JPH06126192A - Production of metallic foil coated with oxide - Google Patents
Production of metallic foil coated with oxideInfo
- Publication number
- JPH06126192A JPH06126192A JP3099900A JP9990091A JPH06126192A JP H06126192 A JPH06126192 A JP H06126192A JP 3099900 A JP3099900 A JP 3099900A JP 9990091 A JP9990091 A JP 9990091A JP H06126192 A JPH06126192 A JP H06126192A
- Authority
- JP
- Japan
- Prior art keywords
- oxide
- foil coated
- plating
- metal
- stainless steel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000011888 foil Substances 0.000 title claims abstract description 21
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 11
- 238000007747 plating Methods 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 24
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000001301 oxygen Substances 0.000 claims abstract description 8
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims description 27
- 239000002184 metal Substances 0.000 claims description 27
- 229910001220 stainless steel Inorganic materials 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 11
- 238000005096 rolling process Methods 0.000 claims description 8
- 238000005097 cold rolling Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 abstract description 12
- 239000007789 gas Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 229910003158 γ-Al2O3 Inorganic materials 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 13
- 239000003054 catalyst Substances 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000010062 adhesion mechanism Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910000859 α-Fe Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、酸化物で被覆された金
属箔の製造方法に関し、特に自動車排ガスコンバーター
に使用されるメタルハニカム用材料、或は、その他多く
の工業過程で行われる触媒反応に使用される触媒装置材
料に適した酸化物で被覆された金属箔の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a metal foil coated with an oxide, and more particularly to a material for a metal honeycomb used in an automobile exhaust gas converter or a catalytic reaction carried out in many other industrial processes. The present invention relates to a method for producing an oxide-coated metal foil suitable for a catalyst device material used in.
【０００２】[0002]
【従来の技術】従来、自動車排ガス浄化用触媒コンバー
ターとしては、セラミック製ハニカム構造体にウオッシ
ュコートを触媒担体としてコーティングした後、Ｐｔ、
Ｒｈなどの触媒をつけたものが使用されている。このセ
ラミック製ハニカム構造体を、耐高温酸化性に優れたス
テンレス鋼箔で製造すると、触媒の支持体が金属である
ため、熱伝導性、強靭性の面でセラミック支持体にまさ
り、触媒性能、エンジン性能の向上を図ることができ
る。2. Description of the Related Art Conventionally, as a catalytic converter for purifying automobile exhaust gas, after a ceramic honeycomb structure is coated with a wash coat as a catalyst carrier, Pt,
The one with a catalyst such as Rh is used. When this ceramic honeycomb structure is manufactured from a stainless steel foil having excellent high temperature oxidation resistance, the catalyst support is a metal, so the thermal conductivity is superior to the ceramic support in terms of toughness, the catalyst performance, It is possible to improve engine performance.
【０００３】しかしながら、ステンレス鋼箔に直接ウオ
ッシュコートをつけた場合には、使用中の温度変化や機
械的震動により触媒担体が剥離する欠点があった。この
欠点を克服する方法として、ステンレス鋼箔の表面にア
ルミナウィスカーを設けて、そのウオッシュコートの耐
剥離性を向上させている。However, when the washcoat was directly applied to the stainless steel foil, there was a defect that the catalyst carrier was peeled off due to temperature change during use or mechanical vibration. As a method of overcoming this drawback, alumina whiskers are provided on the surface of the stainless steel foil to improve the peel resistance of the washcoat.
【０００４】アルミナウィスカーの生成方法として、種
々の方法が提案されている。例えば、特開昭５６−９６
７２６号には１５％≦Ｃｒ≦２５％、３％≦Ａｌ≦６％
を含むフェライトステンレス鋼箔を金属剥離法（ピーリ
ング）により製造し、この箔を８７０℃〜９７０℃の間
で大気酸化させてアルミナウィスカーを箔表面に成長さ
せており、また、特開昭５７−７１８９８号では１５％
≦Ｃｒ≦２５％、３％≦Ａｌ≦６％を含むフェライトス
テンレス鋼箔を酸素分圧０．７５トール以下の炭酸ガ
ス、窒素、水素または稀有ガスの何れかの雰囲気中で８
７５℃〜９２５℃で約１分間加熱した後、空気中で８７
０℃〜９３０℃の間の温度で長時間酸化させる２段階の
熱処理により表面にアルミナウイスカーを成長させてい
る。Various methods have been proposed as a method for producing alumina whiskers. For example, JP-A-56-96
No. 726 has 15% ≤ Cr ≤ 25%, 3% ≤ Al ≤ 6%
A ferritic stainless steel foil containing a is produced by a metal peeling method (peeling), and this foil is oxidized in the atmosphere at 870 ° C to 970 ° C to grow alumina whiskers on the foil surface. No. 71898 15%
Ferrite stainless steel foil containing ≦ Cr ≦ 25%, 3% ≦ Al ≦ 6% in an atmosphere of carbon dioxide, nitrogen, hydrogen or rare gas having an oxygen partial pressure of 0.75 Torr or less 8
After heating at 75 ° C to 925 ° C for about 1 minute, 87 in air
Alumina whiskers are grown on the surface by a two-step heat treatment in which oxidation is performed for a long time at a temperature between 0 ° C and 930 ° C.
【０００５】しかしながら、特開昭５６−９６７２６号
の如く、ピーリング法による金属箔の製造は、大量生産
が困難であること、また、特開昭５７−７１８９８号の
方法は、アルミニウムを３〜６％含有する高Ａｌ含有ス
テンレス鋼を使用しているが、このような高Ａｌ含有フ
ェライトステンレス鋼は、靭性に乏しく大量生産するこ
とは困難である。However, as described in JP-A-56-96726, it is difficult to mass-produce metal foil by the peeling method, and in JP-A-57-71898, aluminum is used in an amount of 3-6. %, A high Al content stainless steel is used, but such a high Al content ferritic stainless steel has poor toughness and is difficult to mass produce.
【０００６】[0006]
【発明が解決しようとする課題】本発明者らは、上記の
欠点を解決すべく種々検討した結果、上記の方法を経る
となく、ウオッシュコートに対して良好な密着性を有す
る酸化物で被覆された金属箔を大量生産可能な方法を見
出し本発明を完成したもので、本発明の目的は、ウオッ
シュコートに対して良好な密着性を有する酸化物で被覆
された金属箔を製造する方法を提供するにある。DISCLOSURE OF THE INVENTION As a result of various investigations to solve the above-mentioned drawbacks, the inventors of the present invention did not go through the above-mentioned method and coated with an oxide having good adhesion to a washcoat. The present invention has been completed to find out a method capable of mass-producing a metal foil, and an object of the present invention is to provide a method for producing an oxide-coated metal foil having good adhesion to a washcoat. To provide.
【０００７】[0007]
【課題を解決するための手段】本発明は、凝着めっき法
により表面に形成された０．５μｍ以上２０μｍ以下の
範囲の厚さのＡｌメッキ層を付与したステンレス鋼を低
酸素分圧下で加熱して表面のＡｌ層のＡｌをステンレス
鋼中に拡散させると共に、表面に酸化物を形成させ、次
いで、これを５０％以上の圧下率で冷間圧延を施して該
表面に微細なクラックを発生させることを特徴とする酸
化物で被覆された金属箔の製造方法である。According to the present invention, a stainless steel provided with an Al plating layer having a thickness in the range of 0.5 μm or more and 20 μm or less formed on the surface by an adhesion plating method is heated under a low oxygen partial pressure. Then, Al in the Al layer on the surface is diffused into the stainless steel, and an oxide is formed on the surface. Then, this is cold-rolled at a rolling reduction of 50% or more to generate fine cracks on the surface. And a method for producing a metal foil coated with an oxide.
【０００８】すなわち、本発明では、従来、酸化物ウィ
スカーで被覆する代わりに、冷間圧延して表面に微細な
クラックを発生させ、これによって、ウオッシュコート
に対する密着性を良好なものとするのである。That is, in the present invention, in place of the conventional coating with oxide whiskers, cold rolling is performed to generate fine cracks on the surface, thereby improving the adhesion to the washcoat. .
【０００９】本発明における凝着めっき法とは凝着機構
によって被めっき物をめっき材に結合させる方法であっ
て、具体的にはメカニカルプレーティングのようなめっ
き方法が好ましい。メカニカルプレーティング法による
めっき方法とは、本発明者らによって、提案された手段
で、純金属或は合金をブラシ状にして金属ブラシとし、
該金属ブラシとめっき金属から成る金属ブロックを摩擦
接触させて、金属ブラシにより金属ブロックの金属の微
少部分を剥ぎ取ると同時に、前記金属ブラシを被めっき
材料と摩擦接触させて、剥ぎ取った金属ブロックの金属
を金属ブラシを介して被めっき材表面に機械的にプレー
テイングさせることを特徴とするメカニカルプレーティ
ング方法である（特願昭６２−２９９７１４号参照）。The adhesion plating method in the present invention is a method of bonding an object to be plated to a plating material by an adhesion mechanism, and specifically, a plating method such as mechanical plating is preferable. The plating method by the mechanical plating method is a means proposed by the present inventors, and a pure metal or alloy is made into a brush shape into a metal brush,
The metal block made of a plated metal is brought into frictional contact with the metal brush to peel off a minute portion of the metal of the metal block, and at the same time, the metal brush is brought into frictional contact with the material to be plated to peel off the metal block. Is a mechanical plating method characterized by mechanically plating the above metal on the surface of a material to be plated through a metal brush (see Japanese Patent Application No. 62-299714).
【００１０】本発明においては、この凝着めっき方法で
Ａｌ金属層を設けるもので、凝着めっき方法を採用した
理由は、他の化学めっき法や溶融めっき法とは異なり、
めっき層を薄くすることができ、まためっき層の厚さを
コントロールすることが容易にできるためである。In the present invention, the Al metal layer is provided by this adhesion plating method. The reason why the adhesion plating method is adopted is different from other chemical plating methods and hot dip plating methods.
This is because the plating layer can be thinned and the thickness of the plating layer can be easily controlled.
【００１１】そして、本発明ではめっき層の厚さとして
０．５μｍ以上２０μｍ以下とするもので、０．５μｍ
以下では薄すぎ、Ａｌの拡散又はＡｌ酸化物の生成に取
って不利である。また、２０μｍを越えると事後の工程
である冷間圧延によって微細なクラックが入りにくいの
である。In the present invention, the thickness of the plating layer is 0.5 μm or more and 20 μm or less.
Below, it is too thin, which is disadvantageous for Al diffusion or Al oxide formation. On the other hand, if it exceeds 20 μm, it is difficult for fine cracks to be formed by cold rolling which is a subsequent process.
【００１２】本発明で使用する素材としては特に限定さ
れるものではないが、Ａｌの拡散を容易にする意味でＡ
ｌ≧３％含有のステンレス鋼板が好ましい。The material used in the present invention is not particularly limited, but A is used to facilitate the diffusion of Al.
A stainless steel plate containing l ≧ 3% is preferable.
【００１３】本発明で使用する素材としては特に限定さ
れるものではなく、Ｆｅ−１８％Ｃｒ−３％Ａｌ、Ｆｅ
−２０％Ｃｒ−５％Ａｌ等のＡｌ含有フェライトステン
レス鋼、あるいはＡｌを含まないＳＵＳ４３０等を用い
ることもできる。The material used in the present invention is not particularly limited, and Fe-18% Cr-3% Al, Fe
Al-containing ferritic stainless steel such as -20% Cr-5% Al, or SUS430 containing no Al can also be used.
【００１４】次に、本発明においては、凝着めっき法に
よって形成されたＡｌめっき層を有するステンレス鋼板
を低酸素分圧下で熱処理を施す。低酸素分圧としてはＰ
ｏ２≦１×１０−３Ｔｏｒｒ程度が好ましい。酸素分圧
が高いとＡｌの優先酸化が生じない。加熱温度は加熱時
間によって種々変更するが、Ｆｅ−１８％Ｃｒ−３％Ａ
ｌについて加熱温度と加熱時間との関係を調べた結果を
図１に示す。条件として、メカニカルプレーティング方
法を用い０．１ｍｍ厚のＦｅ−１８％Ｃｒ−３％Ａｌに
１μｍのＡｌをめっきし、ＮＨ３分解ガス雰囲気中（酸
素分圧８×１０−４Ｔｏｒｒ）で加熱した。Next, in the present invention, the stainless steel plate having the Al plating layer formed by the adhesion plating method is heat-treated under a low oxygen partial pressure. P for low oxygen partial pressure
It is preferably about o 2 ≦ 1 × 10 −3 Torr. When the oxygen partial pressure is high, preferential oxidation of Al does not occur. The heating temperature varies depending on the heating time, but Fe-18% Cr-3% A
The result of examining the relationship between the heating temperature and the heating time for l is shown in FIG. As a condition, 0.1 μm thick Fe-18% Cr-3% Al is plated with 1 μm of Al using a mechanical plating method, and heated in an atmosphere of NH 3 decomposition gas (oxygen partial pressure 8 × 10 −4 Torr). did.
【００１５】また、加熱温度が１０００℃以上の温度で
あると、生ずる酸化物はα−Ａｌ２Ｏ３となってθ−Ａ
ｌ２Ｏ３より酸化速度が遅くなり、使用環境において好
ましい。また、この熱処理において、例えばＦｅ−Ａｌ
のような金属間化合物が生成すると、脆くなり、その後
の処理において支障をきたすので、化合物の生成は避け
なければならない。したがって、温度と時間の関係とし
ては、 ｔ≧−０．９×Ｔ＋１０２０ 但し、ｔ：時間（ｓｅｃ） Ｔ：温度（℃） を満足することが好ましい。When the heating temperature is 1000 ° C. or higher, the resulting oxide becomes α-Al 2 O 3 and θ-A.
Since the oxidation rate is slower than that of l 2 O 3 , it is preferable in the use environment. In this heat treatment, for example, Fe-Al
When such an intermetallic compound is formed, it becomes brittle and interferes with the subsequent processing, so the formation of the compound must be avoided. Therefore, as the relationship between the temperature and the time, it is preferable that t ≧ −0.9 × T + 1020, where t: time (sec) T: temperature (° C.) is satisfied.
【００１６】このようにして表面にＡｌ酸化物被膜を有
する素材を圧延すると、Ａｌ酸化物と素材との延性が異
なるために圧延によって延性に乏しいＡＩ酸化物層に微
小なクラックが生ずる。この際、圧延率は５０％以上と
する。圧延率が５０％未満であると微小なクラックが生
じにくい。また、圧延率が９０％を超えるとクラックが
大きすぎて密着性を低下させる可能性がある。したがっ
て、圧延条件としては５０％ないし９０％の圧下率を適
用することが好ましい。When a material having an Al oxide film on the surface is rolled in this manner, minute cracks are generated in the AI oxide layer having poor ductility due to rolling because the ductility of the Al oxide is different from that of the material. At this time, the rolling rate is 50% or more. If the rolling ratio is less than 50%, minute cracks are unlikely to occur. Further, if the rolling ratio exceeds 90%, the crack may be too large and the adhesion may be deteriorated. Therefore, it is preferable to apply a rolling reduction of 50% to 90% as rolling conditions.
【００１７】[0017]
【実施例】以下、本発明の実施例及び比較例をもって、
更に具体的に説明するが、本発明は、これら実施例に限
定されるものではない。実施例及び比較例では５０ｍｍ
×５０ｍｍの大きさのものを試験片として使用した。EXAMPLES Hereinafter, with examples and comparative examples of the present invention,
More specifically, the present invention is not limited to these examples. 50 mm in Examples and Comparative Examples
A test piece having a size of × 50 mm was used.
【００１８】（実施例１〜６、及び、比較例１〜６）試
験片を表１に示す条件下で凝着めっき、熱処理及び冷間
圧延を行って酸化物で被覆された金属箔を作成した。次
いで、この金属箔にウオッシュコートを塗布し、水中で
超音波洗浄を行い、ウオッシュコートの剥離を目視で観
察し、ウオッシュコートの残存率を％で表わし評価し
た。本発明にかかる酸化物で被覆された金属箔は残存率
が９５％以上であった。(Examples 1 to 6 and Comparative Examples 1 to 6) Test pieces were subjected to adhesion plating, heat treatment and cold rolling under the conditions shown in Table 1 to prepare metal foils coated with oxide. did. Next, a wash coat was applied to this metal foil, ultrasonic cleaning was performed in water, and the peeling of the wash coat was visually observed, and the residual rate of the wash coat was expressed in% and evaluated. The metal foil coated with the oxide according to the present invention had a residual rate of 95% or more.
【００１９】表１において＊印は本発明で規定した条件
に外れることを示した。In Table 1, the mark * indicates that the condition defined by the present invention is not satisfied.
【表１】 [Table 1]
【００２０】[0020]
【発明の効果】以上述べたように、本発明は、特定の方
法によつて表面に形成された０．５μｍ以上２０μｍ以
下の厚さのＡｌメッキ層を特定の熱処理及び冷間圧延に
よって該表面に微細なクラックを発生させ、これによっ
てウオッシュコートとの密着性を改善することができた
ので、従来のウイスカー状酸化物で被覆された高Ａｌ含
有フェライトステンレス鋼の場合に比して、自動車排ガ
スコンバーターに使用されるメタルハニカム用材料に適
した金属箔の大量生産が可能となった。As described above, according to the present invention, an Al plating layer having a thickness of 0.5 μm or more and 20 μm or less formed on a surface by a specific method is subjected to a specific heat treatment and cold rolling to obtain the surface. Since it was possible to improve the adhesion with the washcoat by generating fine cracks in the car, compared with the case of the high Al content ferritic stainless steel coated with conventional whisker-like oxide, Mass production of metal foil suitable for metal honeycomb material used in converters has become possible.
【００２１】[0021]
【図１】本発明方法における熱処理条件の加熱温度と加
熱時間を表す。FIG. 1 shows heating temperature and heating time under heat treatment conditions in the method of the present invention.
Claims (1)
０．５μｍ以上２０μｍ以下の範囲の厚さのＡｌメッキ
層を付与したステンレス鋼を低酸素分圧下で加熱して表
面のＡｌ層のＡｌをステンレス鋼中に拡散させると共
に、表面に酸化物を形成させ、次いで、これを５０％以
上の圧下率で冷間圧延を施して該表面に微細なクラック
を発生させることを特徴とする酸化物で被覆された金属
箔の製造方法。1. A stainless steel having an Al plating layer having a thickness in the range of 0.5 μm or more and 20 μm or less formed on the surface by an adhesion plating method is heated under a low oxygen partial pressure to form an Al of the surface Al layer. Oxide is diffused into stainless steel, and an oxide is formed on the surface, and then cold rolling is performed at a rolling reduction of 50% or more to generate fine cracks on the surface. A method for producing a metal foil coated with.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3099900A JPH06126192A (en) | 1991-02-04 | 1991-02-04 | Production of metallic foil coated with oxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP3099900A JPH06126192A (en) | 1991-02-04 | 1991-02-04 | Production of metallic foil coated with oxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH06126192A true JPH06126192A (en) | 1994-05-10 |
Family
ID=14259652
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP3099900A Pending JPH06126192A (en) | 1991-02-04 | 1991-02-04 | Production of metallic foil coated with oxide |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH06126192A (en) |
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1991
- 1991-02-04 JP JP3099900A patent/JPH06126192A/en active Pending
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