JP3953944B2 - Metal foil and honeycomb structure - Google Patents
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- JP3953944B2 JP3953944B2 JP2002336049A JP2002336049A JP3953944B2 JP 3953944 B2 JP3953944 B2 JP 3953944B2 JP 2002336049 A JP2002336049 A JP 2002336049A JP 2002336049 A JP2002336049 A JP 2002336049A JP 3953944 B2 JP3953944 B2 JP 3953944B2
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Description
【０００１】
【発明の属する技術分野】
本発明は、触媒担体として好適なハニカム体及びハニカム体を構成する金属箔に関するものである。
【０００２】
【従来の技術】
内燃機関の排気ガスを浄化する目的で、排気ガス経路に触媒を担持した触媒コンバータが配置される。また、メタノール等の炭化水素化合物を水蒸気改質して水素リッチなガスを生成するメタノール改質装置やＣＯをＣＯ2に改質して除去するＣＯ除去装置、あるいはＨ2をＨ2Ｏに燃焼して除去するＨ2燃焼装置においても、同様に触媒を担持した担体が用いられる。これら触媒担体は、ガスが通過する多数のセルを有し、各セルの壁面には触媒がコーティングされ、通過するガスと触媒とが広い接触面積で接触することが可能になっている。
【０００３】
これらの目的で用いられる触媒担体としては、セラミックス触媒担体とメタル触媒担体とがある。メタル触媒担体は、耐熱合金を用いた厚み数十μｍの平箔と波箔とを交互に巻き回し、あるいは積層することによって円筒形のメタルハニカム体とし、このメタルハニカム体を円筒形の金属製の外筒に装入してメタル担体とする。このメタル担体のガス通路となるハニカム体のセルの金属箔の表面に触媒をしみ込ませた触媒担持層を形成し、触媒担体とする。平箔と波箔とを巻き回し積層したハニカム体の該平箔と波箔との接触部は、ロウ付け等の手段によって接合し、ハニカム体を強度のある構造体とする。
【０００４】
触媒担体のガス通路となるメタルハニカム体のセルの金属箔の表面に、ウォッシュコート層と呼ばれるポーラスなγ−アルミナ層をコーティングし、このウォッシュコート層に貴金属等から成る触媒をしみ込ませる方法、または触媒を含んだウォッシュコート層をメタルハニカム体にコーティングする方法等があって、ハニカム体を構成する金属箔表面に触媒を担持させている。メタルハニカム体のセル表面にウォッシュコート層を形成する方法としては、ウォッシュコート液中にハニカム体を浸漬することによってハニカム体のセル表面に該ウォッシュコート液を付着させ、次いで乾燥することによってウォッシュコート層をセル表面に形成する方法が用いられている。
【０００５】
特許文献１には、メタルハニカム体の金属箔表面とウォッシュコート層との密着性を改善するため、Ａｌ含有ステンレス鋼金属箔を用いてハニカム体を形成し、その後大気中で熱処理して鋼中のＡｌを利用してステンレス鋼表面にα−アルミナウィスカーを生成させ、この針状結晶の上にγ−アルミナをコーティングする方法が記載されている。α−アルミナウィスカーの生成を促進するため、Ａｌ含有ステンレス鋼を予めＣＯ2雰囲気などで加熱処理する方法が、特許文献２に記載されている。
【０００６】
【特許文献１】
特公平８−１９７号公報
【特許文献２】
特開昭５７−７１８９８号公報
【０００７】
【発明が解決しようとする課題】
金属箔表面にα−アルミナウィスカーを生成しようとすると、ハニカム体を大気中あるいは雰囲気中で熱処理する必要がある。これではα−アルミナウィスカーのＡｌ源は箔素材であるが、このα−アルミナウィスカーにより箔素材中のＡｌ濃度が減少する。従って、本来もち得る箔の耐酸化性を発揮することができない。
【０００８】
触媒担体を用いた排気ガスの浄化において、ハニカム体のセルを通過する排気ガスとセル表面の触媒との間の物質移動が活発になるほど触媒反応が進行し、排気ガスの浄化効率が向上する。
【０００９】
本発明は、メタルハニカム体の金属箔表面とウォッシュコート層との密着性を改善することのできる金属箔及びハニカム体を提供することを第１の目的とする。本発明はまた、ハニカム体のセルを通過するガスと触媒との間の物質移動を活発化することのできる金属箔及びハニカム体を提供することを第２の目的とする。
【００１０】
【課題を解決するための手段】
即ち、本発明の要旨とするところは以下の通りである。
（１） 熱間圧延と冷間圧延を経た厚さが１００μｍ以下のステンレス鋼金属箔であって、金属箔表面に高さ１μｍ以上の突起が１００個／ｃｍ2以上存在し、箔中のＡｌ濃度が６．５質量％超１５質量％以下であり、突起が金属であり、突起中のＡｌ濃度が金属箔中のＡｌ濃度よりも高いことを特徴とする金属箔。
（２） 前記突起は、平均粒径０．１〜５０μｍのＡｌ粉末を溶融、固化してなる突起であることを特徴とする上記（１）に記載の金属箔。
（３） 箔の成分が質量％で、Ｓｉ：０．１％以上１．０％以下、Ｍｎ：０．５％以下、Ａｌ：６．５％超１５％以下、Ｃｒ：１０％以上３０％以下、残部Ｆｅ及び不可避不純物からなることを特徴とする上記（１）又は（２）に記載の金属箔。
（４） 箔の成分が質量％でさらに、Ｔｉ：０．０２％以上０．１％以下とＮｂ：０．０２％以上０．３％以下の一方又は両方、Ｌａ：０．０１％以上０．１％以下、Ｃｅ：０．０１％以上０．１％以下、Ｐ：０．０１％以上０．０５％以下を含むことを特徴とする上記（３）に記載の金属箔。
【００１１】
（５） 上記（１）乃至（４）のいずれかに記載の金属箔によって構成されてなることを特徴とするハニカム体。
【００１２】
（６） Ａｌ含有量が６．５質量％以下の連続鋳造鋳片を熱間圧延し、その後冷間圧延を経て金属箔とし、金属箔の表面にＡｌ粉末を塗布し、次いで金属箔を焼成することを特徴とする上記（１）乃至（４）のいずれかに記載の金属箔の製造方法。
（７） 金属箔の表面に平均粒径０．１〜５０μｍのＡｌ粉末と樹脂と溶剤からなる１０〜５０００ｃｐの粘度のＡｌペイントを塗布し、次いで金属箔を６００℃以上１０００℃以下で焼成することを特徴とする上記（６）に記載の金属箔の製造方法。
（８） 前記焼成雰囲気が不活性雰囲気である上記（７）に記載の金属箔の製造方法。
（９） Ａｌ含有量が６．５質量％以下の連続鋳造鋳片を熱間圧延し、その後冷間圧延を経て金属箔とした上で、該金属箔を用いてハニカム体を形成し、ハニカム体を構成する金属箔の表面にＡｌ粉末を塗布し、次いでハニカム体を焼成することを特徴とする上記（５）に記載のハニカム体の製造方法。
（１０） ハニカム体を構成する金属箔の表面に平均粒径０．１〜５０μｍのＡｌ粉末と樹脂と溶剤からなる１０〜５０００ｃｐの粘度のＡｌペイントを塗布し、次いでハニカム体を６００℃以上１０００℃以下で焼成することを特徴とする上記（９）に記載のハニカム体の製造方法。
（１１） ハニカム体を構成する金属箔の表面に接着剤を塗布し、その後該ハニカム体に平均粒径０．１〜５０μｍのＡｌ粉末を振りかけ、金属箔表面の接着剤塗布部にＡｌ粉末を被着させ、次いで金属箔を６００℃以上１０００℃以下で焼成することを特徴とする上記（９）に記載のハニカム体の製造方法。
（１２） 前記焼成雰囲気が不活性雰囲気である上記（１０）又は（１１）に記載のハニカム体の製造方法。
【００１３】
【発明の実施の形態】
本発明のハニカム体において、ハニカム体を構成する金属箔の表面に高さ１μｍ以上の突起が１００個／ｃｍ2以上存在すると、このハニカム体にウォッシュコート層を形成するに際し、ウォッシュコート層の食いつきがよくなり、金属箔表面とウォッシュコート層との密着性を改善することができる。また、ハニカム体のセル表面を形成する金属箔の表面に突起が存在するため、セル表面に凹凸が生じ、セルを通過するガスの乱流化が進み、乱流効果によってセル表面と接触するガスの入れ替わりが促進され、触媒反応を促進することができる。ここでいう突起とは、箔表面にイボ状に飛び出しているものをいう。
【００１４】
金属箔表面に形成される突起高さは１μｍ以上であることが必要である。１μｍ未満では、ウォッシュコートの接着性を上げる効果が得られない。突起高さは２μｍ以上であるとより好ましい。また、突起の存在密度は１００個／ｃｍ2以上であることが必要である。これにより、突起を用いたウォッシュコート層の密着性を改善効果を確実に上げることができる。本発明の金属箔の厚さを１００μｍ以下と限定する理由は、１００μｍを超えると、ハニカム体としたときに圧力損失が大きくなりすぎるからである。
【００１７】
本発明の金属箔は、表面に突起を有することにより、この金属箔を用いてハニカム体を形成したときに、上記と同様の効果を得ることができる。
【００１８】
本発明の金属箔及びハニカム体を構成する金属箔としては、箔の成分が質量％で、Ｓｉ：０．１％以上１．０％以下、Ｍｎ：０．５％以下、Ａｌ：６．５％超１５％以下、Ｃｒ：１０％以上３０％以下、残部Ｆｅ及び不可避不純物からなる金属箔を用いると耐酸化性が向上し好ましい。
【００１９】
Ｍｎを０．５％以下とするのは、これによって金属箔の耐酸化性を確保するためである。
【００２０】
Ｓｉを０．１％以上含有することにより、金属箔の耐酸化性を向上させることができる。ただし、Ｓｉ含有量が１．０％を超えると金属箔の脆化が進むので、上限を１．０％とする。
【００２１】
Ａｌを６．５％超含有することにより、金属箔の耐酸化性を向上させることができる。ただし、Ａｌ含有量が１５％を超えると金属箔の脆化が進むので、上限を１５％とする。
【００２２】
Ｃｒを１０％以上含有することにより、金属箔の耐酸化性を向上させることができる。ただし、Ｃｒ含有量が３０％を超えると金属箔の脆化が進むので、上限を３０％とする。
【００２３】
本発明の金属箔及びハニカム体を構成する金属箔は、さらに、Ｔｉ：０．０２％以上０．１％以下とＮｂ：０．０２％以上０．３％以下の一方又は両方、Ｌａ：０．０１％以上０．１％以下、Ｃｅ：０．０１％以上０．１％以下、Ｐ：０．０１％以上０．０５％以下を含むこととすると好ましい。
【００２４】
Ｔｉ：０．０２％以上、Ｎｂ：０．０２％以上の一方又は両方を含有することにより、金属箔の靭性を改善することができる。ただし、Ｔｉが０．１％、Ｎｂが０．３％を超えると金属箔の耐酸化性に悪影響を及ぼすので、これらの値を上限とした。
【００２５】
Ｌａ：０．０１％以上、Ｃｅ：０．０１％以上を含有することにより、金属箔の耐酸化性を向上することができる。ただし、Ｌａが０．１％、Ｃｅが０．１％を超えると熱延割れの原因となるので、これらの値を上限とした。
【００２６】
Ｐを０．０１％以上含有すると、Ｌａ、Ｃｅ含有時の熱延割れ発生を防止する効果がある。ただし、Ｐ含有量が０．０５％を超えると耐酸化性の劣化を招くので、この値を上限とした。
【００２７】
本発明の金属箔の表面に高さ１μｍ以上、１００個／ｃｍ2以上の突起を生成するための金属箔の製造方法について説明する。
【００２８】
ステンレス鋼箔表面にＡｌを付着させる手段としては、箔表面にＡｌペイントを塗布する方法を採用することができる。Ａｌ粉末と樹脂と溶剤とからなるペイントを準備する。Ａｌ粉末は平均粒径０．１〜５０μｍ程度のものが使用できる。また、Ａｌ粉末として、フレーク状のものを使用すれば、さらに好ましい効果が得られる。樹脂は、乾燥により溶剤を揮発せしめた後、セル壁面に固着させておくのに必要である。エチルセルロース、フェノール等一般的に使用される樹脂を用いればよい。溶剤としても、工業用灯油やキシレン等を用いればよい。溶剤の量はペイントの粘度を管理するのに重要である。ペイント粘度は１０〜５０００ｃｐの間に保っておくと良い結果が得られる。このペイントを金属箔表面に塗布する。塗布の方法としては、ペイント液中にハニカム体を浸漬する方法を用いることができる。その後ペイントを塗布した金属箔を焼成する。焼成雰囲気は、大気中でも不活性雰囲気でも良いが、不活性雰囲気がより好ましい。Ａｌ粉末を溶融させるため、焼成温度は６００℃以上とする。ペイント中に樹脂を含む場合には、この焼成によって樹脂が熱分解除去される。
【００２９】
ペイントを塗布した金属箔を焼成した結果として、ペイント中のＡｌ粉末が溶融し、金属箔の表面に多数の溶融Ａｌ液滴が形成される。溶融Ａｌ液滴と接する金属箔から、金属箔の成分が液滴中に拡散し、この成分と液滴中のＡｌとが合金化かつ固相化する。この状態で金属箔の温度を低下させると、液滴部が突起を形成する。このようにして形成した突起は金属である。また、突起部の組成は、突起中のＡｌ濃度が金属箔中のＡｌ濃度よりも高い値の組成となる。
【００３０】
以上の方法を用いて形成した金属箔表面の突起は、突起の高さを１μｍ以上とすることができ、また突起の密度を１００個／ｃｍ2以上とすることができる。
【００３１】
金属箔表面に塗布したペイント中のＡｌ粉末は、その一部は上記のように金属箔表面に多数の溶融Ａｌ液滴を形成し、最終的に突起を形成する。一方、その他のＡｌ粉末は焼成時に溶融し、金属箔中に拡散し、金属箔中の構成成分と合金化する。
【００３２】
本発明のＡｌ含有ステンレス鋼金属箔を製造するに際しては、通常は連続鋳造鋳片を熱間圧延し、その後冷間圧延を経て金属箔とする。熱間圧延前の鋳片中のＡｌ含有量が６．５％を超えていると、熱間圧延において加工性が悪く、良好な圧延を行うことができない。本発明においては、熱間圧延前の鋳片中Ａｌ含有量は６．５％以下としておき、金属箔の段階で表面にＡｌ粉末を含有するペイントを塗布し、焼成によって金属箔中にＡｌを拡散させ、これによって金属箔中のＡｌ含有量を６．５％超とすることができる。Ａｌ含有量を６．５％超とすることにより、この金属箔は極めて良好な耐酸化性を具備することとなる。
【００３３】
金属箔表面へのＡｌ粉末塗布は、上記のように、ハニカム体を形成する前の金属箔に塗布することとしても良いが、ハニカム体を形成した後の金属箔に塗布することとするとより好ましい。ハニカム体を構成する金属箔の表面へのＡｌ粉末の塗布は、上記のようにＡｌ粉末と樹脂と溶剤からなるペイント中にハニカム体を浸漬することによって行うことができる。あるいは、ハニカム体を構成する金属箔の表面に接着剤を塗布し、その後ハニカム体にＡｌ粉末を振りかけ、金属箔表面の接着剤塗布部にＡｌ粉末を被着させる方法を採用しても良い。Ａｌ粉末を塗布後にハニカム体を焼成することにより、上記金属箔の場合と同様、ハニカム体を構成する金属箔表面に突起を形成することができ、同時に金属箔中のＡｌ含有量を増大させることができる。上記焼成は、上記金属箔の焼成と同様の条件を採用することができ、あるいはハニカム体の金属箔接触部をろう付けするための熱処理を兼ねて行うことができる。
【００３９】
【実施例】
含有成分が質量％で、Ｃ：０．００７％、Ｓｉ：０．３％、Ｍｎ：０．３％、Ｐ：０．０３％、Ｓ：０．００１％、Ａｌ：５％、Ｔｉ：０．０３％、Ｃｒ：２０％、Ｎｂ：０．０３％、Ｌａ：０．０５％、Ｃｅ：０．０５％、Ｎ：０．００７％のステンレス鋼を熱間圧延、冷間圧延を経て厚さ３０μｍのステンレス鋼箔とした。
【００４０】
実施例１においては、ステンレス鋼箔にＡｌ粉末を含有するペイントを、厚さを変えて塗布し、温度１０００℃、４時間で焼成した。Ａｌ粉末を含有するペイントは、平均粒径１０μｍのＡｌ粉末を含有量５０質量％と、エチルセルロースを含有量５０質量％の比率のもとに、キシレンを添加し粘度が１００ｃｐになるように調整した。その結果、ステンレス鋼箔の表面には突起が形成された。高さ１μｍ以上の突起の密度は、Ｎｏ．１、２、３、４がそれぞれ１０、５０、１００、２００個／ｃｍ2であった。
【００４２】
実施例２（Ｎｏ．５）においては、なんら処理を行わなかった。ステンレス鋼箔の表面粗さはＲａで０．８μｍであり、突起は形成されていない。
【００４３】
以上のように準備したステンレス鋼箔をそのまま用いた平箔と、ステンレス鋼箔にコルゲート処理を施した波箔とを準備し、この平箔と波箔とをスパイラル状に交互に巻き回してメタルハニカム体とし、同じくステンレス鋼製外筒４に挿入してメタル担体とした。メタル担体の直径は１００ｍｍ、長さは１１０ｍｍ、波箔の波高さは１．２５ｍｍ、波ピッチは２ｍｍとした。
【００４４】
このメタル担体をウォッシュコート液中に浸漬し、次いで乾燥することによりセル内部に平均２５μｍ厚さのウォッシュコート層を形成した。このウォッシュコート層中に貴金属からなる触媒をしみ込ませてメタル触媒担体を完成した。
【００４５】
ウォッシュコート層の密着性はエンジン熱サイクル試験を行って調査した。触媒担体の排ガス入側の温度を１０００℃とし、エンジン運転１０分、エンジン停止１０分の熱サイクルを付与し、ウォッシュコートの剥離の有無によって評価した。
【００４６】
排ガス性能については、以上のようにして製造したメタル触媒担体を自動車の排ガス系に設置し、１１モードにてＨＣ排出量を評価した。
【００４７】
結果を表１に示す。
【００４８】
【表１】
表１に示すとおり、本発明範囲の突起密度を有する箔を用いた触媒担体は、ウォッシュコート密着性が良好であり、ＨＣ排出量も良好であった。
【００５１】
【発明の効果】
本発明は、ハニカム体を構成する金属箔の表面に高さ１μｍ以上の突起を形成することにより、ウォッシュコート層の密着性を改善することができ、さらに乱流効果によって触媒反応を促進させることができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a honeycomb body suitable as a catalyst carrier and a metal foil constituting the honeycomb body.
[0002]
[Prior art]
For the purpose of purifying the exhaust gas of the internal combustion engine, a catalytic converter carrying a catalyst is disposed in the exhaust gas path. Also, a methanol reformer that steam-reforms hydrocarbon compounds such as methanol to produce a hydrogen-rich gas, a CO removal device that reforms and removes CO to CO 2 , or burns H 2 to H 2 O Similarly, in the H 2 combustion apparatus to be removed, a carrier carrying a catalyst is used. These catalyst carriers have a large number of cells through which the gas passes, and the walls of each cell are coated with the catalyst, so that the gas passing through and the catalyst can come into contact with each other with a wide contact area.
[0003]
Examples of the catalyst carrier used for these purposes include a ceramic catalyst carrier and a metal catalyst carrier. The metal catalyst carrier is a cylindrical metal honeycomb body formed by alternately winding or laminating flat foils and corrugated foils with a thickness of several tens of μm using a heat-resistant alloy, and this metal honeycomb body is made of cylindrical metal. The metal carrier is inserted into the outer cylinder. A catalyst carrier layer in which a catalyst is impregnated is formed on the surface of the metal foil of the honeycomb body cell that becomes the gas passage of the metal carrier, to obtain a catalyst carrier. A contact portion between the flat foil and the corrugated foil of the honeycomb body obtained by winding and laminating the flat foil and the corrugated foil is joined by means such as brazing to make the honeycomb body a strong structural body.
[0004]
A method in which a porous γ-alumina layer called a washcoat layer is coated on the surface of a metal foil of a cell of a metal honeycomb body serving as a gas passage of the catalyst carrier, and a catalyst made of a noble metal or the like is impregnated into the washcoat layer, or There is a method of coating a metal honeycomb body with a washcoat layer containing a catalyst, and the catalyst is supported on the surface of the metal foil constituting the honeycomb body. As a method for forming a washcoat layer on the cell surface of the metal honeycomb body, the washcoat liquid is adhered to the cell surface of the honeycomb body by immersing the honeycomb body in the washcoat liquid, and then the washcoat layer is dried. A method of forming a layer on the cell surface is used.
[0005]
In Patent Document 1, in order to improve the adhesion between the surface of the metal foil of the metal honeycomb body and the washcoat layer, a honeycomb body is formed using an Al-containing stainless steel metal foil, and then heat-treated in the atmosphere to form steel. A method is described in which α-alumina whiskers are produced on the surface of stainless steel using Al of the above, and γ-alumina is coated on the acicular crystals. In order to promote the production of α-alumina whiskers, Patent Document 2 discloses a method in which an Al-containing stainless steel is preheated in a CO 2 atmosphere or the like.
[0006]
[Patent Document 1]
Japanese Patent Publication No. 8-197 [Patent Document 2]
JP-A-57-71898 [0007]
[Problems to be solved by the invention]
In order to produce α-alumina whiskers on the metal foil surface, it is necessary to heat treat the honeycomb body in the air or in the atmosphere. In this case, the Al source of the α-alumina whisker is a foil material, but this α-alumina whisker reduces the Al concentration in the foil material. Therefore, the oxidation resistance of the foil that can originally be held cannot be exhibited.
[0008]
In the exhaust gas purification using the catalyst carrier, the catalytic reaction progresses as the mass transfer between the exhaust gas passing through the cells of the honeycomb body and the catalyst on the cell surface becomes active, and the exhaust gas purification efficiency is improved.
[0009]
The first object of the present invention is to provide a metal foil and a honeycomb body that can improve the adhesion between the surface of the metal foil of the metal honeycomb body and the washcoat layer. Another object of the present invention is to provide a metal foil and a honeycomb body capable of activating mass transfer between a gas passing through the cells of the honeycomb body and the catalyst.
[0010]
[Means for Solving the Problems]
That is, the gist of the present invention is as follows.
(1) A following stainless steel metal foil thickness that has undergone hot rolling and cold rolling 100 [mu] m, height 1μm or more protrusions exist 100 pieces / cm 2 or more on the surface of the metal foil, Al in the foil concentration is not more than 6.5 wt percent 15 wt%, projections is a metal, metal foil Al concentration in the projections being higher than the Al concentration of the metal foil in.
(2) The metal foil according to (1), wherein the protrusion is a protrusion formed by melting and solidifying Al powder having an average particle size of 0.1 to 50 μm.
( 3 ) The component of the foil is mass%, Si: 0.1% or more and 1.0% or less, Mn: 0.5% or less, Al: more than 6.5%, 15% or less, Cr: 10% or more, 30% The metal foil according to (1) or (2) above, comprising the remaining Fe and inevitable impurities.
( 4 ) The component of the foil is mass%, and Ti: 0.02% or more and 0.1% or less and Nb: 0.02% or more and 0.3% or less, La: 0.01% or more and 0 0.1% or less, Ce: 0.01% or more and 0.1% or less, P: 0.01% or more and 0.05% or less, The metal foil as described in ( 3 ) above.
[0011]
( 5 ) A honeycomb body comprising the metal foil according to any one of (1) to ( 4 ) above.
[0012]
( 6 ) A continuous cast slab having an Al content of 6.5% by mass or less is hot-rolled, and then cold-rolled to form a metal foil. The surface of the metal foil is coated with Al powder, and then the metal foil is fired. The method for producing a metal foil according to any one of (1) to ( 4 ), wherein:
( 7 ) The surface of the metal foil is coated with Al paint having an average particle diameter of 0.1 to 50 μm , a resin and a solvent and having a viscosity of 10 to 5000 cp , and then the metal foil is fired at 600 ° C. or more and 1000 ° C. or less . The method for producing a metal foil as described in (6) above, wherein
(8) The method of producing metal foil according to the said firing atmosphere is an inert atmosphere (7).
( 9 ) A continuous cast slab having an Al content of 6.5% by mass or less is hot-rolled and then cold-rolled to form a metal foil, and then a honeycomb body is formed using the metal foil. The method for manufacturing a honeycomb body according to ( 5 ) above, wherein Al powder is applied to the surface of the metal foil constituting the body, and then the honeycomb body is fired.
(10) An Al paint having an average particle diameter of 0.1 to 50 μm and a viscosity of 10 to 5000 cp is applied to the surface of the metal foil constituting the honeycomb body, and then the honeycomb body is heated to 600 ° C. or more and 1000 The method for manufacturing a honeycomb body according to ( 9 ) , wherein firing is performed at a temperature of less than or equal to ° C.
(11) An adhesive is applied to the surface of the metal foil constituting the honeycomb body, and then Al powder having an average particle size of 0.1 to 50 μm is sprinkled on the honeycomb body, and the Al powder is applied to the adhesive application portion on the surface of the metal foil. The method for manufacturing a honeycomb body according to the above (9), characterized in that the metal foil is deposited and then fired at 600 ° C. or higher and 1000 ° C. or lower.
(12) The method for manufacturing a honeycomb body according to (10) or (11), wherein the firing atmosphere is an inert atmosphere.
[0013]
DETAILED DESCRIPTION OF THE INVENTION
In the honeycomb body of the present invention, if there are 100 / cm 2 or more protrusions having a height of 1 μm or more on the surface of the metal foil constituting the honeycomb body, the washcoat layer is bitten when the washcoat layer is formed on the honeycomb body. And the adhesion between the metal foil surface and the washcoat layer can be improved. In addition, since the protrusions are present on the surface of the metal foil forming the cell surface of the honeycomb body, the cell surface is uneven, the turbulence of the gas passing through the cell proceeds, and the gas that contacts the cell surface due to the turbulence effect Can be promoted and the catalytic reaction can be promoted. As used herein, the protrusion refers to a protrusion protruding on the surface of the foil.
[0014]
The height of the protrusion formed on the metal foil surface needs to be 1 μm or more. If it is less than 1 μm, the effect of increasing the adhesion of the washcoat cannot be obtained. The protrusion height is more preferably 2 μm or more. The density of protrusions needs to be 100 / cm 2 or more. As a result, the effect of improving the adhesion of the washcoat layer using the protrusions can be reliably increased. The reason why the thickness of the metal foil of the present invention is limited to 100 μm or less is that when it exceeds 100 μm, pressure loss becomes too large when a honeycomb body is formed.
[0017]
Metal foil of the present invention, by having projections on the surface, at the time of forming the honeycomb body with the metal foil, it is possible to obtain the same effect as described above.
[0018]
As the metal foil constituting the metal foil and honeycomb body of the present invention, the components of the foil are mass%, Si: 0.1% or more and 1.0% or less, Mn: 0.5% or less, Al: 6.5 More than 15% and 15% or less, Cr: 10% or more and 30% or less, the use of a metal foil composed of the balance Fe and inevitable impurities is preferable because oxidation resistance is improved.
[0019]
The reason why Mn is 0.5% or less is to ensure the oxidation resistance of the metal foil.
[0020]
By containing 0.1% or more of Si, the oxidation resistance of the metal foil can be improved. However, if the Si content exceeds 1.0%, the metal foil becomes more brittle, so the upper limit is made 1.0%.
[0021]
By containing Al in excess of 6.5%, the oxidation resistance of the metal foil can be improved. However, if the Al content exceeds 15%, the metal foil becomes more brittle, so the upper limit is made 15%.
[0022]
By containing 10% or more of Cr, the oxidation resistance of the metal foil can be improved. However, if the Cr content exceeds 30%, the metal foil becomes more brittle, so the upper limit is made 30%.
[0023]
The metal foil of the present invention and the metal foil constituting the honeycomb body further includes one or both of Ti: 0.02% to 0.1% and Nb: 0.02% to 0.3%, La: 0. 0.01% or more and 0.1% or less, Ce: 0.01% or more and 0.1% or less, and P: 0.01% or more and 0.05% or less are preferable.
[0024]
By containing one or both of Ti: 0.02% or more and Nb: 0.02% or more, the toughness of the metal foil can be improved. However, if Ti exceeds 0.1% and Nb exceeds 0.3%, the oxidation resistance of the metal foil is adversely affected, so these values were made the upper limit.
[0025]
By containing La: 0.01% or more and Ce: 0.01% or more, the oxidation resistance of the metal foil can be improved. However, if La exceeds 0.1% and Ce exceeds 0.1%, it causes hot rolling cracks, so these values were made the upper limit.
[0026]
When P is contained in an amount of 0.01% or more, there is an effect of preventing the occurrence of hot rolling cracks when La and Ce are contained. However, if the P content exceeds 0.05%, the oxidation resistance is deteriorated, so this value was made the upper limit.
[0027]
More height 1μm on the surface of the metal foil of the present invention will be described 100 / cm 2 or more of the manufacturing method of the metal foil to produce a projection.
[0028]
As a means for attaching Al to the stainless steel foil surface, a method of applying Al paint to the foil surface can be employed. A paint composed of Al powder, resin and solvent is prepared. Al powder having an average particle size of about 0.1 to 50 μm can be used. Further, if a flaky powder is used as the Al powder, a more preferable effect can be obtained. The resin is necessary for fixing the solvent to the cell wall after volatilizing the solvent by drying. A commonly used resin such as ethyl cellulose or phenol may be used. As the solvent, industrial kerosene, xylene or the like may be used. The amount of solvent is important in managing the viscosity of the paint. Good results are obtained when the paint viscosity is kept between 10 and 5000 cp. This paint is applied to the surface of the metal foil. As a coating method, a method of immersing the honeycomb body in the paint liquid can be used. Thereafter, the metal foil coated with the paint is fired. The firing atmosphere may be air or an inert atmosphere, but an inert atmosphere is more preferable. In order to melt the Al powder, the firing temperature is set to 600 ° C. or higher. When the resin is contained in the paint, the resin is thermally decomposed and removed by this baking.
[0029]
As a result of firing the metal foil coated with paint, the Al powder in the paint is melted, and a large number of molten Al droplets are formed on the surface of the metal foil. A component of the metal foil diffuses into the droplet from the metal foil in contact with the molten Al droplet, and this component and Al in the droplet are alloyed and solid-phased. When the temperature of the metal foil is lowered in this state, the droplet portion forms a protrusion. The protrusion formed in this way is a metal. Further, the composition of the protrusions is such that the Al concentration in the protrusions is higher than the Al concentration in the metal foil.
[0030]
The protrusions on the surface of the metal foil formed by the above method can have a protrusion height of 1 μm or more and a protrusion density of 100 pieces / cm 2 or more.
[0031]
Part of the Al powder in the paint applied to the surface of the metal foil forms a large number of molten Al droplets on the surface of the metal foil as described above, and finally forms protrusions. On the other hand, other Al powders melt at the time of firing, diffuse into the metal foil, and alloy with the components in the metal foil.
[0032]
In producing the Al-containing stainless steel metal foil of the present invention, a continuous cast slab is usually hot-rolled and then cold-rolled to obtain a metal foil. When the Al content in the slab before hot rolling exceeds 6.5%, workability is poor in hot rolling, and good rolling cannot be performed. In the present invention, the Al content in the slab before hot rolling is set to 6.5% or less, a paint containing Al powder is applied to the surface at the stage of the metal foil, and Al is added to the metal foil by firing. By diffusion, the Al content in the metal foil can be made to exceed 6.5%. By making the Al content more than 6.5%, this metal foil has extremely good oxidation resistance.
[0033]
As described above, the Al powder application to the metal foil surface may be applied to the metal foil before forming the honeycomb body, but it is more preferable to apply to the metal foil after forming the honeycomb body. . Application of the Al powder to the surface of the metal foil constituting the honeycomb body can be performed by immersing the honeycomb body in the paint composed of the Al powder, the resin, and the solvent as described above. Alternatively, a method may be employed in which an adhesive is applied to the surface of the metal foil constituting the honeycomb body, and then Al powder is sprinkled on the honeycomb body to adhere the Al powder to the adhesive application portion on the surface of the metal foil. By firing the honeycomb body after applying the Al powder, as in the case of the metal foil, protrusions can be formed on the surface of the metal foil constituting the honeycomb body and at the same time increasing the Al content in the metal foil. Can do. The firing may be performed under the same conditions as the firing of the metal foil, or may be performed as a heat treatment for brazing the metal foil contact portion of the honeycomb body.
[0039]
【Example】
Containing component is mass%, C: 0.007%, Si: 0.3%, Mn: 0.3%, P: 0.03%, S: 0.001%, Al: 5%, Ti: 0 0.03%, Cr: 20%, Nb: 0.03%, La: 0.05%, Ce: 0.05%, N: 0.007% stainless steel is hot-rolled and thickened after cold rolling A stainless steel foil having a thickness of 30 μm was used.
[0040]
In Example 1, a paint containing Al powder was applied to a stainless steel foil at different thicknesses, and baked at a temperature of 1000 ° C. for 4 hours. The paint containing Al powder was adjusted so that the viscosity was 100 cp by adding xylene based on a ratio of 50% by mass of Al powder having an average particle size of 10 μm and 50% by mass of ethyl cellulose. . As a result, protrusions were formed on the surface of the stainless steel foil. The density of protrusions with a height of 1 μm or more is No. 1, 2, 3, and 4 were 10, 50, 100, and 200 / cm 2 , respectively.
[0042]
In Example 2 (No. 5), was not carried out what we processing. The surface roughness of the stainless steel foil is 0.8 μm in Ra, and no protrusion is formed.
[0043]
Prepare a flat foil using the stainless steel foil prepared as described above and a corrugated foil obtained by corrugating the stainless steel foil. The flat foil and the corrugated foil are alternately wound in a spiral shape to form a metal. A honeycomb body was also inserted into the stainless steel outer cylinder 4 to obtain a metal carrier. The diameter of the metal carrier was 100 mm, the length was 110 mm, the wave height of the corrugated foil was 1.25 mm, and the wave pitch was 2 mm.
[0044]
This metal carrier was immersed in a washcoat solution and then dried to form a washcoat layer having an average thickness of 25 μm inside the cell. A catalyst made of a noble metal was soaked into the washcoat layer to complete a metal catalyst carrier.
[0045]
The adhesion of the washcoat layer was investigated by performing an engine thermal cycle test. The temperature on the exhaust gas inlet side of the catalyst carrier was set to 1000 ° C., a thermal cycle of 10 minutes for engine operation and 10 minutes for engine stop was applied, and evaluation was performed based on whether or not the washcoat was peeled off.
[0046]
Regarding the exhaust gas performance, the metal catalyst carrier produced as described above was installed in an exhaust gas system of an automobile, and the HC emission amount was evaluated in 11 modes.
[0047]
The results are shown in Table 1.
[0048]
[Table 1]
As shown in Table 1, the catalyst carrier using the foil having the projection density in the range of the present invention had good washcoat adhesion and good HC emission.
[0051]
【The invention's effect】
The present invention can improve the adhesion of the washcoat layer by forming protrusions having a height of 1 μm or more on the surface of the metal foil constituting the honeycomb body, and further promote the catalytic reaction by the turbulent flow effect. Can do.
Claims (12)
Priority Applications (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002336049A JP3953944B2 (en) | 2002-11-20 | 2002-11-20 | Metal foil and honeycomb structure |
| EP03774096.6A EP1580288B1 (en) | 2002-11-20 | 2003-11-20 | High al stainless steel sheet, honeycomb bodies employing the steel sheet and use of the steel sheet for a honeycomb body |
| PCT/JP2003/014832 WO2004046406A1 (en) | 2002-11-20 | 2003-11-20 | HIGH-Al STAINLESS STEEL PLATE AND DOUBLE-LAYERED PLATE, PROCESS FOR PRODUCING THE SAME, A HONEYCOMB STRUCTURE THEREFROM AND PROCESS FOR PRODUCING THE HONEYCOMB STRUCTURE |
| EP09150743A EP2048258A1 (en) | 2002-11-20 | 2003-11-20 | Honeycomb bodies employing high Al stainless steel sheet and process for production thereof |
| US10/535,602 US7601672B2 (en) | 2002-11-20 | 2003-11-20 | High Al stainless steel sheet and honeycomb bodies employing them |
| US11/981,933 US20080069717A1 (en) | 2002-11-20 | 2007-10-31 | High A1 stainless steel sheet and double layered sheet, process for their fabrication, honeycomb bodies employing them and process for their production |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002336049A JP3953944B2 (en) | 2002-11-20 | 2002-11-20 | Metal foil and honeycomb structure |
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| JP2004169111A JP2004169111A (en) | 2004-06-17 |
| JP3953944B2 true JP3953944B2 (en) | 2007-08-08 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4842025B2 (en) | 2006-06-19 | 2011-12-21 | 日揮触媒化成株式会社 | Method for forming metal oxide fine particle layer on conductive substrate |
| JP5278641B2 (en) * | 2006-06-23 | 2013-09-04 | 日産自動車株式会社 | Metal substrate manufacturing method |
| US20100158775A1 (en) * | 2008-12-18 | 2010-06-24 | Basf Catalysts Llc | Catalyst Systems and Methods for Treating Aircraft Cabin Air |
| JP5504778B2 (en) * | 2009-09-16 | 2014-05-28 | Ｊｆｅスチール株式会社 | Stainless foil that is difficult to diffuse and bond and its manufacturing method |
| JP5872179B2 (en) | 2011-03-10 | 2016-03-01 | 株式会社エフ・シー・シー | Method for producing catalyst carrier for exhaust gas purification |
| KR101344890B1 (en) * | 2012-02-15 | 2014-02-05 | 한국과학기술연구원 | Diesel Particulate Filter using metal structure having unevenness on the surface |
| JP6740104B2 (en) * | 2015-12-17 | 2020-08-12 | 花王株式会社 | Film catalyst |
| US10610829B2 (en) | 2017-02-28 | 2020-04-07 | Nippon Steel Chemical & Material, Co., Ltd. | Honeycomb substrate for catalyst support, and catalytic converter for exhaust gas purification |
| CN114293070A (en) * | 2021-12-31 | 2022-04-08 | 镇江龙源铝业有限公司 | Aluminum foil for brazing-free air conditioner heater and preparation method thereof |
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| JP2004169111A (en) | 2004-06-17 |
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