JP2004169111A - Metal foil, and honeycomb structure - Google Patents
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- JP2004169111A JP2004169111A JP2002336049A JP2002336049A JP2004169111A JP 2004169111 A JP2004169111 A JP 2004169111A JP 2002336049 A JP2002336049 A JP 2002336049A JP 2002336049 A JP2002336049 A JP 2002336049A JP 2004169111 A JP2004169111 A JP 2004169111A
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Abstract
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発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）表面に高さ１μｍ以上の突起が１００個／ｃｍ２以上存在し、厚さが１００μｍ以下であることを特徴とする金属箔。
（２）箔中のＡｌ濃度が６．５質量％超であることを特徴とする上記（１）に記載の金属箔。
（３）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上記（１）又は（２）に記載の金属箔。
（４）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）乃至（３）のいずれかに記載の金属箔。
（５）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（４）に記載の金属箔。
（６）表面粗さがＲａで２μｍ以上であることを特徴とする金属箔。
（７）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（６）に記載の金属箔。
（８）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（７）に記載の金属箔。
【００１１】
（９）上記（１）乃至（５）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。
（１０）上記（６）乃至（８）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】
（１１）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（５）のいずれかに記載の金属箔の製造方法。
（１２）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（９）に記載のハニカム体の製造方法。
（１３）金属箔の表面にＡｌを真空蒸着し、次いで金属箔を焼成することを特徴とする上記（６）乃至（８）のいずれかに記載の金属箔の製造方法。
【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。
【００１５】
本発明のハニカム体はまた、ハニカム体を構成する金属箔の表面粗さをＲａで２μｍ以上とすることにより、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、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凹凸が存在するため、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。表面粗度はＪＩＳ２０００で規定されているＲａのことである。
【００１６】
金属箔表面の表面粗さをＲａで２μｍ以上とするのは、これによってウォッシュコート層の密着性を発揮させることが可能になるからである。表面粗さはＲａで４μｍ以上とするとより好ましい。
【００１７】
本発明の金属箔は、表面に突起を有し、又は所定の表面粗度を有していることにより、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。
【００３４】
本発明の金属箔の表面粗さがＲａで２μｍ以上とするための金属箔の製造方法について説明する。
【００３５】
金属箔の表面にＡｌを真空蒸着する。蒸着厚さは成膜速度０．５μｍ／分以上の条件で平均膜厚１μｍ以上とすると良い。Ａｌを蒸着後、金属箔を焼成する。表面にＡｌ膜を有する金属箔を焼成すると、金属箔の表面が粗くなり、Ｒａで２μｍ以上の粗度を持たせることができる。焼成条件は例えば１０００℃程度で２時間、真空雰囲気で焼成すればよい。また、ハニカム体に形成する前の金属箔を焼成しても、あるいはＡｌを蒸着した金属箔をハニカム体に形成し、その後焼成しても良い。
【００３６】
金属箔表面に形成されたＡｌ膜は、上記のように金属箔の表面粗度を粗くする作用を有するほか、焼成時にＡｌが金属箔中に拡散し、金属箔のＡｌ含有量を増大させる作用も有する。従って、熱間圧延前のＡｌ含有量は６．５％以下としておき、Ａｌ膜形成後の金属箔を焼成すること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。
【００３７】
金属箔の表面にＡｌ膜を形成する手段としては、上記金属箔の表面にＡｌを真空蒸着する方法の他、箔圧延前の金属板の表面にＡｌメッキを施し、その後箔圧延を行うこととしても良い。
【００３８】
以上の方法を用いることにより、金属箔の表面粗度をＲａで２μｍ以上とすることができる。
【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。
【００４１】
実施例２においては、ステンレス鋼箔にＡｌを真空蒸着して厚さ０．５〜４μｍのＡｌ膜を形成し、温度１０００℃、２時間で焼成した。その結果、ステンレス鋼箔の表面粗さは、Ｎｏ．５、６、７、８かそれぞれＲａで１、２、３、４μｍとなった。
【００４２】
実施例３（Ｎｏ．９）においては、なんらＡｌ膜を形成する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。
【００５０】
同じく表１に示すとおり、本発明範囲の表面粗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。
【００５２】
本発明はまた、ハニカム体を構成する金属箔の表面粗さをＲａで２μｍ以上とすることにより、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]
TECHNICAL FIELD OF THE INVENTION
TECHNICAL FIELD 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 exhaust gas of an internal combustion engine, a catalytic converter carrying a catalyst is disposed in an exhaust gas path. In addition, a methanol reformer that generates a hydrogen-rich gas by steam reforming a hydrocarbon compound such as methanol, a CO remover that reforms and removes CO into CO 2 , or burns H 2 to H 2 O also in H 2 combustion apparatus to remove carrier carrying similarly catalyst is used. These catalyst carriers have a large number of cells through which gas passes, and the wall surface of each cell is coated with a catalyst, so that the passing gas and the catalyst can come into contact with a wide contact area.
[0003]
Catalyst carriers used for these purposes include ceramic catalyst carriers and metal catalyst carriers. The metal catalyst carrier is a cylindrical metal honeycomb body formed by alternately winding or laminating a flat foil and a corrugated foil having a thickness of several tens of μm using a heat-resistant alloy, and forming the metal honeycomb body into a cylindrical metal honeycomb body. Into a metal carrier. A catalyst supporting layer in which a catalyst is impregnated is formed on the surface of a metal foil of a honeycomb cell serving as a gas passage of the metal carrier, and is used as a catalyst carrier. The contact portion between the flat foil and the corrugated foil of the honeycomb body in which the flat foil and the corrugated foil are wound and laminated is joined by means such as brazing to make the honeycomb body a strong structure.
[0004]
A method of coating a porous γ-alumina layer called a wash coat layer on a surface of a metal foil of a cell of a metal honeycomb body serving as a gas passage of a catalyst carrier, and impregnating a catalyst made of a noble metal or the like into the wash coat layer, or There is a method of coating a metal honeycomb body with a wash coat layer containing a catalyst, and the catalyst is carried on the surface of a metal foil constituting the honeycomb body. As a method of forming a wash coat layer on the cell surface of a metal honeycomb body, the wash coat liquid is adhered to the cell surface of the honeycomb body by immersing the honeycomb body in a wash coat liquid, and then dried. A method of forming a layer on the cell surface has been used.
[0005]
In Patent Document 1, in order to improve the adhesion between the metal foil surface of the metal honeycomb body and the wash coat layer, a honeycomb body is formed using an Al-containing stainless steel metal foil, and then heat-treated in the air to form a honeycomb body. Describes a method in which α-alumina whiskers are formed on the surface of stainless steel using Al, and the needle crystals are coated with γ-alumina. Patent Literature 2 describes a method in which Al-containing stainless steel is heat-treated in advance in a CO 2 atmosphere or the like in order to promote the formation of α-alumina whiskers.
[0006]
[Patent Document 1]
Japanese Patent Publication No. 8-197 [Patent Document 2]
JP-A-57-71898
[Problems to be solved by the invention]
In order to form α-alumina whiskers on the surface of the metal foil, 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 the α-alumina whisker reduces the Al concentration in the foil material. Therefore, the oxidation resistance of the foil which can be originally obtained cannot be exhibited.
[0008]
In purifying the exhaust gas using the catalyst carrier, the more the mass transfer between the exhaust gas passing through the cell of the honeycomb body and the catalyst on the cell surface becomes active, the more the catalytic reaction proceeds, and the purification efficiency of the exhaust gas is improved.
[0009]
SUMMARY OF THE INVENTION It is a first object of the present invention to provide a metal foil and a honeycomb body that can improve the adhesion between a metal emitting surface of a metal honeycomb body and a washcoat layer. A second object of the present invention is to provide a metal foil and a honeycomb body capable of activating mass transfer between a gas and a catalyst passing through cells of the honeycomb body.
[0010]
[Means for Solving the Problems]
That is, the gist of the present invention is as follows.
(1) A metal foil having 100 projections / cm 2 or more with a height of 1 μm or more on its surface and a thickness of 100 μm or less.
(2) The metal foil according to the above (1), wherein the Al concentration in the foil is more than 6.5% by mass.
(3) The metal foil according to the above (1) or (2), wherein the projection is a metal, and the Al concentration in the projection is higher than the Al concentration in the metal foil.
(4) The component of the foil is% by mass, Si: 0.1% or more and 1.0% or less, Mn: 0.5% or less, Al: more than 6.5% and 15% or less, Cr: 10% or more and 30% Hereinafter, the metal foil according to any one of the above (1) to (3), comprising a balance of Fe and unavoidable impurities.
(5) The component of the foil is mass%, and one or both of Ti: 0.02% to 0.1% and Nb: 0.02% to 0.3%, La: 0.01% to 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 (4) above,
(6) A metal foil having a surface roughness of 2 μm or more in Ra.
(7) The component of the foil is% by mass, Si: 0.1% to 1.0%, Mn: 0.5% or less, Al: more than 6.5% to 15%, Cr: 10% to 30% Hereinafter, the metal foil according to the above (6), comprising the balance of Fe and unavoidable impurities.
(8) The component of the foil is mass%, and one or both of Ti: 0.02% to 0.1% and Nb: 0.02% to 0.3%, La: 0.01% to 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 (7) above,
[0011]
(9) A honeycomb body comprising the metal foil according to any one of the above (1) to (5).
(10) A honeycomb body comprising the metal foil according to any one of (6) to (8).
[0012]
(11) The method for producing a metal foil according to any one of (1) to (5), wherein an Al powder is applied to a surface of the metal foil, and then the metal foil is fired.
(12) The method for manufacturing a honeycomb body according to the above (9), wherein an Al powder is applied to a surface of a metal foil constituting the honeycomb body, and then the honeycomb body is fired.
(13) The method for producing a metal foil as described in any of (6) to (8) above, wherein Al is vacuum-deposited on the surface of the metal foil, and then the metal foil is fired.
[0013]
BEST MODE FOR CARRYING OUT THE INVENTION
In the honeycomb body of the present invention, when the protrusions having a height of 1 μm or more are present on the surface of the metal foil constituting the honeycomb body at 100 or more / cm 2 or more, when the wash coat layer is formed on the honeycomb body, the wash coat layer bites. And the adhesion between the surface of the metal foil and the washcoat layer can be improved. In addition, since projections are present on the surface of the metal foil forming the cell surface of the honeycomb body, irregularities are generated on the cell surface, and the gas passing through the cell becomes turbulent. Is promoted, and the catalytic reaction can be promoted. Here, the protrusion refers to a protrusion protruding from the foil surface in a wart shape.
[0014]
The height of the projections formed on the surface of the metal foil needs to be 1 μm or more. If it is less than 1 μm, the effect of increasing the adhesiveness of the washcoat cannot be obtained. More preferably, the height of the protrusion is 2 μm or more. Further, the density of the protrusions needs to be 100 protrusions / cm 2 or more. Thereby, the effect of improving the adhesion of the wash coat layer using the projections can be reliably improved. The reason for limiting the thickness of the metal foil of the present invention to 100 μm or less is that if it exceeds 100 μm, the pressure loss becomes too large when the honeycomb body is used.
[0015]
In the honeycomb body of the present invention, when the surface roughness of the metal foil constituting the honeycomb body is set to 2 μm or more in Ra, when forming the wash coat layer on the honeycomb body, the metal foil surface and the wash coat layer Adhesion can be improved. In addition, since there is unevenness on the surface of the metal foil forming the cell surface of the honeycomb body, turbulence of the gas passing through the cell progresses, and the turbulence effect promotes replacement of the gas that comes into contact with the cell surface, and the catalyst The reaction can be accelerated. The surface roughness is Ra defined in JIS2000.
[0016]
The reason why the surface roughness of the metal foil surface is set to 2 μm or more in Ra is that it becomes possible to exert the adhesion of the washcoat layer. The surface roughness is more preferably 4 μm or more in Ra.
[0017]
The metal foil of the present invention has the same effects as above when a honeycomb body is formed using the metal foil by having projections on the surface or having a predetermined surface roughness. Can be.
[0018]
As the metal foil and the metal foil constituting the honeycomb body of the present invention, the components of the foil are in mass%, and Si: 0.1% or more and 1.0% or less, Mn: 0.5% or less, Al: 6.5 or less. % And 15% or less, Cr: 10% or more and 30% or less, and the use of a metal foil comprising the balance of Fe and unavoidable impurities improves the oxidation resistance, which is preferable.
[0019]
The reason that Mn is set to 0.5% or less is to secure 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%, embrittlement of the metal foil proceeds, so the upper limit is made 1.0%.
[0021]
By containing more than 6.5% of Al, the oxidation resistance of the metal foil can be improved. However, if the Al content exceeds 15%, embrittlement of the metal foil proceeds, so the upper limit is set to 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%, embrittlement of the metal foil proceeds, so the upper limit is set to 30%.
[0023]
The metal foil of the present invention and the metal foil constituting the honeycomb body further include one or both of Ti: 0.02% to 0.1% and Nb: 0.02% to 0.3%, La: 0 It is preferable to contain 0.01% to 0.1%, Ce: 0.01% to 0.1%, and P: 0.01% to 0.05%.
[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 the content of Ti exceeds 0.1% and the content of Nb exceeds 0.3%, the oxidation resistance of the metal foil is adversely affected.
[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 cracking, so these values were made the upper limits.
[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 deteriorates, so this value was made the upper limit.
[0027]
A method for producing a metal foil for producing protrusions having a height of 1 μm or more and 100 protrusions / cm 2 or more on the surface of the metal foil of the present invention will be described.
[0028]
As a means for attaching Al to the surface of the stainless steel foil, a method of applying Al paint to the foil surface can be adopted. 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 flake-like material is used as the Al powder, more preferable effects can be obtained. The resin is necessary for allowing the solvent to evaporate by drying and then fixing the resin to the cell wall surface. A commonly used resin such as ethyl cellulose and phenol may be used. As the solvent, industrial kerosene or xylene may be used. The amount of solvent is important in controlling the viscosity of the paint. Good results are obtained if the paint viscosity is kept between 10 and 5000 cp. This paint is applied to the metal foil surface. As a method of application, a method of dipping the honeycomb body in a 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 a 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 to which the paint is applied, the Al powder in the paint is melted, and a number of molten Al droplets are formed on the surface of the metal foil. From the metal foil in contact with the molten Al droplet, a component of the metal foil diffuses into the droplet, and this component and Al in the droplet are alloyed and solidified. When the temperature of the metal foil is lowered in this state, the droplets form projections. 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 protrusions / cm 2 or more.
[0031]
Part of the Al powder in the paint applied to the metal foil surface forms a large number of molten Al droplets on the metal foil surface as described above, and finally forms projections. On the other hand, other Al powders melt during firing, diffuse into the metal foil, and alloy with the components in the metal foil.
[0032]
When producing the Al-containing stainless steel metal foil of the present invention, usually, a continuously cast slab is hot-rolled and then cold-rolled to obtain a metal foil. If the Al content in the slab before hot rolling exceeds 6.5%, workability in hot rolling is poor, 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 the Al is added to the metal foil by firing. Diffusion allows the Al content in the metal foil to exceed 6.5%. By setting the Al content to more than 6.5%, the metal foil has extremely good oxidation resistance.
[0033]
As described above, the application of the Al powder to the metal foil surface may be applied to the metal foil before forming the honeycomb body, but is more preferably applied to the metal foil after forming the honeycomb body. . The 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 adopted in which an adhesive is applied to the surface of the metal foil constituting the honeycomb body, and then the Al powder is sprinkled on the honeycomb body, and the Al powder is applied to the adhesive applied portion on the metal foil surface. By firing the honeycomb body after applying the Al powder, projections can be formed on the surface of the metal foil constituting the honeycomb body as in the case of the metal foil, and simultaneously increasing the Al content in the metal foil. Can be. The calcination can be performed under the same conditions as the calcination of the metal foil, or can be performed together with a heat treatment for brazing the metal foil contact portion of the honeycomb body.
[0034]
A method for producing a metal foil for making the surface roughness of the metal foil according to the present invention Ra 2 μm or more will be described.
[0035]
Al is vacuum-deposited on the surface of the metal foil. The average thickness is preferably 1 μm or more at a deposition rate of 0.5 μm / min or more. After depositing Al, the metal foil is fired. When a metal foil having an Al film on the surface is baked, the surface of the metal foil becomes rough, and it is possible to give a roughness of 2 μm or more in Ra. The firing conditions may be, for example, firing at about 1000 ° C. for 2 hours in a vacuum atmosphere. Alternatively, the metal foil before being formed on the honeycomb body may be fired, or a metal foil on which Al is deposited may be formed on the honeycomb body and fired thereafter.
[0036]
The Al film formed on the surface of the metal foil has the effect of increasing the surface roughness of the metal foil as described above, and the effect of diffusing Al into the metal foil during firing and increasing the Al content of the metal foil. Also have. Therefore, the Al content before hot rolling is set to 6.5% or less, and the Al content in the metal foil can be increased to more than 6.5% by firing the metal foil after forming the Al film.
[0037]
As means for forming an Al film on the surface of the metal foil, in addition to the method of vacuum-depositing Al on the surface of the metal foil, Al plating is performed on the surface of the metal plate before foil rolling, and then foil rolling is performed. Is also good.
[0038]
By using the above method, the surface roughness of the metal foil can be set to 2 μm or more in Ra.
[0039]
【Example】
The contained components are in 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 subjected to hot rolling and cold rolling to obtain a thickness. 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 while changing its thickness, and baked at a temperature of 1000 ° C. for 4 hours. The paint containing Al powder was adjusted to have a viscosity of 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 the protrusions having a height of 1 μm or more is determined by 1, 2, 3, and 4 were 10, 50, 100, and 200 cells / cm 2 , respectively.
[0041]
In Example 2, Al was vacuum-deposited on a stainless steel foil to form an Al film having a thickness of 0.5 to 4 μm, and baked at a temperature of 1000 ° C. for 2 hours. As a result, the surface roughness of the stainless steel foil was no. 5, 6, 7, and 8 respectively became 1, 2, 3, and 4 μm in Ra.
[0042]
In Example 3 (No. 9), no treatment for forming an Al film was performed. The surface roughness of the stainless steel foil is 0.8 μm in Ra, and no projection is formed.
[0043]
A flat foil using the stainless steel foil prepared as described above as it is, and a corrugated foil obtained by subjecting the stainless steel foil to corrugation treatment are prepared. A honeycomb body was 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 comprising a noble metal was impregnated into the wash coat layer to complete a metal catalyst carrier.
[0045]
The adhesion of the washcoat layer was investigated by performing an engine heat cycle test. The temperature on the exhaust gas inlet side of the catalyst carrier was set to 1000 ° C., a heat cycle was applied for 10 minutes while the engine was running and the engine was stopped for 10 minutes, and evaluation was made based on whether or not the wash coat was peeled off.
[0046]
Regarding the exhaust gas performance, the metal catalyst carrier produced as described above was installed in an automobile exhaust gas system, and the HC emission was evaluated in 11 modes.
[0047]
Table 1 shows the results.
[0048]
[Table 1]
As shown in Table 1, the catalyst carrier using the foil having the projection density within the range of the present invention had good washcoat adhesion and good HC emission.
[0050]
As also shown in Table 1, the catalyst carrier using the foil having the surface roughness 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 a washcoat layer by forming protrusions having a height of 1 μm or more on the surface of a metal foil constituting a honeycomb body, and further promote a catalytic reaction by a turbulent flow effect. Can be.
[0052]
The present invention can also improve the adhesion of the wash coat layer by setting the surface roughness of the metal foil constituting the honeycomb body to 2 μm or more in Ra, and further promote the catalytic reaction by a turbulent flow effect. Can be.
Claims (13)
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 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002336049A JP3953944B2 (en) | 2002-11-20 | 2002-11-20 | Metal foil and honeycomb structure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2004169111A true JP2004169111A (en) | 2004-06-17 |
| JP3953944B2 JP3953944B2 (en) | 2007-08-08 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2002336049A Expired - Fee Related JP3953944B2 (en) | 2002-11-20 | 2002-11-20 | Metal foil and honeycomb structure |
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| Country | Link |
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| JP (1) | JP3953944B2 (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2007148642A1 (en) | 2006-06-19 | 2007-12-27 | Jgc Catalysts And Chemicals Ltd. | Method of forming metal oxide microparticle layer on conductive substratum |
| EP2033709A1 (en) * | 2006-06-23 | 2009-03-11 | Nissan Motor Co., Ltd. | Metal base, method for producing the same, and catalyst |
| JP2011063833A (en) * | 2009-09-16 | 2011-03-31 | Jfe Steel Corp | Stainless foil hard to be diffusion-bonded and manufacturing method therefor |
| JP2012512787A (en) * | 2008-12-18 | 2012-06-07 | ビー・エイ・エス・エフ、コーポレーション | Catalyst system and method for aircraft cabin air treatment |
| DE112012001175T5 (en) | 2011-03-10 | 2013-12-05 | Kabushiki Kaisha F.C.C. | Catalyst device for exhaust gas purification |
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| JP2017113747A (en) * | 2015-12-17 | 2017-06-29 | 花王株式会社 | Film-like catalyst |
| WO2018159556A1 (en) * | 2017-02-28 | 2018-09-07 | 新日鉄住金マテリアルズ株式会社 | Honeycomb substrate for catalyst support, and catalytic converter for exhaust gas purification |
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| US7901742B2 (en) | 2006-06-19 | 2011-03-08 | Jgc Catalysts And Chemicals Ltd. | Method for forming metal oxide fine particle layer on conductive substrate |
| WO2007148642A1 (en) | 2006-06-19 | 2007-12-27 | Jgc Catalysts And Chemicals Ltd. | Method of forming metal oxide microparticle layer on conductive substratum |
| EP2033709A1 (en) * | 2006-06-23 | 2009-03-11 | Nissan Motor Co., Ltd. | Metal base, method for producing the same, and catalyst |
| EP2033709A4 (en) * | 2006-06-23 | 2014-08-13 | Nissan Motor | Metal base, method for producing the same, and catalyst |
| JP2012512787A (en) * | 2008-12-18 | 2012-06-07 | ビー・エイ・エス・エフ、コーポレーション | Catalyst system and method for aircraft cabin air treatment |
| JP2011063833A (en) * | 2009-09-16 | 2011-03-31 | Jfe Steel Corp | Stainless foil hard to be diffusion-bonded and manufacturing method therefor |
| DE112012001175B4 (en) | 2011-03-10 | 2023-04-20 | Kabushiki Kaisha F.C.C. | Catalyst device for exhaust gas purification |
| DE112012001175T5 (en) | 2011-03-10 | 2013-12-05 | Kabushiki Kaisha F.C.C. | Catalyst device for exhaust gas purification |
| KR101344890B1 (en) * | 2012-02-15 | 2014-02-05 | 한국과학기술연구원 | Diesel Particulate Filter using metal structure having unevenness on the surface |
| JP2017113747A (en) * | 2015-12-17 | 2017-06-29 | 花王株式会社 | Film-like catalyst |
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| JP6466629B1 (en) * | 2017-02-28 | 2019-02-06 | 日鉄ケミカル＆マテリアル株式会社 | Honeycomb substrate for catalyst support, catalytic converter for exhaust gas purification |
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