いるセラミックス多孔体は、気孔率が５０〜９９％でかつ気孔径が１０〜３００μｍの、円筒形状でその内部が不連通である細孔（独立の細孔）を主とするものであることが好ましい。このような、不連通の細孔を多数有する、高気孔率のセラミックス多孔体は、従来より高温断熱性が求められる材料として用いられている。本発明者らは、このような優れたセラミックス多孔体を、その高い機能が損なわれないようにして、金属と結合できれば、断熱効率の向上が求められるエンジンやタービン部品に容易に組み込むことができ、断熱効率をより高めるための断熱材としてより有用な、優れた複合化断熱材にできると考えて鋭意検討した結果、本発明に至ったものである。 The ceramic porous body used in the present invention mainly has pores (independent pores) having a porosity of 50 to 99% and a pore diameter of 10 to 300 μm, and the inside of which is discontinuous. Preferably there is. Such a high-porosity ceramic porous body having many discontinuous pores is conventionally used as a material that requires high-temperature heat insulation. The present inventors can easily incorporate such an excellent ceramic porous body into an engine or turbine component that requires improvement in heat insulation efficiency if it can be bonded to a metal without impairing its high function. As a result of diligent research on the idea that an excellent composite heat insulating material more useful as a heat insulating material for increasing the heat insulating efficiency can be obtained, the present invention has been achieved.
本発明で用いるセラミックス多孔体は、その材質の種類に制限がなく、コストや最終製品の熱的特性や強度などを考慮して、種々の材料からなるセラミックスを適宜に選択すればよい。例えば、公知のセラミックス原料を、１種或いは異なる２種以上を配合してなるセラミックス多孔体を使用することができる。本発明に使用できる具体的なセラミックス材料としては、例えば、アルミナ、シリカ、ジルコニア、炭化硼素、窒化珪素、コーディエライト又はグラファイトを挙げることができる。 The ceramic porous material used in the present invention is not limited in the type of material, and ceramics made of various materials may be appropriately selected in consideration of cost, thermal characteristics and strength of the final product. For example, it is possible to use a ceramic porous body formed by blending known ceramic raw materials with one kind or two or more kinds. Specific examples of the ceramic material that can be used in the present invention include alumina, silica, zirconia, boron carbide, silicon nitride, cordierite, and graphite.
さらに、本発明者らの検討によれば、本発明に用いるセラミックス多孔体として、本発明者らが開発した、特開２０１１−１９５４３７号公報に記載の、セラミックス原料粉体と、ゲル化剤溶解液とを含む材料から作製したゲル化剤由来の筒状のマクロ細孔内部に多数の節状の隔壁が形成されてなる特有の隔壁構造を有する多孔質セラミックスを用いることが特に好ましい。図５に示したように、該多孔質セラミックスは、円筒状のマクロ細孔の内壁に直立して架け渡された状態の、多数の節状の膜が隔壁を形成してなる微細な隔壁構造を有するが、この隔壁構造は、熱やガスを通しにくく断熱材として極めて有用であることが確認されている。本発明者らの検討によれば、該多孔質セラミックスを本発明の方法によって金属と結合させた場合、円筒状のマクロ細孔はそのままの状態で、電子ビームが照射された部分にあった骨格部の表面が変質し、かつ隔壁の少なくとも一部が失われて、このような状態の上記マクロ細孔内部まで結合させた金属が侵入した状態の微構造が形成される。この結果、より高いアンカー効果がもたらされ、２０〜５００μｍと厚みの薄い中間層でありながら、より強固な結合が達成され、上記特有の隔壁構造によって達成した、熱やガスを通しにくく断熱材としての機能が十分に維持された耐久性に優れるセラミックス多孔体−金属断熱材となる。 Further, according to the study by the present inventors, as a ceramic porous body used in the present invention, the ceramic raw material powder described in Japanese Patent Application Laid-Open No. 2011-195437, which has been developed by the present inventors, is dissolved in a gelling agent. It is particularly preferable to use a porous ceramic having a unique partition structure in which a large number of node-like partition walls are formed inside cylindrical macropores derived from a gelling agent prepared from a material containing a liquid. As shown in FIG. 5, the porous ceramic has a fine partition structure in which a large number of nodular films form partition walls in a state of being erected on the inner wall of a cylindrical macropore. However, it has been confirmed that this partition wall structure is extremely useful as a heat insulating material through which heat and gas hardly pass. According to the study by the present inventors, when the porous ceramic is bonded to the metal by the method of the present invention, the skeleton that was in the portion irradiated with the electron beam with the cylindrical macropores intact. The surface of the portion is altered and at least a part of the partition walls is lost, and a microstructure in which the metal bonded to the inside of the macropores in such a state has entered is formed. As a result, a higher anchor effect is achieved, and a stronger bond is achieved while being an intermediate layer having a thin thickness of 20 to 500 μm. As a ceramic porous body-metal heat insulating material excellent in durability in which the function as the above is sufficiently maintained.
以下、本発明のセラミックス多孔体−金属断熱材の製造方法における各工程について説明する。まず、本発明の製造方法では、上記で説明したようなセラミックス多孔体表面に、汎用の電子ビーム面加工装置等を用い、電子ビームを照射する。本発明者らの検討によれば、（１）の工程で、セラミックス多孔体の表面に、カソードに対する加速印加電圧を１０ｋＶ〜３０ｋＶ、電子銃ハウジング内の希ガスのガス圧を０．０３ＭＰａ〜０．０９ＭＰａの範囲の条件で、電子ビームの照射エネルギー密度が０．１〜１０Ｊ／ｃｍ2の範囲に制御された電子ビームを照射すれば、図２に示したように、電子ビームを照射した表面部分の多孔の性状が明らかに変化し、表面が改質される。そして、このセラミックス多孔体表面に形成される改質層は、その後に行われる（２）セラミックス多孔体と金属との結合工程において、強固な結合をもたらす中間層を形成するための前駆の層として位置づけられる。 Hereinafter, each process in the manufacturing method of the ceramic porous body-metal heat insulating material of this invention is demonstrated. First, in the manufacturing method of the present invention, the surface of the ceramic porous body as described above is irradiated with an electron beam using a general-purpose electron beam surface processing apparatus or the like. According to the study by the present inventors, in the step (1), the acceleration applied voltage to the cathode is 10 kV to 30 kV and the gas pressure of the rare gas in the electron gun housing is 0.03 MPa to 0 on the surface of the ceramic porous body. The surface irradiated with the electron beam as shown in FIG. 2 when irradiated with an electron beam whose electron beam irradiation energy density is controlled within the range of 0.1 to 10 J / cm 2 under the condition of 0.09 MPa. The porosity of the part is clearly changed and the surface is modified. The modified layer formed on the surface of the ceramic porous body is a precursor layer for forming an intermediate layer that provides strong bonding in the bonding step of (2) the ceramic porous body and the metal performed thereafter. Positioned.
本発明の製造方法で使用する電子ビーム面加工装置は、例えば、その内面を鏡面処理する等、金型等の表面処理を主な目的とする装置であり、従来公知であるプラズマ電子銃から大面積の低エネルギーパルス電子ビームを被照射体に照射する装置などを用いることができる。その中でも、電子銃をソレノイドの励磁により閉じ込め、ビームの束が拡散・収斂することなく断面積の大きい電子ビームを照射できる大面積電子ビーム面加工装置を用いることが好ましい。このような装置を用いると、断面積の大きい低エネルギー密度電子ビームを被照射体に照射することができるので、本発明で行う、セラミックス多孔体の表面の改質に特に好ましい。 The electron beam surface processing apparatus used in the manufacturing method of the present invention is an apparatus mainly for surface treatment of a mold or the like, for example, by mirror-treating the inner surface thereof, and is large from a conventionally known plasma electron gun. An apparatus that irradiates an irradiated object with a low-energy pulsed electron beam having an area can be used. Among them, it is preferable to use a large-area electron beam surface processing apparatus that can confine the electron gun by solenoid excitation and irradiate an electron beam having a large cross-sectional area without diffusing and converging the beam bundle. When such an apparatus is used, it is possible to irradiate the irradiated body with a low energy density electron beam having a large cross-sectional area, which is particularly preferable for the modification of the surface of the ceramic porous body performed in the present invention.
大面積電子ビーム面加工装置は、低気圧電離気体を充填し、所定の低ガス圧状態で、電子ビーム照射を行う。このとき電子ビームの照射エネルギー密度は０．１〜１０Ｊ／ｃｍ2の範囲とすることが好ましく、本発明の目的を達成した断熱材を得るためには、カソード電圧を１０〜３０ｋＶ、及び電子銃ハウジング内の希ガスのガス圧を０．０３〜０．０９Ｐａ程度の範囲で実施することが好ましい。また、カソードと被照射体であるセラミックス多孔体の照射面との距離（照射距離）は、目的とする照射エネルギー密度の電子ビームが、所望の照射面に照射されるように１５〜５０ｍｍ程度であることが好ましい。この範囲よりも照射距離が小さいと、照射される電子ビームのエネルギー密度が高くなり、被照射体表面であるセラミックス多孔体の変形や荒れが顕著となるので好ましくない。一方、照射距離が上記した範囲よりも大きいと、照射される電子ビームの照射エネルギー密度が小さ過ぎて、表面の改質が十分に行えない場合があるので好ましくない。 The large-area electron beam surface processing apparatus is filled with low-pressure piezoelectric gas separation and performs electron beam irradiation in a predetermined low gas pressure state. At this time, the irradiation energy density of the electron beam is preferably in the range of 0.1 to 10 J / cm 2. In order to obtain a heat insulating material that achieves the object of the present invention, the cathode voltage is 10 to 30 kV, and the electron gun It is preferable to implement the gas pressure of the rare gas in the housing in the range of about 0.03 to 0.09 Pa. Further, the distance (irradiation distance) between the cathode and the irradiated surface of the ceramic porous body, which is an object to be irradiated, is about 15 to 50 mm so that the desired irradiation surface is irradiated with an electron beam having a desired irradiation energy density. Preferably there is. If the irradiation distance is shorter than this range, the energy density of the irradiated electron beam becomes high, and the deformation and roughness of the ceramic porous body, which is the surface of the irradiated object, becomes remarkable, which is not preferable. On the other hand, if the irradiation distance is larger than the above range, the irradiation energy density of the irradiated electron beam is too small, and the surface may not be sufficiently modified.
セラミックス多孔体上に、上記したような電子ビーム照射により形成される前駆層の厚さは、上記照射条件によって２〜３００μｍに制御されるが、より強固な結合を実現するためには５〜１００μｍの範囲となるように制御することが好ましい。 The thickness of the precursor layer formed by electron beam irradiation as described above on the ceramic porous body is controlled to 2 to 300 μm depending on the irradiation conditions, but 5 to 100 μm is required to realize stronger bonding. It is preferable to control to be in the range.
本発明の製造方法では、電子ビーム照射によるセラミックス多孔体の表面改質後、セラミックス多孔体と金属とを積層させて結合させる前に、セラミックス多孔体の表面改質部分に、結合に用いる金属以外の金属の箔や金属粉末をさらに接着及び含浸させ、表面改質部分と金属箔や金属粉末の接着・含浸部分をあわせて、一つの前駆層としてもよい。この場合に使用する金属箔又は金属粉末は、材質に特に制限はない。積層して結合する際に用いる金属と同素材の金属箔や金属粉末を用いてもよいが、本発明者らの検討によれば、この場合に用いる金属箔又は金属粉末として、結合させるセラミックス多孔体と金属の中間の熱膨張係数を示すものを選択することが好ましい。金属箔又は金属粉末を利用して異種材料を結合して得られる金属層を表面の一部に少なくとも有する本発明のセラミックス多孔体−金属断熱材は、例えば、断熱効率が求められるエンジンやタービン等の金属部品等に容易に組み込むことができる。本発明の断熱材をこれらの金属部品等に組み入れてセラミックス多孔質断熱材として使用した場合、急昇温及び降温する際にセラミックス多孔体と金属との熱膨張係数差によって生じる応力を緩和することもでき、その耐久性をより高めたものとなる。例えば、ジルコニア製の多孔体と金属アルミニウム板を積層複合化する場合、両素材の中間の熱膨張係数を示す、金や銀、銅等を選択して使用することが好ましい。 In the manufacturing method of the present invention, after the surface modification of the ceramic porous body by electron beam irradiation, before the ceramic porous body and the metal are laminated and bonded, the surface modified portion of the ceramic porous body other than the metal used for bonding The metal foil or metal powder may be further bonded and impregnated, and the surface modified portion and the metal foil or metal powder bonded / impregnated portion may be combined to form one precursor layer. The metal foil or metal powder used in this case is not particularly limited in material. A metal foil or metal powder of the same material as the metal used for stacking and bonding may be used, but according to the study by the present inventors, the ceramic porous to be bonded as the metal foil or metal powder used in this case is used. It is preferable to select one that exhibits a thermal expansion coefficient intermediate between the body and the metal. The ceramic porous body-metal heat insulating material of the present invention having at least a part of the surface of a metal layer obtained by bonding different materials using metal foil or metal powder is, for example, an engine or a turbine that requires heat insulation efficiency. Can be easily incorporated into metal parts and the like. When the heat insulating material of the present invention is incorporated into these metal parts and used as a ceramic porous heat insulating material, the stress caused by the difference in thermal expansion coefficient between the ceramic porous body and the metal is reduced when the temperature is rapidly increased or decreased. It is possible to improve the durability. For example, when a zirconia porous body and a metal aluminum plate are laminated and composited, it is preferable to select and use gold, silver, copper, or the like that exhibits an intermediate thermal expansion coefficient between the two materials.
セラミックス多孔体の表面改質層の形成の際に追加して金属箔又は金属粉末を接着及び含浸させる方法は、セラミックス多孔体表面を電子ビーム処理した方法と同等のものや、金属皮膜形成法の一つであるコールドスプレーや、通常金属表面の硬化処理法として知られているショットピーニングにおいて、基材に衝突させるショット材を目的の金属粉末にする方法などを選択することができる。このうち、電子ビーム処理法を選択すれば、表面処理も金属箔又は金属粉末の接着・含浸も、先に説明したと同一の電子ビーム面加工装置を用いることができるのでより好ましい。電子ビーム処理においては、接着・含浸させる金属をセラミックス多孔体上に設置した状態でビーム照射するため、金属粉末では飛散のおそれがあるため、金属箔を用いる方が好ましい。照射条件は、先述したと同様の条件で電子ビームを照射すればよい。 The method of adhering and impregnating metal foil or metal powder in addition to the formation of the surface modified layer of the ceramic porous body is equivalent to the method in which the surface of the ceramic porous body is subjected to electron beam treatment, or the method of forming a metal film. In one cold spray or shot peening, which is generally known as a method of hardening a metal surface, a method of making a shot material that collides with a base material into a target metal powder can be selected. Among these, it is more preferable to select an electron beam treatment method because both the surface treatment and the adhesion / impregnation of metal foil or metal powder can be performed using the same electron beam surface processing apparatus as described above. In the electron beam treatment, since the metal to be bonded and impregnated is irradiated with the beam placed on the ceramic porous body, the metal powder may be scattered, so it is preferable to use a metal foil. The irradiation conditions may be irradiation with an electron beam under the same conditions as described above.
用いる金属箔の厚さは、電子ビーム照射によりセラミックス多孔体の表面に、金属化して接着することが可能な範囲であればよく、１０〜１００μｍ程度が好ましい。それよりも薄い厚さでは、電子ビーム照射時の衝撃により金属箔が飛散し、十分に接着することができず、金属箔を利用したことによる十分な効果が得られ難い。一方、金属箔の厚みが上記範囲よりも厚い場合は、電子ビームのエネルギーが金属箔内までで留まってしまうおそれがあり、この場合は、セラミックス多孔体表面まで到達せず、金属箔をセラミックス多孔体の表面に接着することができないことが生じるおそれがあるので好ましくない。 The thickness of the metal foil to be used may be within a range that can be metalized and adhered to the surface of the ceramic porous body by electron beam irradiation, and is preferably about 10 to 100 μm. When the thickness is smaller than that, the metal foil is scattered due to the impact at the time of electron beam irradiation and cannot be sufficiently bonded, and it is difficult to obtain a sufficient effect by using the metal foil. On the other hand, if the thickness of the metal foil is larger than the above range, the energy of the electron beam may remain in the metal foil. In this case, the metal foil does not reach the surface of the ceramic porous body, and the metal foil is not porous. Since it may occur that it cannot adhere to the surface of the body, it is not preferable.
用いる金属粉末の粒径はセラミックス多孔体改質層表面への接着及び、円筒状の細孔内部への含浸が可能な大きさであれば良く、１０〜３００μｍ程度が好ましく、含浸を十分に行うためには１０〜１００μｍがより好ましい。 The particle size of the metal powder to be used may be a size that allows adhesion to the surface of the ceramic porous body modified layer and impregnation into the cylindrical pores, and is preferably about 10 to 300 μm, and sufficiently impregnates. Therefore, 10-100 micrometers is more preferable.
セラミックス多孔体に結合させる金属の材質は、特に限定されず、また、純金属であってもよいが、２種以上の金属を含有する合金であってもよい。２種以上の金属を含有するものとしては、例えば、鋼とその合金、鉄とその合金、アルミニウムとその合金、ニッケルとその合金が挙げられ、いずれであってもよい。これらの中から、その後に組み入れて複合体を形成する場合の金属部品や装置等の材質を考慮に入れて適宜に決定すればよい。また、セラミックス多孔体に結合させる金属の厚みは特に限定されず、用途に合わせて適宜に決定すればよいが、好ましくは、１００〜５，０００μｍ程度あれば十分である。すなわち、このような厚みの金属をセラミックス多孔体に結合させれば、良好な中間層が形成でき、しかも金属を主とする部品や装置等にろう付け等の方法で簡便に組み入れた場合に、良好な状態に複合化することができ、この結果、機能性に優れるセラミックスと金属との異種材料からなる複合体とできる。 The material of the metal bonded to the ceramic porous body is not particularly limited, and may be a pure metal or an alloy containing two or more metals. Examples of the material containing two or more metals include steel and its alloys, iron and its alloys, aluminum and its alloys, and nickel and its alloys. What is necessary is just to determine suitably from these, taking into consideration the material of a metal component, an apparatus, etc. in the case of incorporating after that and forming a composite_body | complex. Further, the thickness of the metal to be bonded to the ceramic porous body is not particularly limited, and may be appropriately determined according to the use, but it is preferably about 100 to 5,000 μm. In other words, if a metal with such a thickness is bonded to a porous ceramic body, a good intermediate layer can be formed, and when the metal is simply incorporated into a component or device mainly comprising metal by a method such as brazing, The composite can be formed in a good state, and as a result, a composite made of a heterogeneous material of ceramic and metal having excellent functionality can be obtained.
本発明のセラミックス多孔体−金属断熱材の製造方法では、先に挙げたような電子ビーム面加工装置を用い、上記で説明したような方法で前駆層を形成させ、この前駆層を有するセラミックス多孔体と、上記したような金属とを、前駆層の部分で接触させた状態で積層させ、この状態で、冶具等を用いて固定し、結合のための加熱を行う。本発明の製造方法では、結合させた金属がセラミックス多孔体の細孔内部まで侵入させた状態とするため、冶具等を用いて、セラミックス多孔体と金属とを固定する場合に、セラミックス多孔体と金属が接触した状態を保持できるように固定することを要する。 In the method for producing a ceramic porous body-metal heat insulating material of the present invention, a precursor layer is formed by the method described above using the electron beam surface processing apparatus as mentioned above, and the ceramic porous body having this precursor layer is formed. The body and the metal as described above are laminated while being in contact with each other at the portion of the precursor layer, and in this state, the body is fixed using a jig or the like, and heating for bonding is performed. In the manufacturing method of the present invention, in order to make the bonded metal penetrate into the pores of the ceramic porous body, when fixing the ceramic porous body and the metal using a jig or the like, It is necessary to fix the metal so that it can be kept in contact.
本発明のセラミックス多孔体−金属断熱材の製造方法で行う、結合のための加熱温度は、積層体を構成する金属と用いるセラミックス多孔体上の前駆層とが反応し結合できる温度であれば、いずれでもよい。すなわち、セラミックス多孔体の表面改質層と結合させる金属が反応できる温度、或いはセラミックス多孔体の表面改質層上に接着・含浸した金属箔又は金属粉末と積層する金属が反応できる温度であれば、いずれでもよい。例えば、銅箔を接着・含浸したセラミックス多孔体とアルミニウム板を結合する場合は、加熱雰囲気にもよるが、銅とアルミニウムで共晶反応を起こし、合金を形成できる約５５０℃以上とすることが好ましい。 The heating temperature for bonding performed in the method for producing a ceramic porous body-metal heat insulating material of the present invention is a temperature at which the metal constituting the laminate and the precursor layer on the ceramic porous body used can react and bond, Either is acceptable. That is, the temperature at which the metal bonded to the surface modified layer of the ceramic porous body can react, or the temperature at which the metal laminated on the surface modified layer of the ceramic porous body or the metal laminated with the metal powder can react Any of them may be used. For example, when bonding a ceramic porous body bonded and impregnated with copper foil and an aluminum plate, although it depends on the heating atmosphere, the eutectic reaction may occur between copper and aluminum and the alloy may be formed at about 550 ° C. or higher. preferable.
加熱雰囲気は、真空や不活性雰囲気であることを要するが、不活性雰囲気としては、例えば、アルゴンや窒素などを用いることができる。 The heating atmosphere needs to be a vacuum or an inert atmosphere, and as the inert atmosphere, for example, argon or nitrogen can be used.
図４は上記発明の実施形態によって電子ビームによる表面改質を施したセラミックス多孔体と金属とを積層複合化した複合体断熱材の断面ＳＥＭ写真である。セラミックス多孔体と金属の界面にコントラストの異なる中間層が形成されていることが確認できる。本発明者らは、この中間層は、セラミックス多孔体が、先に述べた（１）の工程で、低圧電離気体雰囲気下で電子ビームの照射を受けた結果、セラミックス多孔体の円筒状の細孔の骨格部表面が改質し、かつ隔壁の少なくとも一部が失われて、先に述べた（２）の工程で、結合させる金属を積層させ、接触させた状態で加熱した際に、該金属が該セラミックス多孔体内部に浸入し、表面改質部と浸入した金属とが反応し、この結果、機能性に優れた本発明の断熱材となったと考えている。本発明では、表面電子ビーム処理を施したセラミックス多孔体の処理面と複合化する金属を面で接触させ、接触した状態を保持しながら真空または不活性雰囲気中で加熱する。この結果、セラミックス多孔体の表面電子ビーム処理面（以下単にビーム処理面とも表記する）におけるセラミックスが改質した部分と、接触している金属との間で反応が起こり強固に結合されるが、例えば、先に述べた特有の微細な隔壁構造を有する多孔質セラミックスを用いた場合には、該反応がより効率よく円筒状のマクロ細孔内部で起こるので、セラミックス多孔体と金属とがより強固に結合された、より断熱材としての機能性に優れた、より耐久性に優れる複合化断熱材を得ることができたものと考えられる。 FIG. 4 is a cross-sectional SEM photograph of a composite heat insulating material in which a porous ceramic body subjected to surface modification by an electron beam according to the embodiment of the present invention and a metal are combined. It can be confirmed that intermediate layers having different contrasts are formed at the interface between the ceramic porous body and the metal. The inventors of the present invention have found that the intermediate layer has a cylindrical porous body formed of a ceramic porous body as a result of being irradiated with an electron beam in a low piezoelectric degassing atmosphere in the step (1) described above. When the surface of the pore skeleton is modified and at least a part of the partition wall is lost and the metal to be bonded is laminated and heated in the contact state in the step (2) described above, It is considered that the metal penetrates into the ceramic porous body, the surface reforming part reacts with the infiltrated metal, and as a result, the heat insulating material of the present invention having excellent functionality is obtained. In the present invention, the metal to be combined with the treated surface of the ceramic porous body subjected to the surface electron beam treatment is brought into contact with the surface and heated in a vacuum or an inert atmosphere while maintaining the contacted state. As a result, a reaction occurs between the ceramic-modified portion of the surface electron beam treated surface of the ceramic porous body (hereinafter also simply referred to as a beam treated surface) and the metal in contact, and the ceramic is firmly bonded. For example, when the porous ceramic having the above-mentioned specific fine partition structure is used, the reaction occurs more efficiently inside the cylindrical macropores, so that the ceramic porous body and the metal are stronger. It is considered that a composite heat insulating material that is more excellent in functionality as a heat insulating material and superior in durability can be obtained.
次に、実施例及び比較例に基づいて本発明をさらに具体的に説明する。
＜実施例１〜４、参考例１＞
実施例１〜４および参考例１では、気孔率が約８０％である、その気孔径が１０〜３００μｍの範囲にあり、平均気孔径が１００μｍであって、その大半が不連通（独立）の細孔である、５０ｍｍ（縦）×５０ｍｍ（横）×２０ｍｍ（厚み）の板状のジルコニア多孔体を用いた。図５に、その断面のＳＥＭ写真の図を示したが、上記で用いたジルコニア多孔体は、先に説明した特開２０１１−１９５４３７号公報に記載の、筒状のマクロ気孔内部に多数の節状の膜が架け渡され隔壁構造が存在する多孔質セラミックスである。このジルコニア多孔体に結合させる金属としては、上記のジルコニア多孔体と同様の大きさの平面を有する、厚みが５ｍｍの金属アルミニウム板（アルミニウム含有量９９％、ニラコ製）を用意した。
Next, the present invention will be described more specifically based on examples and comparative examples.
<Examples 1-4, Reference Example 1>
In Examples 1 to 4 and Reference Example 1, the porosity is about 80%, the pore diameter is in the range of 10 to 300 μm, the average pore diameter is 100 μm, and most of them are discontinuous (independent). A plate-like zirconia porous body having a pore size of 50 mm (length) × 50 mm (width) × 20 mm (thickness) was used. FIG. 5 shows an SEM photograph of the cross section, and the zirconia porous material used above has a number of nodes inside the cylindrical macropores described in JP-A-2011-195437 described above. Porous ceramics in which a film-like film is bridged and a partition wall structure exists. As a metal to be bonded to the zirconia porous body, a metal aluminum plate (aluminum content 99%, manufactured by Niraco) having a plane having the same size as the zirconia porous body and a thickness of 5 mm was prepared.
そして、これらの異種材料同士を、以下の手順で、結合・複合化させた。まず、電子ビーム装置（ソディック社製）を用い、上記ジルコニア多孔体表面の全面に、表１に示したようにしてカソード電圧を５〜５０ｋＶの範囲で変化させて、アルゴンガス圧０．０３ＭＰａで電子ビームを照射し、その表面改質を行い、ジルコニア多孔体表面に前駆層を形成させた。具体的には、カソード電圧を５〜５０ｋＶの範囲で、５ｋＶ（参考例１）、１５ｋＶ（実施例１）、２０ｋＶ（実施例２）、２５ｋＶ（実施例３）、５０ｋＶ（実施例４）でそれぞれ変化させた。図２（Ａ）は、２０ｋＶで電子ビーム照射後のジルコニア多孔体表面のＳＥＭ写真の図である。 Then, these dissimilar materials were combined and combined by the following procedure. First, using an electron beam apparatus (manufactured by Sodick), the cathode voltage was changed in the range of 5 to 50 kV as shown in Table 1 over the entire surface of the porous zirconia body, and the argon gas pressure was 0.03 MPa. The surface was modified by irradiating an electron beam, and a precursor layer was formed on the surface of the porous zirconia. Specifically, the cathode voltage is in the range of 5 to 50 kV, 5 kV (Reference Example 1), 15 kV (Example 1), 20 kV (Example 2), 25 kV (Example 3), 50 kV (Example 4). Each was changed. FIG. 2A is an SEM photograph of the surface of the porous zirconia after irradiation with an electron beam at 20 kV.
上記のようにしてジルコニア多孔体表面に形成した前駆層の面と、金属アルミニウム板とを接触させて積層した。そして、ジルコニア多孔体と金属アルミニウム板とが接触した状態を保持できるように、カーボン冶具にて固定をし、その状態で、真空条件下、７００℃で１時間加熱を行った。 The surface of the precursor layer formed on the surface of the porous zirconia as described above and the metal aluminum plate were brought into contact with each other and laminated. And it fixed with the carbon jig so that the state which the zirconia porous body and the metal aluminum plate contacted was maintained, and it heated at 700 degreeC on the vacuum conditions for 1 hour in the state.
その結果、ジルコニア多孔体と金属アルミニウム板とが中間層を介して結合してなる、実施例１〜４のセラミックス多孔体−金属断熱材を得た。参考例１は結合していなかった。得られた各断熱材の結合状態は、ジルコニア多孔体と金属アルミニウムとの結合された境界面に、いずれもジルコニアと金属アルミニウムを含む中間層が形成されていたが、その中間層の厚みは、それぞれ表１に示したようであった。なお、表１中に、金属と結合する前におけるジルコニア多孔体表面に形成された前駆体層の厚みも示した。上記で得られた各断熱材の中間層について詳細に検討したところ、いずれもジルコニア多孔体側の中間層の境界において、結合させた金属アルミニウムがジルコニア多孔体の細孔内部まで侵入していることを確認した。 As a result, ceramic porous body-metal heat insulating materials of Examples 1 to 4 in which the zirconia porous body and the metal aluminum plate were bonded via an intermediate layer were obtained. Reference Example 1 was not bonded. As for the bonding state of each obtained heat insulating material, an intermediate layer containing zirconia and metal aluminum was formed on the interface where the zirconia porous body and metal aluminum were bonded, but the thickness of the intermediate layer was Each was as shown in Table 1. In Table 1, the thickness of the precursor layer formed on the surface of the zirconia porous body before being bonded to the metal is also shown. When the intermediate layer of each heat insulating material obtained above was examined in detail, it was confirmed that the bonded metallic aluminum penetrated into the pores of the zirconia porous body at the boundary of the intermediate layer on the zirconia porous body side. confirmed.
＜実施例５＞
本実施例では、実施例１〜４および参考例１で用いた特開２０１１−１９５４３７号公報に記載された特有の隔壁構造が存在するジルコニア多孔体の代わりに、気孔率５０％、平均気孔径が８０μｍの特有の隔壁構造を有さない市販のジルコニア多孔体を用いた。形状は実施例１等と同様のものを用いた。結合させる金属には、実施例１等と同様の形状および厚みの金属アルミニウムを用いた。そして、実施例１等と同様の電子ビーム装置を用い、カソード電圧２０ｋＶ、アルゴンガス圧０．０３ＭＰａで、市販ジルコニア多孔体表面に電子ビーム照射による表面改質を行い、市販ジルコニア多孔体の表面に前駆層を形成させた。その後、市販ジルコニア多孔体表面の前駆層が形成されている部分に、用意した金属アルミニウム板を接触させて積層させた。そして、市販ジルコニア多孔体とアルミニウムそれぞれ接触した状態を保持できるようにカーボン冶具にて固定した。そして、実施例１等でしたと同様に、この状態で、真空条件下、７００℃で１時間加熱を行って結合し、市販ジルコニア多孔体と金属アルミニウムとの断熱材を得た。そして、得られた断熱材の中間層は、ジルコニア多孔体側の中間層の境界において、結合させた金属アルミニウムがジルコニア多孔体の細孔内部まで侵入していることを確認した。
<Example 5>
In this example, in place of the zirconia porous body having a specific partition structure described in JP-A No. 2011-195437 used in Examples 1 to 4 and Reference Example 1, the porosity was 50% and the average pore diameter was A commercially available zirconia porous body having a specific partition wall structure of 80 μm was used. The same shape as in Example 1 was used. As the metal to be bonded, metallic aluminum having the same shape and thickness as in Example 1 or the like was used. Then, using the same electron beam apparatus as in Example 1 and the like, the surface of the commercially available zirconia porous body is subjected to surface modification by electron beam irradiation at a cathode voltage of 20 kV and an argon gas pressure of 0.03 MPa. A precursor layer was formed. Then, the prepared metal aluminum plate was contacted and laminated | stacked on the part in which the precursor layer of the surface of a commercial zirconia porous body was formed. And it fixed with the carbon jig so that the state which each contacted the commercially available zirconia porous body and aluminum each could be hold | maintained. And like Example 1 etc., in this state, it heated and combined at 700 degreeC under vacuum conditions for 1 hour, and obtained the heat insulating material of the commercial zirconia porous body and metal aluminum. It was confirmed that the obtained intermediate layer of the heat insulating material penetrated into the pores of the zirconia porous body at the boundary of the intermediate layer on the zirconia porous body side.
＜実施例６＞
本実施例では、気孔率が８５％で、平均気孔径が５０μｍである、実施例１等で用いたと同様の特有の隔壁構造が存在する板状のアルミナ多孔体を用いた。複合化させる金属には、実施例１等と同様の形状および厚みの金属アルミニウムを用いた。そして、実施例１等と同様の電子ビーム装置を用い、カソード電圧２５ｋＶ、アルゴンガス圧０．０３ＭＰａで、アルミナ多孔体表面の電子ビーム照射による表面改質を行った。その後、本実施例では、アルミナ多孔体改質の表面の改質処理されている部分に、厚さ２０μｍの金箔（ニラコ製）を、上記と同様の条件で、電子ビーム照射により接着させて前駆層とした。その後、アルミナ多孔体表面の前駆層が形成されている部分に、用意した金属アルミニウム板を接触させて積層させた。そして、アルミナ多孔体と金属アルミニウムとが接触した状態を保持できるようにカーボン冶具にて固定をした。そして、実施例１でしたと同様に、この状態で、真空条件下、７００℃で１時間加熱を行って、アルミナ多孔体と金属アルミニウムとが強固に結合した断熱材を得た。そして、得られた断熱材の中間層は、アルミナ多孔体側の中間層の境界において、金属アルミニウムと結合の際に用いた金箔とがアルミナ多孔体の細孔内部まで侵入していることを確認した。
<Example 6>
In this example, a plate-like alumina porous body having a specific partition structure similar to that used in Example 1 and the like having a porosity of 85% and an average pore diameter of 50 μm was used. As the metal to be combined, metallic aluminum having the same shape and thickness as in Example 1 and the like was used. Then, using the same electron beam apparatus as in Example 1 and the like, surface modification by electron beam irradiation of the alumina porous body surface was performed at a cathode voltage of 25 kV and an argon gas pressure of 0.03 MPa. Thereafter, in this example, a 20 μm-thick gold foil (manufactured by Niraco) is adhered to the surface of the alumina porous body modified surface by electron beam irradiation under the same conditions as described above. Layered. Then, the prepared metal aluminum plate was contacted and laminated | stacked on the part in which the precursor layer of the alumina porous body surface is formed. And it fixed with the carbon jig so that the state which the alumina porous body and metal aluminum contacted can be hold | maintained. Then, as in Example 1, in this state, heating was performed at 700 ° C. for 1 hour under vacuum conditions to obtain a heat insulating material in which the alumina porous body and the metal aluminum were firmly bonded. And it was confirmed that the intermediate layer of the obtained heat insulating material penetrated into the pores of the alumina porous body at the boundary of the intermediate layer on the alumina porous body side with the metal aluminum and the gold foil used for bonding. .
＜比較例１＞
アルミナ多孔体の代わりに、気孔率１％以下のアルミナ緻密質体を用いた以外は実施例６と同様にして、アルミナ緻密質体と金属アルミニウムとを結合処理を行ったところ、実施例で見られたような強固な結合を形成することはできなかった。
<Comparative Example 1>
In the same manner as in Example 6 except that an alumina dense body having a porosity of 1% or less was used in place of the alumina porous body, the alumina dense body and metal aluminum were subjected to a bonding treatment. It was not possible to form such a strong bond.
＜実施例７＞
本実施例では、実施例１等と同様の構造を有し、同様の形状であるジルコニア多孔体を用いた。複合化させる金属には、実施例１等と同様の形状の金属アルミニウムを用いた。そして、実施例１等と同様の電子ビーム装置を用い、カソード電圧２０ｋＶ、アルゴンガス圧０．０３ＭＰａで、平板状のジルコニア多孔体表面の５０×５０ｍｍの面の表裏２面に電子ビーム照射による表面改質を行い、ジルコニア多孔体の対峙する２面に前駆層を形成させた。
<Example 7>
In this example, a zirconia porous body having the same structure as that of Example 1 and the like and having the same shape was used. As the metal to be combined, metallic aluminum having the same shape as in Example 1 was used. Then, using the same electron beam apparatus as in Example 1 or the like, the surface by electron beam irradiation on the front and back surfaces of the 50 × 50 mm surface of the flat plate-like zirconia porous body surface at a cathode voltage of 20 kV and an argon gas pressure of 0.03 MPa Modification was performed, and a precursor layer was formed on two opposing surfaces of the zirconia porous body.
上記のようにしてジルコニア多孔体の２面に形成した前駆層の各面と、金属アルミニウム板とを接触させて金属アルミニウム板−ジルコニア多孔体−金属アルミニウム板の順に積層した。そして、ジルコニア多孔体と金属アルミニウム板とが接触した状態を保持できるように、カーボン冶具にて固定をし、その状態で、真空条件下、７００℃で１時間加熱を行った。 Each surface of the precursor layer formed on the two surfaces of the zirconia porous body as described above was brought into contact with the metal aluminum plate and laminated in the order of metal aluminum plate-zirconia porous body-metal aluminum plate. And it fixed with the carbon jig so that the state which the zirconia porous body and the metal aluminum plate contacted was maintained, and it heated at 700 degreeC on the vacuum conditions for 1 hour in the state.
＜評価＞
（１）断熱性
気孔率と特有の隔壁構造の存在の有無が異なるジルコニア多孔体をそれぞれに用い、電子ビームの照射条件を同一として得た実施例３と実施例５のジルコニア多孔体−金属断熱材（以下単に断熱材とも表記する）を用い断熱性を評価した。評価方法は、まず、評価試料とするため、断熱材の金属層側と５０×５０×５０ｍｍのアルミニウム合金（Ａ５００５）とを無機系接着剤を用いて接着させて複合体を得た。そして、入口開放型の電気炉を用い、評価試料のジルコニア多孔体の部分のみを１，０００℃に加熱した電気炉内へ挿入し、アルミニウム合金の部分は大気に触れるようにし、電気炉入口の隙間はアルミナ−シリカ系断熱ファイバーを用い熱が外に漏れないようにし、アルミニウム合金の端面に熱電対を装着し、挿入５分後の温度を測定した。測定の結果、実施例３の評価試料は約２５０℃であったのに対し、実施例５の評価試料は約４００℃であり、その断熱性能が実施例３のものより劣っていた。これは、実施例３の断熱材は、セラミックス多孔体の気孔率が８０％と非常に高く、さらに隔壁構造を有しているため、より断熱性に優れた結果が得られたと考えられる。
<Evaluation>
(1) Thermal insulation The zirconia porous body-metal thermal insulation of Example 3 and Example 5 obtained by using the same irradiating conditions of the electron beam by using zirconia porous bodies having different porosity and presence or absence of a specific partition structure. A heat insulating property was evaluated using a material (hereinafter also simply referred to as a heat insulating material). In the evaluation method, first, in order to obtain an evaluation sample, the metal layer side of the heat insulating material and an aluminum alloy (A5005) of 50 × 50 × 50 mm were bonded using an inorganic adhesive to obtain a composite. Then, using an electric furnace with an open inlet, only the zirconia porous body part of the evaluation sample was inserted into an electric furnace heated to 1,000 ° C., and the aluminum alloy part was exposed to the atmosphere. The gap was made of an alumina-silica heat insulating fiber so that heat did not leak outside, a thermocouple was attached to the end face of the aluminum alloy, and the temperature was measured 5 minutes after insertion. As a result of the measurement, the evaluation sample of Example 3 was about 250 ° C., whereas the evaluation sample of Example 5 was about 400 ° C., and its heat insulation performance was inferior to that of Example 3. This is probably because the heat insulating material of Example 3 had a very high porosity of 80% of the ceramic porous body, and further had a partition structure, so that a better heat insulating result was obtained.
（２）結合性および耐熱衝撃性
電子ビームの照射条件を変えて得た実施例２、実施例４の断熱材と、金属アルミニウム板−ジルコニア多孔体−金属アルミニウム板の３層構造を有する実施例７の断熱材を用い、下記のようにして結合性および耐熱衝撃性を調べた。先に行った断熱性評価に用いた入口開放型電気炉を用い、実施例２及び４の断熱材は同様にジルコニア多孔体の部分のみを、実施例７の断熱材は３層のうちアルミニウム層−ジルコニア多孔体層のみを６００℃で１０分間加熱した後、空冷にて急冷し、その後も加熱と急冷を繰り返して断熱材の変化を観察した。
(2) Bondability and thermal shock resistance Example having three-layer structure of Example 2 and Example 4 obtained by changing electron beam irradiation conditions and metal aluminum plate-porous zirconia-metal aluminum plate Using the heat insulating material of No. 7, the bondability and thermal shock resistance were examined as follows. Using the open-open electric furnace used for the heat insulation evaluation performed previously, the heat insulating materials of Examples 2 and 4 were similarly the zirconia porous body part, and the heat insulating material of Example 7 was an aluminum layer of the three layers. -After heating only a zirconia porous material layer at 600 degreeC for 10 minute (s), it rapidly_cool | quenched by air cooling, The heating and rapid cooling were repeated after that, and the change of the heat insulating material was observed.
上記した操作を１０回繰り返した結果、実施例２の断熱材はジルコニア多孔体層に微細な亀裂が生じたものの、結合部分が剥離することはなかった。これに対し、実施例４の断熱材は３回目の空冷中に結合部分が剥離した。さらに、実施例７の断熱材は加熱されたアルミニウム層が試験中に軟化し表面が荒れたように形状が変化していたものの、ジルコニア多孔体が露出することはなかった。断熱材の結合性の違いは、セラミックス多孔体の電子ビーム照射による表面改質条件が影響しているものと考えられ、実施例４のように、高すぎるカソード電圧で処理するとセラミックス多孔体表面が過度に荒れてしまい、金属との結合性が劣るという結果が得られた。そして、耐熱衝撃性は、実施例７のように３層構造で断熱層であるセラミックス多孔体の上表面を金属でコーティングされたようになっていると有効であることが示唆された。このことは、使用温度域と材質の検討で、爆発的な熱衝撃をともなう内燃機関の断熱材への使用が期待される。 As a result of repeating the above-described operation 10 times, in the heat insulating material of Example 2, although the fine crack was generated in the zirconia porous body layer, the bonded portion was not peeled off. On the other hand, the bonded portion of the heat insulating material of Example 4 was peeled off during the third air cooling. Furthermore, although the shape of the heat insulating material of Example 7 was changed so that the heated aluminum layer softened during the test and the surface was roughened, the zirconia porous body was not exposed. The difference in the bonding property of the heat insulating material is considered to be affected by the surface modification conditions of the ceramic porous body by electron beam irradiation. The result was that the metal was excessively rough and the bonding with the metal was poor. It was suggested that the thermal shock resistance is effective when the upper surface of the ceramic porous body, which is a heat insulating layer, is coated with a metal as in Example 7 in a three-layer structure. This is expected to be used as a heat insulating material for an internal combustion engine with explosive thermal shock in examination of the operating temperature range and material.
（３）セラミックスの気孔率の影響
セラミックス多孔体の表面改質に、結合させる金属とは別に金箔を用いた実施例６及び比較例１におけるセラミックス多孔体又はセラミックス緻密質体表面に形成された前駆層を電子顕微鏡により観察した。この結果、図３（ｂ）に示したように、実施例６のセラミックス多孔体表面は全体に金属箔が表面一面に接着した状態になっており、特に表面に露出している開気孔の箇所に重点的に金属箔が接着されていた。一方、比較例１のセラミックス緻密質体表面では局所的に金属箔の接着が見られたものの、一面には接着していなかった。実施例６で得た断熱材は、比較例１で得た断熱材と比べてその結合強度が極めて高かった。これは、上記したように、実施例６では、比較例１の場合と異なり金属箔が気孔部分に重点的に接着していたことから、金属と結合させた場合に、実施例６の断熱材では、結合させた金属がセラミックス多孔体の細孔内部まで侵入でき、この結果、いわゆるアンカー効果が得られたためと考えられる。
(3) Influence of porosity of ceramics Precursor formed on the surface of the ceramic porous body or the ceramic dense body in Example 6 and Comparative Example 1 using gold foil separately from the metal to be bonded for surface modification of the ceramic porous body The layer was observed with an electron microscope. As a result, as shown in FIG. 3 (b), the surface of the porous ceramic body of Example 6 is in a state where the metal foil is adhered to the entire surface, and in particular, the location of open pores exposed on the surface The metal foil was glued with emphasis on. On the other hand, although the adhesion of the metal foil was observed locally on the surface of the ceramic dense body of Comparative Example 1, it was not adhered to one surface. The heat insulating material obtained in Example 6 had extremely high bond strength as compared with the heat insulating material obtained in Comparative Example 1. This is because, as described above, in Example 6, unlike the case of Comparative Example 1, since the metal foil was preferentially adhered to the pores, the heat insulating material of Example 6 was combined with the metal. Then, it is considered that the bonded metal can penetrate into the pores of the ceramic porous body, and as a result, a so-called anchor effect was obtained.
１：セラミックス多孔体
２：電子ビーム
３ａ：セラミックス多孔体の表面改質層（前駆層ａ）
３ｂ：セラミックス多孔体の表面改質層にさらに金属箔が接着・含浸した層（前駆層ｂ）
４：金属箔
５：金属板
６：前駆層と金属板の結合により生成した中間層
1: Ceramic porous body 2:
3b: Layer in which a metal foil is further adhered and impregnated on the surface modified layer of the ceramic porous body (precursor layer b)
4: Metal foil 5: Metal plate 6: Intermediate layer formed by bonding of precursor layer and metal plate
Claims (8)
前記セラミックス多孔体が、気孔率が５０〜９９％で、かつ、気孔径が１０〜３００μｍの円筒形状のマクロ細孔を有し、その細孔の内壁に多数の節状の膜が掛け渡され隔壁を形成した、不連通の細孔を有する隔壁構造を主とするものであり、
該セラミックス多孔体と前記金属層とが結合しているセラミックス多孔体と金属との界面に、該セラミックスと該金属とが含有されてなる厚みが２０〜５００μｍの範囲内にある中間層が形成されており、かつ、該中間層のセラミックス多孔体側において、結合させた金属がセラミックス多孔体の細孔内部まで侵入しており、前記結合させた金属がセラミックス多孔体の細孔内部に存在している範囲が、セラミックス多孔体の表面から１０〜３００μｍであることを特徴とするセラミックス多孔体−金属断熱材。 A ceramic porous body-metal heat insulating material that can be easily combined by joining with a mechanical component mainly made of metal, in which a metal layer is firmly bonded to at least a part of the surface of the ceramic porous body,
The ceramic porous body has cylindrical macropores having a porosity of 50 to 99% and a pore diameter of 10 to 300 μm, and a large number of nodular films are spanned on the inner walls of the pores. The main structure is a partition wall structure having discontinuous pores, in which a partition wall is formed,
The interface between the ceramic porous body and the metal to the ceramic porous body and said metal layer is bonded, thickness of the said ceramics and the metal, which are contained in the intermediate layer is formed in the range of 20~500μm and, and, in the ceramic porous body side of the intermediate layer, metallic conjugated have to penetrate the pores of the ceramic porous body, a metal obtained by the coupling is present within the pores of the ceramic porous body range, porous ceramics, characterized in 10~300μm der Rukoto from the surface of the porous ceramics are - metal insulation.
セラミックス多孔体表面に金属層を結合させる部分に、電子ビーム面加工装置を用い、カソードに対する加速印加電圧を１０ｋＶ〜３０ｋＶ、電子銃ハウジング内の希ガスのガス圧を０．０３ＭＰａ〜０．０９ＭＰａの範囲で制御して、電子ビームの照射エネルギー密度が０．１〜１０Ｊ／ｃｍ2の範囲に制御した電子ビームを照射し、照射した部分を表面改質した後、その表面改質部分に、結合させる１００〜５，０００μｍの厚みの金属を接触させた状態で積層させ、セラミックス多孔体と金属が接触した状態を保持できるように冶具にて上記積層状態を固定し、真空条件下或いは不活性雰囲気下、５００℃以上の温度で加熱してセラミックス多孔体と金属とを結合させて金属層を形成することを特徴とするセラミックス多孔体−金属断熱材の製造方法。 A method for producing a ceramic porous body-metal heat insulating material according to any one of claims 1 to 5,
An electron beam surface processing apparatus is used for the portion where the metal layer is bonded to the surface of the ceramic porous body, the acceleration applied voltage to the cathode is 10 kV to 30 kV, and the gas pressure of the rare gas in the electron gun housing is 0.03 MPa to 0.09 MPa. The range is controlled so that the irradiation energy density of the electron beam is controlled within the range of 0.1 to 10 J / cm 2 , and the irradiated portion is surface-modified and then bonded to the surface-modified portion. Lamination is performed in a state where a metal having a thickness of 100 to 5,000 μm is in contact, and the above-mentioned lamination state is fixed with a jig so that the state in which the ceramic porous body and the metal are in contact can be maintained. A ceramic porous body-metal heat insulation characterized by heating at a temperature of 500 ° C. or more to bond the ceramic porous body and metal to form a metal layer A method of manufacturing the material.
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