JPH11179214A - Metallic honeycomb for catalyst excellent in adhesion of wash coat - Google Patents
Metallic honeycomb for catalyst excellent in adhesion of wash coatInfo
- Publication number
- JPH11179214A JPH11179214A JP9353375A JP35337597A JPH11179214A JP H11179214 A JPH11179214 A JP H11179214A JP 9353375 A JP9353375 A JP 9353375A JP 35337597 A JP35337597 A JP 35337597A JP H11179214 A JPH11179214 A JP H11179214A
- Authority
- JP
- Japan
- Prior art keywords
- foil
- less
- stainless steel
- catalyst
- metal honeycomb
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 239000011888 foil Substances 0.000 claims abstract description 71
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 34
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 33
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 23
- 239000010935 stainless steel Substances 0.000 claims abstract description 23
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 14
- 238000009792 diffusion process Methods 0.000 claims abstract description 12
- 150000004767 nitrides Chemical class 0.000 claims abstract description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims description 40
- 239000002184 metal Substances 0.000 claims description 40
- 239000002244 precipitate Substances 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 7
- 238000005219 brazing Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000012535 impurity Substances 0.000 claims description 3
- 229910000831 Steel Inorganic materials 0.000 claims 1
- 239000010959 steel Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 15
- 229910002804 graphite Inorganic materials 0.000 abstract description 10
- 239000010439 graphite Substances 0.000 abstract description 10
- 238000005304 joining Methods 0.000 abstract description 10
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000000034 method Methods 0.000 abstract description 5
- 230000008021 deposition Effects 0.000 abstract 2
- 230000002401 inhibitory effect Effects 0.000 abstract 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 241000264877 Hippospongia communis Species 0.000 description 31
- 229910052761 rare earth metal Inorganic materials 0.000 description 13
- 150000001247 metal acetylides Chemical class 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 238000001556 precipitation Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000010030 laminating Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 238000005098 hot rolling Methods 0.000 description 2
- 238000003780 insertion Methods 0.000 description 2
- 230000037431 insertion Effects 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 238000004804 winding Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 229910001122 Mischmetal Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
Landscapes
- Exhaust Gas After Treatment (AREA)
- Catalysts (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は自動車、自家発電機
等の内燃機関の排気ガス浄化や化学プラント等で使用さ
れる触媒用メタルハニカムに関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal honeycomb for a catalyst used in an exhaust gas purification of an internal combustion engine such as an automobile and a private power generator and a chemical plant.
【０００２】[0002]
【従来の技術】近年、自動車や自家発電機等の内燃機関
の排気ガス浄化や、化学プラント等において使用される
触媒装置の基体として、従来のセラミック製ハニカムに
代え、耐熱ステンレス鋼製のメタルハニカムが使用され
る例が増えつつある。その理由として、メタルハニカム
の壁厚がセラミック製のものより薄いので、通気抵抗が
小さくエンジン出力の損失が少ないこと、また熱容量が
小さいので触媒の作用温度に早く加熱され、エンジン始
動初期の排ガス浄化能が優れていること、さらに温度の
上下が激しい排ガス環境下においても耐久性が優れてい
ること、などが挙げられる。2. Description of the Related Art In recent years, a metal honeycomb made of a heat-resistant stainless steel has been used instead of a conventional ceramic honeycomb as a base of a catalyst device used in an exhaust gas purification of an internal combustion engine such as an automobile or a private power generator or a chemical plant. Examples where are used are increasing. The reason is that the wall thickness of the metal honeycomb is thinner than that of ceramics, so that the ventilation resistance is small and the loss of engine output is small, and because the heat capacity is small, it is quickly heated to the operating temperature of the catalyst, and the exhaust gas purification at the initial stage of engine startup High performance, and also excellent durability even in an exhaust gas environment where the temperature rises and falls sharply.
【０００３】従来のメタルハニカムは、耐熱ステンレス
鋼箔の平箔と波箔を重ねて巻回または積層し、平箔と波
箔の接触部を接合して製造される。接合は真空加熱炉に
て、ろう付けまたは拡散接合により行われる。また、メ
タルハニカムを外筒に挿入したものについては、挿入
後、平箔と波箔の接触部およびハニカムと外筒の間が同
時に接合される。これら外筒に挿入され、あるいは挿入
されてないメタルハニカムの多数の通気孔をなす箔表面
に、ウォッシュコートと呼ばれるγアルミナ主体の多孔
質層を形成し、このウォッシュコートにＰｔ等の貴金属
からなる触媒を担持させ、排ガス経路に装着して、浄化
装置が構成される。A conventional metal honeycomb is manufactured by laminating and winding or laminating a flat foil of heat-resistant stainless steel foil and a corrugated foil, and joining a contact portion between the flat foil and the corrugated foil. Bonding is performed by brazing or diffusion bonding in a vacuum heating furnace. When the metal honeycomb is inserted into the outer cylinder, after the insertion, the contact portion between the flat foil and the corrugated foil and between the honeycomb and the outer cylinder are simultaneously joined. A porous layer mainly composed of γ-alumina, called a wash coat, is formed on the surface of a foil forming a large number of air holes of a metal honeycomb inserted or not inserted into these outer tubes, and the wash coat is made of a precious metal such as Pt. A purification device is configured by supporting a catalyst and mounting the catalyst in an exhaust gas path.
【０００４】ところで、上記ろう付けや拡散接合を工業
的規模で行うための大型の真空熱処理炉は、そのほとん
どがグラファイトヒーターによる加熱方式を採用してい
る。この方式で、ＴｉやＮｂを含有するステンレス鋼製
のメタルハニカム、あるいは該メタルハニカムを外筒に
挿入してなるメタル担体を熱処理すると、加熱時にヒー
ターから放出されるカーボンと、ステンレス鋼中のＴｉ
やＮｂとが、メタルハニカムの表面で反応して、Ｔｉや
Ｎｂの炭化物が生成し析出する。これら炭化物は、ウォ
ッシュコート層の密着性を阻害し、著しい場合は触媒使
用中にウォッシュコート層ごと触媒が剥離するという問
題が生じる。[0004] Most of the large-scale vacuum heat treatment furnaces for performing the above-mentioned brazing and diffusion bonding on an industrial scale employ a heating method using a graphite heater. In this method, when a stainless steel metal honeycomb containing Ti or Nb or a metal carrier obtained by inserting the metal honeycomb into an outer tube is heat-treated, carbon released from the heater at the time of heating and Ti in the stainless steel are heated.
And Nb react on the surface of the metal honeycomb to generate and precipitate carbides of Ti and Nb. These carbides hinder the adhesion of the washcoat layer, and in a significant case, there is a problem that the catalyst is peeled off together with the washcoat layer during use of the catalyst.
【０００５】本発明者らはその対策として、ＴｉやＮｂ
を含有する耐熱ステンレス鋼箔のメタルハニカムや、該
メタルハニカムを外筒に挿入してなるメタル担体の製造
に際し、平箔と波箔の接合、あるいはハニカムと外筒を
接合するための真空熱処理工程において、グラファイト
を除く加熱源、たとえばＭｏ，Ｔａ，Ｗなどからなるヒ
ーターにより加熱する方法を提案し、特開平９−８５１
０３号公報に開示されている。[0005] The present inventors have taken measures against such problems as Ti and Nb.
In the manufacture of a metal honeycomb made of a heat-resistant stainless steel foil or a metal carrier obtained by inserting the metal honeycomb into an outer cylinder, a vacuum heat treatment step for joining a flat foil and a corrugated foil or for joining a honeycomb and an outer cylinder In Japanese Patent Application Laid-Open No. 9-851, a method of heating with a heating source excluding graphite, for example, a heater made of Mo, Ta, W or the like is proposed.
No. 03 is disclosed.
【０００６】[0006]
【発明が解決しようとする課題】しかし、メタルハニカ
ム、あるいはメタルハニカムを外筒に挿入してなるメタ
ル担体を製造するにあたって、グラファイトヒーターを
加熱源とする汎用の真空熱処理炉を採用することも必要
であり、上記公報に提案した以外の対策も要望されてい
る。また、箔表面にＴｉやＮｂの窒化物や炭窒化物が析
出している場合もウォッシュコート層の密着性が阻害さ
れるということが判明した。However, in manufacturing a metal honeycomb or a metal carrier in which a metal honeycomb is inserted into an outer cylinder, it is necessary to employ a general-purpose vacuum heat treatment furnace using a graphite heater as a heating source. Therefore, measures other than those proposed in the above publication are also demanded. It was also found that the adhesion of the washcoat layer was also inhibited when nitrides or carbonitrides of Ti or Nb were precipitated on the foil surface.
【０００７】そこで本発明は、内燃機関の排ガス浄化や
化学プラント等において使用される触媒装置の基体とし
てのメタルハニカムであって、ＴｉやＮｂを含有する耐
熱ステンレス鋼製の平箔と波箔で形成され、必要に応じ
て外筒に挿入されたもののウォッシュコート密着性を向
上し、使用中の触媒剥離の問題を解消することを目的と
する。Accordingly, the present invention provides a metal honeycomb as a base of a catalyst device used in purification of exhaust gas of an internal combustion engine, a chemical plant, etc., which is made of a flat foil and a corrugated foil made of heat-resistant stainless steel containing Ti or Nb. It is an object of the present invention to improve the washcoat adhesion of the formed and inserted into the outer cylinder as necessary, and to solve the problem of catalyst peeling during use.
【０００８】また、平箔と波箔の接合、あるいはハニカ
ムと外筒の接合を行う真空熱処理工程で、グラファイト
ヒーターを加熱源とした場合でも、箔表面にＴｉやＮｂ
の炭化物が析出するのを抑制し、また窒化物や炭窒化物
の析出をも抑制することで、ウォッシュコート層との密
着性を良好に保ち、触媒剥離の問題を解消することを目
的とする。In a vacuum heat treatment step of joining a flat foil and a corrugated foil or joining a honeycomb and an outer cylinder, even when a graphite heater is used as a heating source, Ti or Nb
The purpose of the present invention is to suppress the precipitation of carbides, and also suppress the precipitation of nitrides and carbonitrides, thereby maintaining good adhesion with the washcoat layer and eliminating the problem of catalyst peeling. .
【０００９】[0009]
【課題を解決するための手段】上記目的を達成するため
の本発明は、耐熱ステンレス鋼箔の平箔と波箔が重ねて
巻回または積層され、前記平箔と前記波箔の接触部がろ
う付けまたは拡散接合により接合されたメタルハニカム
において、前記ステンレス鋼箔がＴｉとＮｂの一方また
は双方を含有し、かつ前記平箔および波箔の表面には、
ＴｉおよびＮｂの一方または双方の炭化物、窒化物、ま
たは炭窒化物からなる析出物がないか、または該析出物
の面積率が３０％以下であることを特徴とするウォッシ
ュコート密着性に優れた触媒用メタルハニカムである。According to the present invention, there is provided a heat-resistant stainless steel foil comprising a flat foil and a corrugated foil which are wound or laminated so that a contact portion between the flat foil and the corrugated foil is formed. In the metal honeycomb joined by brazing or diffusion joining, the stainless steel foil contains one or both of Ti and Nb, and the surface of the flat foil and the corrugated foil has
Excellent in washcoat adhesion, characterized in that there is no precipitate composed of carbide, nitride or carbonitride of one or both of Ti and Nb, or the area ratio of the precipitate is 30% or less. It is a metal honeycomb for a catalyst.
【００１０】そして、前記ステンレス鋼箔の成分組成に
おいて、ＴｉとＮｂの一方または双方の含有量がＣ量お
よびＮ量との関係で、（１）式を満足する範囲であるこ
とが好ましい。 Ｎｂ＋２Ｔｉ−８（Ｃ＋Ｎ）＜０．２ （１） ただし、Ｎｂ，Ｔｉ，Ｃ、およびＮは、それぞれＮｂ，
Ｔｉ，Ｃ、およびＮの含有量（重量％）。[0010] In the component composition of the stainless steel foil, the content of one or both of Ti and Nb is preferably in a range satisfying the expression (1) in relation to the C content and the N content. Nb + 2Ti-8 (C + N) <0.2 (1) where Nb, Ti, C, and N are Nb,
Content of Ti, C, and N (% by weight).
【００１１】また前記ステンレス鋼箔の成分組成が、重
量％にて、 Ｃ ：０．０２５％以下、 Ｎ ：０．０２％以下、 Ｃ＋Ｎ：０．０３％以下、 Ｓｉ：０．５％以下、 Ｍｎ：１．０％以下、 Ｃｒ：１２〜３０％ Ａｌ：２〜１０％以下 であり、ＴｉとＮｂの一方または双方を、 Ｔｉ：０．０２〜０．２０％、 Ｎｂ：０．０５〜０．３５％ の範囲で含有し、残部がＦｅおよび不可避的不純物から
なるものとすることができる。In addition, the composition of the stainless steel foil is as follows: C: 0.025% or less; N: 0.02% or less; C + N: 0.03% or less; Si: 0.5% or less; Mn: 1.0% or less, Cr: 12 to 30% Al: 2 to 10% or less, one or both of Ti and Nb, Ti: 0.02 to 0.20%, Nb: 0.05 to It can be contained in the range of 0.35%, with the balance being Fe and unavoidable impurities.
【００１２】そして、さらに重量％にて Ｐ：３１／２３３×（ＲＥＭ＋０．０２１）％〜０．１
％、 ＲＥＭ：０．０６％超〜０．１５％ を含有するものとするのが好ましい。Further, in weight%, P: 31/233 × (REM + 0.021)%-0.1
%, REM: more than 0.06% to 0.15%.
【００１３】[0013]
【発明の実施の形態】本発明の触媒用メタルハニカム
は、ＴｉとＮｂの一方または双方を含む耐熱ステンレス
鋼箔の帯状の平箔と波箔を重ねて渦巻状に巻回し、ある
いは所定寸法に切断した平箔と波箔を交互にして積層
し、平箔と波箔の接触部をろう付けまたは拡散接合によ
り接合して製造される。なお本発明のメタルハニカム
は、外筒に挿入された状態のメタル担体であってもよ
く、その場合は、外筒に挿入したのち、平箔と波箔の接
合およびメタルハニカム最表面と外筒内面の接合が同時
に行われる。BEST MODE FOR CARRYING OUT THE INVENTION A metal honeycomb for a catalyst according to the present invention is obtained by laminating a belt-shaped flat foil and a corrugated foil of a heat-resistant stainless steel foil containing one or both of Ti and Nb, and spirally winding the foil. It is manufactured by alternately laminating the cut flat foil and corrugated foil, and joining the contact portions between the flat foil and the corrugated foil by brazing or diffusion bonding. Note that the metal honeycomb of the present invention may be a metal carrier inserted in an outer cylinder, in which case, after insertion into the outer cylinder, bonding of the flat foil and corrugated foil and the outermost surface of the metal honeycomb and the outer cylinder Bonding of the inner surface is performed simultaneously.
【００１４】そしてハニカムを構成する平箔および波箔
の表面には、ＴｉとＮｂの一方または双方の炭化物、窒
化物または炭窒化物からなる析出物がないか、またはこ
れら析出物の面積率が３０％以下である。この面積率は
箔表面の全面積に対する析出物の面積の平均的な割合で
あり、析出物は、部分的に著しく集中することなく、適
当に分散した状態で存在する。On the surface of the flat foil and corrugated foil constituting the honeycomb, there is no precipitate made of carbide, nitride or carbonitride of one or both of Ti and Nb, or the area ratio of these precipitates is reduced. 30% or less. This area ratio is an average ratio of the area of the precipitate to the entire area of the foil surface, and the precipitate exists in an appropriately dispersed state without being significantly concentrated locally.
【００１５】本発明者らは、上記炭化物、窒化物、炭窒
化物の析出状態が種々異なるメタルハニカムについて、
ウォッシュコート層を形成し、触媒使用時を想定した試
験によるウォッシュコートの剥離状況を調べた。その結
果、箔表面の全面積に対する上記析出物の面積率が３０
％以下であれば、ウォッシュコートが剥離しないか、ま
たは剥離しても実害が生じるおそれのない程度であるこ
とが判明した。したがって本発明のメタルハニカムを上
記のように限定した。The present inventors have proposed metal honeycombs having various precipitation states of the carbides, nitrides, and carbonitrides described above.
A washcoat layer was formed, and the state of peeling of the washcoat was examined by a test assuming the use of a catalyst. As a result, the area ratio of the precipitate to the total area of the foil surface was 30%.
%, It was found that the washcoat was not peeled off, or even if peeled off, there was no risk of causing actual harm. Therefore, the metal honeycomb of the present invention is limited as described above.
【００１６】本発明で採用するステンレス鋼箔の成分組
成において、Ｔｉ，Ｎｂの含有量は、Ｃ量およびＮ量に
応じて上記（１）式を満足する範囲とするのが好まし
い。この範囲であれば、平箔と波箔の接合、あるいはさ
らにハニカムと外筒の接合に際し、グラファイトヒータ
ーによる加熱方式の装置で真空熱処理を行っても、上記
析出物の面積率が３０％以下となる。Ｍｏ，Ｔａ，Ｗな
ど、グラファイトを除く加熱源からなるヒーターによる
加熱方式の装置で行えば、上記析出物の面積率をより低
めることができ、析出物のない状態とすることもでき
る。In the component composition of the stainless steel foil used in the present invention, the contents of Ti and Nb are preferably in a range satisfying the above-mentioned formula (1) according to the amounts of C and N. Within this range, the area ratio of the precipitates is 30% or less even when vacuum heat treatment is performed by a heating device using a graphite heater when bonding the flat foil and the corrugated foil or further bonding the honeycomb and the outer cylinder. Become. When the heating is performed by a heater using a heater including a heating source other than graphite, such as Mo, Ta, or W, the area ratio of the precipitates can be further reduced and a state without precipitates can be achieved.
【００１７】また上記接合に際し、拡散促進剤としてカ
ーボンを塗布し液相接合すること（たとえば特開平６−
１０６０７２号公報）が効果的な接合手段として採用さ
れるが、Ｔｉ，Ｎｂの含有量を（１）式の範囲とするこ
とで、塗布したカーボンの影響で炭化物が析出しても、
上記析出物の面積率が３０％以下となる。 なお、 Ｎｂ＋２Ｔｉ−８（Ｃ＋Ｎ）＜０．０５ （２） を満足する範囲とするのがより好ましい。At the time of the above-mentioned bonding, carbon is applied as a diffusion accelerator and liquid-phase bonding is performed (for example, see Japanese Patent Application Laid-Open
No. 106072) is adopted as an effective joining means. However, by setting the contents of Ti and Nb in the range of the formula (1), even if carbides are precipitated due to the influence of the applied carbon,
The area ratio of the precipitate is 30% or less. It is more preferable to set the range to satisfy Nb + 2Ti-8 (C + N) <0.05 (2).
【００１８】その他の成分については、つぎのようなＣ
ｒ−Ａｌ系の成分系とすることができる。すなわち、重
量％にて、Ｃｒ：１２〜３０％およびＡｌ：２〜１０％
を含み、Ｃ：０．０２５％以下、Ｎ：０．０２％以下、
Ｃ＋Ｎ：０．０３％以下、Ｓｉ：０．５％以下、Ｍｎ：
１．０％以下とし、ＴｉとＮｂの一方または双方を、Ｔ
ｉ：０．０２〜０．２０％、Ｎｂ：０．０５〜０．３５
％の範囲で含み、残部がＦｅおよび不可避的不純物から
なる。そして、好ましくはさらに、Ｐ：３１／２３３×
（ＲＥＭ＋０．０２１）％〜０．１％、およびＲＥＭ：
０．０６％超〜０．１５％を含有する。As for other components, the following C
An r-Al-based component system can be used. That is, in weight%, Cr: 12 to 30% and Al: 2 to 10%
C: 0.025% or less, N: 0.02% or less,
C + N: 0.03% or less, Si: 0.5% or less, Mn:
1.0% or less, and one or both of Ti and Nb
i: 0.02 to 0.20%, Nb: 0.05 to 0.35
%, With the balance being Fe and unavoidable impurities. And preferably, P: 31/233 ×
(REM + 0.021)%-0.1%, and REM:
Contains> 0.06% to 0.15%.
【００１９】Ｃｒはステンレス鋼の耐食性を確保するた
めの基本元素である。本成分系にあっては、高温排ガス
に対する耐酸化性はＡｌ2 Ｏ3 皮膜によりもたらされる
が、Ｃｒが不足すると該皮膜の密着性や保護性が低下す
る。一方Ｃｒが過剰になると熱延板の靭性が低下し、製
造性が損なわれる。したがってＣｒ含有量を１２％以上
３０％以下とした。Cr is a basic element for ensuring the corrosion resistance of stainless steel. In this component system, oxidation resistance to high-temperature exhaust gas is provided by the Al 2 O 3 film, but if Cr is insufficient, the adhesion and protection of the film deteriorate. On the other hand, when Cr is excessive, the toughness of the hot-rolled sheet is reduced, and the productivity is impaired. Therefore, the Cr content is set to 12% or more and 30% or less.
【００２０】Ａｌは本成分系にあっては上記のようにＡ
ｌ2 Ｏ3 を生成し、高温排ガスに対する耐酸化性を確保
するための基本元素である。不足すると箔の異常酸化が
たやすく発生し、触媒の担体としての使用に耐えなくな
る。一方過剰になると、熱延板の靭性が低下するほか箔
の膨張係数が大きくなり、触媒担体として使用時に、加
熱と冷却の繰返しによる熱疲労が大きくなる。したがっ
てＡｌ含有量を２％以上１０％以下とした。Al is A in the present component system as described above.
It is a basic element for producing l 2 O 3 and ensuring oxidation resistance to high-temperature exhaust gas. If the amount is insufficient, abnormal oxidation of the foil easily occurs, and the foil cannot be used as a catalyst carrier. On the other hand, when it is excessive, the toughness of the hot-rolled sheet is reduced and the expansion coefficient of the foil is increased, and when used as a catalyst carrier, thermal fatigue due to repeated heating and cooling is increased. Therefore, the Al content is set to 2% or more and 10% or less.
【００２１】ＣおよびＮは、本成分系にあってはともに
熱延版の靭性を低下させる。この影響はＴｉやＮｂの作
用により抑えることができるが、Ｃが０．０２５％を超
える場合、Ｎが０．０２％を超える場合、またはＣ＋Ｎ
が０．０３％を超える場合は、ＴｉやＮｂの作用をもっ
てしても靭性低下による問題を解消することが困難とな
る。したがって、Ｃ含有量を０．０２５％以下、Ｎ含有
量を０．０２％以下、Ｃ＋Ｎを０．０３％以下とした。C and N both reduce the toughness of the hot-rolled plate in the present component system. This effect can be suppressed by the action of Ti or Nb, but when C exceeds 0.025%, when N exceeds 0.02%, or when C + N
Exceeds 0.03%, it becomes difficult to solve the problem due to the decrease in toughness even with the action of Ti or Nb. Therefore, the C content is set to 0.025% or less, the N content is set to 0.02% or less, and the C + N is set to 0.03% or less.
【００２２】Ｓｉは本成分系にあっては熱延版の靭性を
低下させるので、少量に抑えることが望ましく、０．５
％以下とした。Ｍｎはごく初期の酸化皮膜中に濃化し、
以後のＡｌ2 Ｏ3 皮膜の形成に害を及ぼすので低い方が
望ましく、１．０％以下とした。Since Si lowers the toughness of the hot-rolled slab in this component system, it is desirable to keep it to a small amount.
% Or less. Mn is concentrated in the very early oxide film,
A lower value is desirable because it adversely affects the formation of the subsequent Al 2 O 3 film, and is set to 1.0% or less.
【００２３】ＴｉおよびＮｂは、炭化物、窒化物あるい
は炭窒化物を形成し、固溶ＣおよびＮを固定することで
熱延版の靭性低下を抑える作用がある。このためＴｉと
Ｎｂの一方または双方を、Ｔｉにあっては０．０２％以
上、Ｎｂにあっては０．０５％以上添加する。この場
合、ＴｉとＮｂを複合添加することで固溶Ｎｂが増加
し、固溶強化によって高温強度がさらに向上する。Ti and Nb form carbides, nitrides or carbonitrides, and fix solid solution C and N to suppress a decrease in toughness of the hot-rolled plate. Therefore, one or both of Ti and Nb are added at 0.02% or more in Ti and 0.05% or more in Nb. In this case, solid solution Nb increases by adding Ti and Nb in combination, and the high temperature strength is further improved by solid solution strengthening.
【００２４】Ｔｉは、過剰に添加するとＴｉＮ等の粗大
なＴｉ系析出物や介在物が生成し、靭性が低下するの
で、０．２０％を上限とする。Ｎｂは、過剰に添加する
とＮｂ系金属間化合物が生成し、熱間加工性や熱延版の
靭性が低下するので、０．３５％を上限とする。If Ti is added excessively, coarse Ti-based precipitates and inclusions such as TiN are formed, and the toughness is reduced. Therefore, the upper limit is 0.20%. If Nb is excessively added, an Nb-based intermetallic compound is generated, and the hot workability and the toughness of the hot-rolled plate decrease, so the upper limit is 0.35%.
【００２５】Ｐは、本成分系においてはＲＥＭとの関係
で、熱間加工性を改善するため必要に応じて添加する。
本成分系においては、ＲＥＭを添加することで排ガス環
境における耐高温酸化性が著しく向上するが、熱間加工
性が劣化し、熱間圧延工程での問題が生じるおそれがあ
った。そこで、ＲＥＭ添加量に応じてＰを３１／２３３
×（ＲＥＭ＋０．０２１）％以上添加することで、熱間
加工性を向上させ、熱間圧延工程での量産化を可能とし
た。しかし０．１％を超えてＰを添加すると靭性が低下
する。したがって、Ｐは３１／２３３×（ＲＥＭ＋０．
０２１）％以上０．１％以下添加することとした。In the present component system, P is added as necessary in order to improve hot workability in relation to REM.
In this component system, the addition of REM significantly improves high-temperature oxidation resistance in an exhaust gas environment, but deteriorates hot workability and may cause a problem in a hot rolling step. Therefore, P is set to 31/233 according to the amount of REM added.
By adding at least × (REM + 0.021)%, hot workability was improved, and mass production in the hot rolling step was enabled. However, if P is added in excess of 0.1%, the toughness decreases. Therefore, P is 31/233 × (REM + 0.
021)% or more and 0.1% or less.
【００２６】ＲＥＭは、Ｌａ，Ｃｅなどの希土類元素の
ほか、Ｌｎ（ランタノイド）と呼ばれる分離されてない
軽希土類元素の集合体（ミッシュメタル）を含む。これ
らを単独または複合で、０．０６％超添加することによ
り、Ａｌ2 Ｏ3 皮膜中にＦｅ、Ｃｒを主体とした粒状酸
化物が生成するのを抑制し、耐高温酸化性が向上する。
しかし、０．１５％を超えて添加すると、燐化物の影響
で冷間圧延性などの製造性に悪影響が出る。したがって
ＲＥＭは０．０６％超０．１５％以下添加することとし
た。The REM includes, in addition to rare earth elements such as La and Ce, an aggregate of unseparated light rare earth elements (misch metal) called Ln (lanthanoid). Addition of more than 0.06% of these alone or in combination suppresses generation of a particulate oxide mainly composed of Fe and Cr in the Al 2 O 3 film, and improves high-temperature oxidation resistance.
However, if it is added in excess of 0.15%, the phosphide adversely affects the productivity such as cold rolling. Therefore, REM is added in an amount of more than 0.06% and 0.15% or less.
【００２７】[0027]
【実施例】［実施例１］：表１に示す成分組成からなる
５０μｍ厚の帯状ステンレス鋼箔の平箔と、該平箔を波
付け加工した波箔を重ねて渦巻状に巻回し、メタルハニ
カムとした。これを内径８０mmφのステンレス鋼製外筒
に挿入して、平箔と波箔の接触部およびメタルハニカム
の外周面と外筒の内周面を拡散接合し、メタル担体とし
た。拡散接合は、汎用の真空熱処理炉にて、グラファイ
トヒーターにより１２００℃で９０分加熱して行った。[Example 1] A 50 μm-thick flat stainless steel foil having the component composition shown in Table 1 and a corrugated foil obtained by corrugating the flat foil were superposed and spirally wound to form a metal. Honeycomb. This was inserted into a stainless steel outer cylinder having an inner diameter of 80 mmφ, and the contact portion between the flat foil and the corrugated foil, and the outer peripheral surface of the metal honeycomb and the inner peripheral surface of the outer cylinder were diffusion-bonded to obtain a metal carrier. Diffusion bonding was performed by heating at 1200 ° C. for 90 minutes using a graphite heater in a general-purpose vacuum heat treatment furnace.
【００２８】なお、表１において、成分に下線を付した
のは好ましい範囲を外れたものである。本発明例につい
ては対応する請求項を示した。また、拡散接合後の箔表
面を観察して、ＴｉおよびＮｂの一方または双方の炭化
物、窒化物、または炭窒化物からなる析出物の面積率を
評価し、そのランクを表１に示した。本発明例はいずれ
も面積率３０％以下であり、比較例はいずれも３０％を
超えていた。In Table 1, the underlined components are out of the preferred range. Corresponding claims are given for the examples of the present invention. Also, the foil surface after diffusion bonding was observed, and the area ratio of a precipitate formed of carbide, nitride, or carbonitride of one or both of Ti and Nb was evaluated. All of the examples of the present invention had an area ratio of 30% or less, and all of the comparative examples exceeded 30%.
【００２９】拡散接合後のメタル担体にウォッシュコー
トを施した。ウォッシュコートはγアルミナを主体とす
るスラリー液をメタルハニカムに数回ふりかけ、圧縮空
気で余剰のスラリーを落とし、十分に乾燥したうえ７０
０℃で１時間焼付け処理を行って形成した。冷却後、圧
縮空気を用いて剥離試験を行い、ウォッシュコートの剥
離状況を評価した結果を表２に示す。A wash coat was applied to the metal carrier after the diffusion bonding. Wash coat is to spray a slurry liquid mainly composed of γ-alumina several times on a metal honeycomb, drop excess slurry with compressed air, dry it sufficiently, and dry it.
It was formed by baking at 0 ° C. for 1 hour. After cooling, a peeling test was performed using compressed air, and the results of evaluating the peeling state of the washcoat are shown in Table 2.
【００３０】本発明例は、No．１に若干の剥離が認めら
れたものの、その他はいずれも剥離なしであった。本発
明例のNo．１は、Ｎｂ＋２Ｔｉ−８（Ｃ＋Ｎ）の値を示
すように（１）式を満足しないので、若干の剥離が認め
られたと考えられるが、通常の使用では問題にならない
程度のものである。比較例はいずれも、（１）式を満足
せず、かつ析出物の面積率が３０％を超えているので、
多量の剥離が認められた。The examples of the present invention are as follows. Although slight peeling was observed in Sample No. 1, no peeling was observed in all others. No. of the present invention example. No. 1 does not satisfy the expression (1) so as to indicate the value of Nb + 2Ti-8 (C + N), so it is considered that slight peeling was recognized, but it is of a degree that does not cause a problem in normal use. In each of the comparative examples, the formula (1) was not satisfied, and the area ratio of the precipitate exceeded 30%.
A large amount of peeling was observed.
【００３１】［実施例２］：上記実施例１における本発
明例の一部および比較例について、ウォッシュコート層
の上に貴金属触媒を担持させ、これらをエンジンベンチ
試験に供した。試験条件は、排気量２０００ccの４気筒
ガソリンエンジンのエキゾーストマニホールド直下に、
フランジを介して触媒を担持したメタル担体を装着し、
５０００rpm でスロットル全開運転１０分間と、エンジ
ン停止、外部からファン冷却１５分の工程を１５０回繰
返した。なお高速運転中のメタル担体への入りガス温度
は８５０℃になるように調整した。その後、メタル担体
を切断し実体顕微鏡でウォッシュコート層の剥離状況を
調べた。その結果を表２に併せて示す。本発明例は、N
o．１に、通常の使用では問題にならない程度の若干の
剥離が認められたものの、その他はいずれも剥離なしで
あった。これに対して、比較例はいずれも多量の剥離が
認められた。[Example 2]: With respect to a part of the present invention example and the comparative example in the above Example 1, a noble metal catalyst was supported on the wash coat layer, and these were subjected to an engine bench test. The test conditions were directly below the exhaust manifold of a 2000 cc 4-cylinder gasoline engine.
Attach a metal carrier supporting the catalyst via the flange,
The process of fully opening the throttle at 5000 rpm for 10 minutes, stopping the engine, and externally cooling the fan for 15 minutes was repeated 150 times. The temperature of the gas entering the metal carrier during high-speed operation was adjusted to 850 ° C. Thereafter, the metal carrier was cut and the state of peeling of the washcoat layer was examined with a stereoscopic microscope. The results are also shown in Table 2. The present invention example, N
o. First, although slight peeling was observed, which was not a problem in normal use, no peeling was observed in all other cases. In contrast, a large amount of peeling was observed in all of the comparative examples.
【００３２】[0032]
【表１】 [Table 1]
【００３３】[0033]
【表２】 [Table 2]
【００３４】[0034]
【発明の効果】本発明のメタルハニカムは、Ｔｉまたは
／およびＮｂを含有する耐熱ステンレス鋼箔で形成さ
れ、箔表面におけるＴｉやＮｂの炭化物、窒化物、炭窒
化物の量を制限することで、ウォッシュコート密着性を
向上させ、使用中における触媒剥離の問題を解決するこ
とができる。そして、グラファイトヒーターを加熱源と
する汎用の真空熱処理炉でろう付けや拡散接合が行われ
た場合でも、箔表面の炭化物析出を抑え、また窒化物や
炭窒化物の析出も抑え、さらに接合工程で拡散促進剤と
してカーボンを塗布する液相接合を行っても、炭化物の
析出を抑えることができ、ウォッシュコート密着性の優
れたものである。The metal honeycomb of the present invention is formed of a heat-resistant stainless steel foil containing Ti and / or Nb, and limits the amount of carbides, nitrides and carbonitrides of Ti and Nb on the foil surface. This improves the washcoat adhesion and solves the problem of catalyst peeling during use. Even when brazing or diffusion bonding is performed in a general-purpose vacuum heat treatment furnace using a graphite heater as a heating source, carbide precipitation on the foil surface is suppressed, and nitride and carbonitride are also prevented from being deposited. Thus, even when liquid phase bonding is performed in which carbon is applied as a diffusion accelerator, the precipitation of carbides can be suppressed, and the washcoat adhesion is excellent.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.6 識別記号 ＦＩ Ｆ０１Ｎ 3/28 ３０１ Ｆ０１Ｎ 3/28 ３０１Ｐ ３１１ ３１１Ｒ ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 6 Identification code FI F01N 3/28 301 F01N 3/28 301P 311 311R
Claims (4)
て巻回または積層され、前記平箔と前記波箔の接触部が
ろう付けまたは拡散接合により接合されたメタルハニカ
ムにおいて、前記ステンレス鋼箔がＴｉとＮｂの一方ま
たは双方を含有し、かつ前記平箔および波箔の表面に
は、ＴｉおよびＮｂの一方または双方の炭化物、窒化
物、または炭窒化物からなる析出物がないか、または該
析出物の面積率が３０％以下であることを特徴とするウ
ォッシュコート密着性に優れた触媒用メタルハニカム。1. A metal honeycomb in which a flat foil and a corrugated foil of a heat-resistant stainless steel foil are overlapped and wound or laminated, and a contact portion between the flat foil and the corrugated foil is joined by brazing or diffusion bonding. The steel foil contains one or both of Ti and Nb, and the surface of the flat foil and the corrugated foil is free of precipitates made of carbide, nitride, or carbonitride of one or both of Ti and Nb. Or a catalyst honeycomb excellent in washcoat adhesion, wherein the area ratio of the precipitate is 30% or less.
て、ＴｉとＮｂの一方または双方の含有量がＣ量および
Ｎ量との関係で、（１）式を満足する範囲であることを
特徴とする請求項１記載のウォッシュコート密着性に優
れた触媒用メタルハニカム。 Ｎｂ＋２Ｔｉ−８（Ｃ＋Ｎ）＜０．２ （１） ただし、Ｎｂ，Ｔｉ，Ｃ、およびＮは、それぞれＮｂ，
Ｔｉ，Ｃ、およびＮの含有量（重量％）。2. The composition of the stainless steel foil, wherein the content of one or both of Ti and Nb is in a range satisfying the expression (1) in relation to the C content and the N content. The catalyst metal honeycomb according to claim 1, which has excellent washcoat adhesion. Nb + 2Ti-8 (C + N) <0.2 (1) where Nb, Ti, C, and N are Nb,
Content of Ti, C, and N (% by weight).
％にて、 Ｃ ：０．０２５％以下、 Ｎ ：０．０２％以下、 Ｃ＋Ｎ：０．０３％以下、 Ｓｉ：０．５％以下、 Ｍｎ：１．０％以下、 Ｃｒ：１２〜３０％ Ａｌ：２〜１０％以下 であり、ＴｉとＮｂの一方または双方を、 Ｔｉ：０．０２〜０．２０％、 Ｎｂ：０．０５〜０．３５％ の範囲で含有し、残部がＦｅおよび不可避的不純物から
なることを特徴とする請求項２記載のウォッシュコート
密着性に優れた触媒用メタルハニカム。3. The composition of the stainless steel foil is as follows: C: 0.025% or less, N: 0.02% or less, C + N: 0.03% or less, Si: 0.5% or less by weight%. , Mn: 1.0% or less, Cr: 12 to 30% Al: 2 to 10% or less, one or both of Ti and Nb, Ti: 0.02 to 0.20%, Nb: 0.05 The metal honeycomb for a catalyst having excellent wash coat adhesion according to claim 2, wherein the metal honeycomb is contained in an amount of up to 0.35%, with the balance being Fe and inevitable impurities.
に重量％にて、 Ｐ：３１／２３３×（ＲＥＭ＋０．０２１）％〜０．１
％、 ＲＥＭ：０．０６％超〜０．１５％を含有することを特
徴とする請求項３記載のウォッシュコート密着性に優れ
た触媒用メタルハニカム。4. The composition of the stainless steel foil further includes: P: 31/233 × (REM + 0.021)% to 0.1% by weight.
The metal honeycomb for a catalyst having excellent wash coat adhesion according to claim 3, wherein the metal honeycomb contains more than 0.06% to 0.15%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9353375A JPH11179214A (en) | 1997-12-22 | 1997-12-22 | Metallic honeycomb for catalyst excellent in adhesion of wash coat |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP9353375A JPH11179214A (en) | 1997-12-22 | 1997-12-22 | Metallic honeycomb for catalyst excellent in adhesion of wash coat |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH11179214A true JPH11179214A (en) | 1999-07-06 |
Family
ID=18430420
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP9353375A Pending JPH11179214A (en) | 1997-12-22 | 1997-12-22 | Metallic honeycomb for catalyst excellent in adhesion of wash coat |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH11179214A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007275831A (en) * | 2006-04-11 | 2007-10-25 | Nippon Steel Materials Co Ltd | Metallic base material usable for depositing catalyst and excellent in cryogenic durability |
-
1997
- 1997-12-22 JP JP9353375A patent/JPH11179214A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007275831A (en) * | 2006-04-11 | 2007-10-25 | Nippon Steel Materials Co Ltd | Metallic base material usable for depositing catalyst and excellent in cryogenic durability |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105431562B (en) | Ferrite-group stainless steel paper tinsel | |
| US20060166029A1 (en) | High a1 stainless steel sheet and double layered sheet, process for their fabrication, honeycomb bodies employing them and process for their production | |
| JPS63266044A (en) | High al rolled metallic foil for catalyst carrier | |
| JP4198446B2 (en) | Stainless steel plate and honeycomb structure using the same | |
| JP4233628B2 (en) | Austenitic stainless steel for hydrogen generator with excellent scale peeling resistance | |
| JP3751994B2 (en) | Metal carrier for catalysts with excellent oxidation resistance and durability | |
| JP2007518879A (en) | Method for producing austenitic alloy products and use thereof | |
| JP3816974B2 (en) | Diffusion bonded metal carrier for catalyst having strong bonding strength and method for producing the same | |
| JPH11179214A (en) | Metallic honeycomb for catalyst excellent in adhesion of wash coat | |
| JP2002507249A (en) | Ferritic stainless steel and its use as a substrate for catalytic converters | |
| JP3953944B2 (en) | Metal foil and honeycomb structure | |
| WO1994017911A1 (en) | Metallic honeycomb for use as catalyst and process for producing the same | |
| JP3238561B2 (en) | Metal honeycomb for catalyst | |
| US20080069717A1 (en) | High A1 stainless steel sheet and double layered sheet, process for their fabrication, honeycomb bodies employing them and process for their production | |
| JP3335647B2 (en) | Fe-Cr-Al alloy excellent in durability and catalyst carrier using the same | |
| JPH05283149A (en) | Heater material with excellent surface insulation property and its manufacture | |
| JPH07233451A (en) | Al plated stainless steel sheet excellent in high temperature oxidation resistance | |
| JPH0226643A (en) | Catalyst carrier | |
| JPH08168680A (en) | Metal carrier for purifying exhaust gas of low thermal capacity and low back pressure | |
| JP2006009119A (en) | STAINLESS STEEL SHEET SUPERIOR IN POTASSIUM-CORROSION RESISTANCE, MANUFACTURING METHOD THEREFOR, AND CARRIER FOR NOx-OCCLUDING CATALYST | |
| JP3283286B2 (en) | Fe-Cr-Al alloy foil for highly heat-resistant metal carrier for automobile exhaust gas purification catalyst | |
| JPH01159384A (en) | Fe-cr-al alloy foil | |
| US20030049483A1 (en) | Composite of metal foils with a soldering material | |
| JP2004169114A (en) | Metal foil, and honeycomb structure | |
| JPH09279311A (en) | Iron-chrome-alum. alloy having heat resistance and oxidation resistance and excellent in diffusion joining property |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20040227 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20060825 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20060905 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20061026 |
|
| A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20061219 |
|
| A711 | Notification of change in applicant |
Free format text: JAPANESE INTERMEDIATE CODE: A712 Effective date: 20061208 |