JP3238561B2 - Metal honeycomb for catalyst - Google Patents
Metal honeycomb for catalystInfo
- Publication number
- JP3238561B2 JP3238561B2 JP01270594A JP1270594A JP3238561B2 JP 3238561 B2 JP3238561 B2 JP 3238561B2 JP 01270594 A JP01270594 A JP 01270594A JP 1270594 A JP1270594 A JP 1270594A JP 3238561 B2 JP3238561 B2 JP 3238561B2
- Authority
- JP
- Japan
- Prior art keywords
- less
- foil
- stainless steel
- honeycomb
- 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.)
- Expired - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 23
- 239000002184 metal Substances 0.000 title claims description 23
- 239000003054 catalyst Substances 0.000 title claims description 18
- 239000011888 foil Substances 0.000 claims description 55
- 229910001220 stainless steel Inorganic materials 0.000 claims description 23
- 238000009792 diffusion process Methods 0.000 claims description 20
- 239000010935 stainless steel Substances 0.000 claims description 19
- 239000012535 impurity Substances 0.000 claims description 16
- 239000011651 chromium Substances 0.000 claims description 13
- 239000007791 liquid phase Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 12
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 229910052758 niobium Inorganic materials 0.000 claims description 8
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims description 2
- 229910000423 chromium oxide Inorganic materials 0.000 claims description 2
- 241000264877 Hippospongia communis Species 0.000 description 34
- 239000000463 material Substances 0.000 description 25
- 230000003647 oxidation Effects 0.000 description 17
- 238000007254 oxidation reaction Methods 0.000 description 17
- 229910000831 Steel Inorganic materials 0.000 description 9
- 239000010959 steel Substances 0.000 description 9
- 238000010438 heat treatment Methods 0.000 description 8
- 238000005304 joining Methods 0.000 description 7
- 238000005219 brazing Methods 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- 238000003466 welding Methods 0.000 description 6
- 239000007789 gas Substances 0.000 description 5
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052698 phosphorus Inorganic materials 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 230000005856 abnormality Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 238000007689 inspection Methods 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000000994 depressogenic effect Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Description
【０００１】[0001]
【産業上の利用分野】本発明は内燃機関の排気ガス淨化
用の触媒装置や化学プラントの触媒装置に用いられるメ
タルハニカムに関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a metal honeycomb used for a catalyst device for purifying exhaust gas of an internal combustion engine and a catalyst device for a chemical plant.
【０００２】[0002]
【従来の技術】近年内燃機関とりわけ自動車用のガソリ
ンエンジンの排気ガス淨化用の触媒装置にメタルハニカ
ムが用いられるケースが増えてきた。これは従来用いら
れてきたセラミックスハニカムに比べてメタルハニカム
の開孔率が大きいうえ、温度の上下が激しい環境下にお
いてもメタルハニカムは耐久性に優れているなどの利点
があるからである。このメタルハニカムは、耐熱性の優
れたステンレス鋼箔で厚さ５０μｍ程度の平箔と、これ
を波付加工したものを重ね、これらを相互に接合したも
のである。2. Description of the Related Art In recent years, metal honeycombs have been increasingly used as catalyst devices for purifying exhaust gas from internal combustion engines, especially gasoline engines for automobiles. This is because the metal honeycomb has a larger porosity than conventionally used ceramic honeycombs, and has advantages such as excellent durability even in an environment where the temperature rises and falls sharply. This metal honeycomb is formed by superimposing a flat foil having a thickness of about 50 μm, which is a stainless steel foil having excellent heat resistance, and a corrugated flat foil, and joining them together.
【０００３】ステンレス鋼箔としては特公昭５８−２３
１３８号公報、特公昭５４−１５０３５号公報、特開昭
５６−９６７２６号公報などに記載されているように、
耐酸化性に優れたＦｅ−Ｃｒ−Ａｌ系合金箔が用いられ
る。これらの箔は高温で表面に酸化アルミニウム皮膜を
生じてきわめて優れた耐酸化性を保持する。また接合方
法としては特開昭６１−１９９５７４号公報の記載にあ
るようなろう付け、特開昭６４−４０１８０号公報の記
載にあるような抵抗溶接、特開昭５４−１３４６２号公
報の記載にあるようなレーザービーム溶接や電子ビーム
溶接など各種のものが用いられている。As a stainless steel foil, Japanese Patent Publication No. 58-23
138, JP-B-54-15035, JP-A-56-96726, etc.
An Fe-Cr-Al-based alloy foil having excellent oxidation resistance is used. These foils form an aluminum oxide film on the surface at high temperatures and retain extremely good oxidation resistance. Examples of the joining method include brazing as described in JP-A-61-199574, resistance welding as described in JP-A-64-40180, and description of JP-A-54-13462. Various types of laser beam welding and electron beam welding are used.
【０００４】[0004]
【発明が解決しようとする課題】ハニカム材として使用
されているＦｅ−Ｃｒ−Ａｌ合金箔例えば２０Ｃｒ−５
Ａｌ鋼箔は耐酸化性は優れているものの、その製造性は
きわめて悪く、製造コストが高い。また実使用環境は最
高でも８００℃程度で使われる場合が多く、この材料の
持つ耐酸化性は過剰品質である場合が多い。また接合方
法もろう付けでは使用するろう材が高価で、これを行う
工程もバインダーの塗布→ろう材の付着→真空熱処理と
複雑を極める。抵抗溶接は生産性の低い製造方法で量産
には向かない。またレーザービーム溶接は溶接装置がき
わめて高価になるなどの欠点を有する。SUMMARY OF THE INVENTION Fe-Cr-Al alloy foil used as a honeycomb material, for example, 20Cr-5
Although Al steel foil has excellent oxidation resistance, its productivity is extremely poor and its production cost is high. Further, the actual use environment is often used at a maximum of about 800 ° C., and the oxidation resistance of this material is often excessive. In addition, the brazing material used in brazing is expensive in the brazing method, and the process for performing the brazing is extremely complicated, such as application of a binder → adhesion of the brazing material → vacuum heat treatment. Resistance welding is a production method with low productivity and is not suitable for mass production. Further, laser beam welding has a disadvantage that a welding apparatus becomes extremely expensive.
【０００５】比較的安価な接合方法として米国特許第４
３００９５６号明細書や特開平１−２７０９４７号公報
の記載に示されている拡散接合の方法もあるが、触媒用
基体として必要な耐酸化性を箔材に確保しようとする
と、用いられる材料が前記のＦｅ−Ｃｒ−Ａｌ系合金で
は、拡散接合を行うための真空熱処理において炉内のわ
ずかな酸素源（ＣＯ，Ｈ2 Ｏ）と反応して箔表面には極
く薄い酸化アルミニウムの皮膜が生じて、１２００℃以
上の高温に加熱してもこれらの皮膜が拡散接合の障害と
なって、接合は局所的かつ不安定なものにならざるを得
ない。また特開平１−２７０９４７号公報に記載のＳＵ
Ｓ４１０Ｌ，同４３０，同４３４等の通常のステンレス
鋼では箔材としての耐酸化性や高温強度が不足して自動
車排ガス用触媒の基材としての耐熱性に欠ける。A relatively inexpensive joining method is disclosed in US Pat.
There are also diffusion bonding methods described in the description of Japanese Patent No. 300956 and Japanese Patent Application Laid-Open No. 1-270947. However, in order to secure the oxidation resistance required for a catalyst base in a foil material, the material used is as described above. in the Fe-Cr-Al alloy, a slight oxygen source in the furnace (CO, H 2 O) in the reaction to the foil surface coating of very thin aluminum oxide occurs in a vacuum heat treatment for performing diffusion bonding However, even if the film is heated to a high temperature of 1200 ° C. or more, these films may hinder diffusion bonding, and the bonding must be local and unstable. In addition, SU described in Japanese Patent Application Laid-Open No. 1-270947
Normal stainless steels such as S410L, 430, and 434 have insufficient oxidation resistance and high-temperature strength as a foil material and lack heat resistance as a base material of a catalyst for automobile exhaust gas.
【０００６】本発明は上記したような現状の問題点を解
決すべくなされたもので、Ｃｒ−Ｎｂ系ステンレス鋼箔
を用いて比較的単純な接合方法で安価な触媒用メタルハ
ニカムを提供することを目的とする。SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned current problems, and it is an object of the present invention to provide an inexpensive metal honeycomb for a catalyst by a relatively simple joining method using a Cr-Nb stainless steel foil. With the goal.
【０００７】[0007]
【課題を解決するための手段】本発明は上記の目的を達
成すべくなされたもので、その要旨とするところは下記
の通りである。 （１）重量比で０．１〜０．６％のＮｂを含有し、かつ
Ａｌの含有量が不純物レベル〜０．８％であって、高温
で酸化アルミニウム皮膜を作らず酸化クロム皮膜を表面
に生成するフェライト系ステンレス鋼箔の平板と波板と
を相互に拡散接合または液相接合してなることを特徴と
する触媒用メタルハニカム。 （２）ステンレス鋼箔の化学組成が重量比で、 Ｃ ：０．２％以下、 Ｓｉ：１％以下、 Ｃｒ：１１〜２５％、 Ｎｂ：０．１〜０．６％、 Ａｌ：不純物レベル〜０．８％、 残部がＦｅおよび不可避不純物よりなる前項（１）記載
の触媒用メタルハニカム。 （３）ステンレス鋼箔の化学組成が重量比で Ｃ ：０．２％以下、 Ｓｉ：１％以下、 Ｃｒ：１１〜２５％、 Ｎｂ：０．１〜０．６％、 Ａｌ：不純物レベル〜０．８％、 およびＹを含む希土類元素の１種または２種以上を合計
で０．０１〜０．２％含み、残部がＦｅおよび不可避不
純物よりなる前項（１）記載の触媒用メタルハニカム。 （４）ステンレス鋼箔の化学組成が重量比で、 Ｃ ：０．２％以下、 Ｓｉ：１％以下、 Ｃｒ：１１〜２５％、 Ｎｂ：０．１〜０．６％、 Ａｌ：不純物レベル〜０．８％、 更に Ｔｉ：０．０５〜０．５％、 Ｚｒ：０．０５〜０．５％、 Ｖ ：０．０３〜０．５％、 Ｍｏ：０．３〜３％、 Ｗ ：０．５〜３％のいずれか１種または２種以上 を含み、残部がＦｅおよび不可避不純物よりなる前項
（１）記載の触媒用メタルハニカム。 （５）ステンレス鋼箔の化学組成が重量比で Ｃ ：０．２％以下、 Ｓｉ：１％以下、 Ｃｒ：１１〜２５％、 Ｎｂ：０．１〜０．６％、 Ａｌ：不純物レベル〜０．８％、 Ｙを含む希土類元素の１種または２種以上を合計で０．
０１〜０．２％含み、更に Ｔｉ：０．０５〜０．５％、 Ｚｒ：０．０５〜０．５％、 Ｖ ：０．０３〜０．５％、 Ｍｏ：０．３〜３％、 Ｗ ：０．５〜３％のいずれか１種または２種以上 を含み、残部がＦｅおよび不可避不純物よりなることを
特徴とする請求項１記載の触媒用メタルハニカムであ
る。SUMMARY OF THE INVENTION The present invention has been made to achieve the above object, and its gist is as follows. (1) containing 0.1 to 0.6% by weight of Nb , and
A diffusion bonding or liquid bonding between a flat plate and a corrugated plate of a ferritic stainless steel foil having an Al content of the impurity level of 0.8% and forming a chromium oxide film on the surface without forming an aluminum oxide film at a high temperature. catalyst metal honeycomb, characterized in that formed by phase bonding. ( 2 ) The chemical composition of the stainless steel foil is by weight: C: 0.2% or less, Si: 1% or less, Cr: 11 to 25%, Nb: 0.1 to 0.6%, Al: impurity level The metal honeycomb for a catalyst according to the above (1), wherein the content is 0.8%, and the balance is Fe and unavoidable impurities. ( 3 ) The chemical composition of the stainless steel foil is C: 0.2% or less by weight, Si: 1% or less, Cr: 11 to 25%, Nb: 0.1 to 0.6%, Al: impurity level or less. The metal honeycomb for a catalyst according to the above item (1), comprising a total of 0.01 to 0.2% of 0.8% and one or two or more rare earth elements containing Y, with the balance being Fe and unavoidable impurities. ( 4 ) The chemical composition of the stainless steel foil is by weight: C: 0.2% or less, Si: 1% or less, Cr: 11 to 25%, Nb: 0.1 to 0.6%, Al: impurity level 0.8%, further Ti: 0.05 to 0.5%, Zr: 0.05 to 0.5%, V: 0.03 to 0.5%, Mo: 0.3 to 3%, W : The metal honeycomb for a catalyst according to the above (1), containing any one or more of 0.5 to 3%, with the balance being Fe and unavoidable impurities. ( 5 ) The chemical composition of the stainless steel foil is, by weight ratio, C: 0.2% or less, Si: 1% or less, Cr: 11 to 25%, Nb: 0.1 to 0.6%, Al: impurity level to 0.8%, one or two or more rare earth elements including Y in total of 0.
0.01 to 0.2%, Ti: 0.05 to 0.5%, Zr: 0.05 to 0.5%, V: 0.03 to 0.5%, Mo: 0.3 to 3% , W: 0.5 to 3%, and the balance is Fe and unavoidable impurities, and the balance is Fe.
【０００８】本発明者らは先に特願平５−２４５１７号
において、箔材に必要な耐酸化性を維持しながら拡散〜
液相接合性を向上させるためにＡｌを低く限定したうえ
１％超〜３．５％のＳｉを添加することを提案したが、
その後の研究によりＳｉを１％以下にしてもＮｂを０．
１〜０．６％添加すれば必要な耐酸化性を維持しながら
拡散〜液相接合性を向上させ得ることを知見して本発明
をなしたものである。すなわち、本発明はメタルハニカ
ムの箔材として、０．１〜０．６％のＮｂを含有するス
テンレス鋼箔を用いることにより拡散または液相接合を
容易にすると同時に必要な耐酸化性を確保し、且つ比較
的工程の単純な拡散または液相接合を用いる際に障害と
なるアルミナ皮膜が生じないようにＡｌ含有量を０．８
％以下に抑えることにより、拡散または液相接合をより
低い温度で円滑に行わしめるものである。しかして本発
明はＦｅ−Ｃｒ−Ａｌ合金系ステンレス鋼箔よりはるか
に製造性の良いＣｒ−Ｎｂ系のステンレス鋼箔を用い
て、比較的工程の単純な拡散または液相接合をより低温
で行わしめることが可能であり、低コストのメタルハニ
カムを提供するものである。The present inventors have previously disclosed in Japanese Patent Application No. Hei 5-24517 a method of diffusing while maintaining the oxidation resistance required for a foil material.
It has been proposed to limit Al to a low level and to add more than 1% to 3.5% of Si in order to improve the liquid phase bonding property.
According to subsequent studies, Nb was reduced to 0.1 even when Si was set to 1% or less.
The present invention has been made based on the finding that the addition of 1 to 0.6% can improve the diffusion to liquid phase bonding while maintaining the required oxidation resistance. That is, the present invention uses a stainless steel foil containing 0.1 to 0.6% Nb as the foil material of the metal honeycomb, thereby facilitating diffusion or liquid phase bonding and securing necessary oxidation resistance. In addition, the Al content is set to 0.8 so that an alumina film which is an obstacle when relatively simple diffusion or liquid phase bonding is used is not generated.
% Or less, diffusion or liquid phase bonding can be performed smoothly at a lower temperature. Thus, the present invention uses a Cr-Nb-based stainless steel foil, which is far more manufacturable than a Fe-Cr-Al alloy-based stainless steel foil, and performs relatively simple diffusion or liquid phase bonding at lower temperatures at lower temperatures. It is possible to provide a low-cost metal honeycomb that can be closed.
【０００９】次に本発明においてハニカムのステンレス
鋼箔の成分を限定した理由を述べる。ＮｂはＡｌやＳｉ
を高位に含まないフェライト系ステンレス鋼において、
その耐酸化性を補強し、また高温強度を高めてハニカム
の耐熱疲労性を改善すると同時にアルミを低位に含有す
る鋼材でも酸化アルミニウム皮膜の形成を阻害して拡散
接合を容易にする。しかしながら０．１％未満ではそれ
らの添加効果が不足し、また０．６％超では材質が劣化
するので添加量を０．１〜０．６％とした。Ｓｉは不可
避的に含有される元素で高めに添加すれば鋼材の耐酸化
性を向上させ、酸化アルミニウム皮膜の形成を阻害する
効果があるので拡散接合を容易にするが、本発明におい
てはＮｂがこの役割を担っているのでＳｉの範囲を１％
以下とした。但しＣｒが１８％以下の場合は箔の耐酸化
性を補強するためにＳｉ含有量を０．６％以上にするの
が望ましい。Next, the reason why the components of the stainless steel foil of the honeycomb are limited in the present invention will be described. Nb is Al or Si
In a ferritic stainless steel that does not contain
The oxidation resistance is reinforced and the high-temperature strength is increased to improve the thermal fatigue resistance of the honeycomb. At the same time, even for a steel material containing aluminum at a low level, the formation of an aluminum oxide film is inhibited and diffusion bonding is facilitated. However, if it is less than 0.1%, the effect of the addition is insufficient, and if it exceeds 0.6%, the material is deteriorated. Si is an element inevitably contained, and if added at a high level, improves the oxidation resistance of the steel material and has the effect of inhibiting the formation of an aluminum oxide film, thereby facilitating diffusion bonding. Because it plays this role, the range of Si is 1%
It was as follows. However, when Cr is 18% or less, it is desirable to make the Si content 0.6% or more to reinforce the oxidation resistance of the foil.
【００１０】ＡｌはＣｒ系ステンレス鋼に１％も添加す
ると高温で酸化アルミニウムの保護性の皮膜を形成して
耐酸化性は向上するものの、本発明においては拡散また
は液相接合の妨げとなるため排除する。但し箔材の変態
点を使用温度より高温側にずらすために酸化アルミニウ
ム皮膜を作らない範囲内ですなわち０．８％以下のＡｌ
を添加することができる。When Al is added as much as 1% to Cr-based stainless steel, a protective film of aluminum oxide is formed at a high temperature to improve the oxidation resistance. However, in the present invention, diffusion or liquid phase bonding is hindered. Exclude. However, in order to shift the transformation point of the foil material to a higher temperature side than the operating temperature, an aluminum oxide film must be formed within a range in which an aluminum oxide film is not formed, ie, 0.8% or less.
Can be added.
【００１１】Ｃは箔材融点を下げて拡散または液相接合
を容易にするが、過剰に添加すると材質を劣化させるの
で上限を０．２％とした。Ｃｒはステンレス鋼の耐酸化
性を維持する基本的な元素で、１１％未満では耐酸化性
が不足し、２５％超では材質を硬くして製造性が悪くな
るので１１〜２５％とした。C lowers the melting point of the foil material to facilitate diffusion or liquid phase bonding. However, excessive addition of C deteriorates the material, so the upper limit was made 0.2%. Cr is a basic element for maintaining the oxidation resistance of stainless steel. If it is less than 11%, the oxidation resistance is insufficient, and if it exceeds 25%, the material is hardened and the productivity is deteriorated.
【００１２】Ｙを含む希土類元素は箔材の耐酸化性を改
善するので、本発明においては必要に応じて添加する。
但しその１種または２種以上の合計で０．０１％未満で
は効果がなく、０．２％超では材料に疵をもたらすため
０．０１〜０．２％とした。Ｔｉ，Ｚｒ，Ｖ，Ｍｏ，Ｗ
は夫々箔材の高温強度を改善するので、必要に応じて添
加する。夫々の下限値未満では添加効果が不充分で、上
限を超えると材質が硬くなり、製造性も悪くなる。また
ジーゼル用の触媒では硫酸露点腐食がハニカムに生じる
場合があり、この場合はＭｏを１％以上添加すると耐露
点腐食性が向上する。Since rare earth elements containing Y improve the oxidation resistance of the foil material, they are added as necessary in the present invention.
However, if the total amount of one or more of them is less than 0.01%, there is no effect, and if it exceeds 0.2%, a flaw is caused in the material, so that the content is set to 0.01 to 0.2%. Ti, Zr, V, Mo, W
Are added as necessary, because they improve the high-temperature strength of the foil material. If the amount is less than the respective lower limits, the effect of addition is insufficient. If the amount exceeds the upper limit, the material becomes hard and the productivity is deteriorated. In the case of a diesel catalyst, sulfuric acid dew point corrosion may occur on the honeycomb. In this case, if Mo is added at 1% or more, the dew point corrosion resistance is improved.
【００１３】表１に本発明ハニカムに使用し得る箔材組
成の例を挙げた。本発明に使用される箔材の化学組成の
うち、Ｍｎ，Ｐ，Ｓについては特に規定していないが、
これらは通常のステンレス鋼に含有されるレベルであれ
ば問題はない。[0013] Table 1 shows examples of foil material compositions that can be used in the honeycomb of the present invention. Among the chemical compositions of the foil material used in the present invention, Mn, P, and S are not particularly specified,
There is no problem if these are levels contained in ordinary stainless steel.
【００１４】[0014]
【表１】 [Table 1]
【００１５】また本発明でいう拡散接合とは、波箔の頂
部と平箔の接触面が固相のまま相互拡散を生じて接合す
るものである。また本発明でいう液相接合とは、上記の
接触面に塗布されたグラファイト粉などの融点降下剤に
より両表面が液相となり接合するものである。The diffusion bonding in the present invention refers to bonding in which the top surface of the corrugated foil and the contact surface of the flat foil are mutually diffused while maintaining a solid phase. The liquid-phase joining in the present invention means joining both surfaces into a liquid phase by a melting point depressant such as graphite powder applied to the contact surface.
【００１６】[0016]
【実施例】〔実施例−１〕 表１のＡ，Ｃ，Ｆ，Ｐの化学組成よりなる５０μｍ厚の
箔を夫々作成し、一部を波付加工して波箔を得、平箔と
重ねて巻回して外径９７mmφ、長さ１００mmのハニカム
を作成した。更に外筒として１９％Ｃｒ鋼の厚さ１．５
mmのステンレス鋼板で外径１００mmφ、長さ１００mmの
円筒を作り、この中に前記のハニカムを挿入した。これ
を真空中で１２００℃×３０分間の熱処理を行い、外筒
とハニカム最外周、ハニカム内の波板と平板を相互に拡
散接合させた。この際ハニカム内の全領域にわたって波
箔と平箔が接合されると、エンジンで使用中に熱疲労破
壊を生じ易いため、図１の断面図で模式的に示すよう
に、ハニカム体の斜線で示した部分３についてはハニカ
ムに巻回するときにチタニアを主成分とする拡散ストッ
プ材を塗布して、この部分については拡散接合が生じな
いようにした。図中１は、ハニカム体を収納した外筒、
２はハニカム体の接合する領域を示す。比較例として２
０Ｃｒ−５Ａｌ鋼の５０μｍ厚の箔材を使用して前記の
ものと同様にしてハニカムを外筒に挿入して真空熱処理
を行った。EXAMPLES [Example 1] Foil having a chemical composition of A, C, F, and P shown in Table 1 and having a thickness of 50 μm was prepared, and a part of the foil was corrugated to obtain a corrugated foil. By stacking and winding, a honeycomb having an outer diameter of 97 mmφ and a length of 100 mm was prepared. Further, as the outer cylinder, a thickness of 19% Cr steel 1.5
A cylinder having an outer diameter of 100 mmφ and a length of 100 mm was made of a stainless steel plate of mm, and the above-mentioned honeycomb was inserted into the cylinder. This was subjected to a heat treatment at 1200 ° C. for 30 minutes in a vacuum, and the outer cylinder and the outermost periphery of the honeycomb, and the corrugated plate and the flat plate in the honeycomb were mutually diffusion bonded. At this time, if the corrugated foil and the flat foil are joined over the entire area in the honeycomb, thermal fatigue destruction is likely to occur during use in the engine. Therefore, as schematically shown in the cross-sectional view of FIG. The portion 3 shown was coated with a diffusion stop material containing titania as a main component when wound around a honeycomb, so that diffusion bonding did not occur in this portion. 1 is an outer cylinder containing a honeycomb body,
Reference numeral 2 denotes a region where the honeycomb bodies are joined. 2 as a comparative example
Using a 50 μm thick foil of 0Cr-5Al steel , a honeycomb was inserted into the outer cylinder in the same manner as described above, and vacuum heat treatment was performed.
【００１７】これら２種の金属基体を排気容量２０００
cc、４気筒のエンジンのエキゾーストパイプの途中に装
着して、５０００mpm で全負荷運転して８００℃×１０
分加熱・エンジン停止２０分冷却の冷熱試験を９００回
行った。その結果表１のＡ，Ｃ，Ｆ，Ｐの箔を使用した
ものでは９００回の冷熱試験後も特に異常はみられなか
ったのに対し、２０Ｃｒ−５Ａｌの箔を用いた比較例の
ものでは冷熱６００回の点検時にハニカムの中央部の３
分の２程度が排ガスの出側にズレを生じていた。調査の
結果、前者のハニカムでは波箔の頂点と平箔は確実に拡
散接合しており、接合は面状に広がりを有していたが、
後者のものでは接合はまばらにしか行われておらず、し
かも接合している部分でも点状の接合しか行われていな
かった。すなわち２０Ｃｒ−５Ａｌの箔では真空熱処理
中に酸化アルミニウムの皮膜が生じて、拡散接合が充分
に行われなかったことを示している。[0017] These two types of metal substrates were evacuated to a displacement capacity of 2000.
Installed in the middle of the exhaust pipe of a cc, 4-cylinder engine and operated at 5000 mpm at full load, 800 ° C x 10
A cooling test was performed 900 times with minute heating and engine stop for 20 minutes. As a result, in the case of using the foils of A, C, F and P in Table 1, no abnormalities were observed even after 900 times of the thermal test, whereas in the case of the comparative example using the foil of 20Cr-5Al, During the cold and hot inspection 600 times, 3
About two-thirds had a shift on the outlet side of the exhaust gas. As a result of the investigation, in the former honeycomb, the vertex of the corrugated foil and the flat foil were surely diffusion-bonded, and the bonding had a planar spread,
In the latter case, the bonding was performed only sparsely, and only the point-like bonding was performed in the bonding part. In other words, this indicates that the aluminum oxide film was formed during the vacuum heat treatment on the 20Cr-5Al foil, and diffusion bonding was not sufficiently performed.
【００１８】〔実施例−２〕表１のＡ，Ｃ，Ｍ，Ｏの化
学組成の５０μｍ厚の箔を作成し、実施例−１と同様に
して金属基体を作成した。但し、この場合は接合すべき
波箔の頂点にはグラファイト粉をペースト状にして塗布
し、真空熱処理は１１５０℃で行った。同時に熱処理し
た調査用のハニカムを調べたところ、グラファイト粉を
塗布したところでは箔表面が溶融して液相接合が行われ
ていた。比較例としてＳＵＳ４３０（１６％Ｃｒ鋼）の
５０μｍ厚の箔を作成し、前記と同様にして金属基体を
作成した。Example 2 A 50 μm thick foil having the chemical composition of A, C, M and O in Table 1 was prepared, and a metal substrate was prepared in the same manner as in Example 1. In this case, however, graphite powder was applied as paste to the top of the corrugated foil to be joined, and the vacuum heat treatment was performed at 1150 ° C. At the same time, the heat treatment of the research honeycomb was examined. When the graphite powder was applied, the foil surface melted and liquid phase bonding was performed. As a comparative example, a SUS430 (16% Cr steel) foil having a thickness of 50 μm was prepared, and a metal substrate was prepared in the same manner as described above.
【００１９】これら２種の金属基体を実施例−１と同様
にしてエンジンベンチによる冷熱試験を行った。その結
果前者の金属基体は冷熱９００回後も特段の異常はみと
められなかったが、後者のものでは、冷熱６００回の点
検時に排ガスの入側のハニカム面の箔が部分的に黒変し
て一部が欠けて消失していたので試験を中止した。調査
の結果、後者の金属基体のハニカムでは拡散接合は充分
に行われていたが、ハニカムの内部がかなり酸化されて
一部に空洞が生じていた。すなわちＳＵＳ４３０の箔で
は耐酸化性が不足であることを示している。These two types of metal substrates were subjected to a cooling test using an engine bench in the same manner as in Example-1. As a result, no particular abnormality was found in the former metal substrate even after 900 times of cold heat, but in the latter case, the foil of the honeycomb surface on the exhaust gas entrance side was partially blackened during the 600 times of cold heat inspection. The test was discontinued because part of it was missing. As a result of the investigation, it was found that diffusion bonding was sufficiently performed in the latter metal-substrate honeycomb, but the inside of the honeycomb was considerably oxidized and a cavity was formed in part. That is, it shows that the SUS430 foil has insufficient oxidation resistance.
【００２０】[0020]
【発明の効果】上記の実施例が示す通り、本発明は比較
的安価な箔材を用いて単純な接合方法により低コストの
触媒用ハニカムを提供するもので、公害対策技術に寄与
するところ大である。As shown in the above embodiments, the present invention provides a low cost catalyst honeycomb by a simple joining method using a relatively inexpensive foil material, which greatly contributes to pollution control technology. It is.
【図１】本発明を実施するための金属基体の接合構造の
例を模式的に示す断面図。FIG. 1 is a cross-sectional view schematically showing an example of a bonding structure of a metal base for implementing the present invention.
１ 外筒 ２ ハニカムの接合する領域 ３ ハニカムの接合しない領域 1 outer cylinder 2 area where honeycomb is joined 3 area where honeycomb is not joined
───────────────────────────────────────────────────── フロントページの続き (72)発明者 石川 泰 愛知県東海市東海町５−３ 新日本製鐵 株式会社 名古屋製鐵所内 (72)発明者 中川 俊和 愛知県東海市東海町５−３ 新日本製鐵 株式会社 名古屋製鐵所内 (72)発明者 八代 正男 愛知県東海市東海町５−３ 新日本製鐵 株式会社 名古屋製鐵所内 (56)参考文献 特開 平５−208140（ＪＰ，Ａ) 特許2598242（ＪＰ，Ｂ２) (58)調査した分野(Int.Cl.7，ＤＢ名) B01J 21/00 - 37/36 B01D 53/86 C22C 38/00 ──────────────────────────────────────────────────の Continued on the front page (72) Inventor Yasushi Ishikawa 5-3 Tokai-cho, Tokai City, Aichi Prefecture Nippon Steel Corporation Nagoya Works (72) Inventor Toshikazu Nakagawa 5-3 Tokai-cho, Tokai City, Aichi Prefecture New Nippon Steel Corporation Nagoya Works (72) Inventor Masao Yatsushiro 5-3 Tokaicho, Tokai City, Aichi Prefecture Nippon Steel Corporation Nagoya Works (56) References JP-A-5-208140 (JP, A ) Patent 2598242 (JP, B2) (58) Fields investigated (Int. Cl. 7 , DB name) B01J 21/00-37/36 B01D 53/86 C22C 38/00
Claims (5)
し、かつＡｌの含有量が不純物レベル〜０．８％であっ
て、高温で酸化アルミニウム皮膜を作らず酸化クロム皮
膜を表面に生成するフェライト系ステンレス鋼箔の平板
と波板とを相互に拡散接合または液相接合してなること
を特徴とする触媒用メタルハニカム。1. The method according to claim 1 , wherein said alloy contains 0.1 to 0.6% by weight of Nb and has an Al content of about 0.8%.
Te, chromium oxide skin without forming the aluminum oxide film at high temperatures
A metal honeycomb for a catalyst, wherein a flat plate made of a ferritic stainless steel foil and a corrugated plate that form a film on the surface are diffusion bonded or liquid phase bonded to each other.
る請求項１記載の触媒用メタルハニカム。2. The chemical composition of the stainless steel foil is as follows: C: 0.2% or less; Si: 1% or less; Cr: 11 to 25%; Nb: 0.1 to 0.6%; 2. The metal honeycomb for a catalyst according to claim 1, wherein 0.8% and the balance are Fe and unavoidable impurities.
で０．０１〜０．２％含み、残部がＦｅおよび不可避不
純物よりなることを特徴とする請求項１記載の触媒用メ
タルハニカム。3. The chemical composition of the stainless steel foil is as follows: C: 0.2% or less, Si: 1% or less, Cr: 11 to 25%, Nb: 0.1 to 0.6%, Al: An impurity level of 0.8% and one or more rare earth elements including Y in a total amount of 0.01 to 0.2%, with the balance being Fe and unavoidable impurities. The metal honeycomb for a catalyst according to the above.
特徴とする請求項１記載の触媒用メタルハニカム。4. The chemical composition of the stainless steel foil is as follows: C: 0.2% or less, Si: 1% or less, Cr: 11 to 25%, Nb: 0.1 to 0.6%, Al: Impurity level: 0.8%, Ti: 0.05 to 0.5%, Zr: 0.05 to 0.5%, V: 0.03 to 0.5%, Mo: 0.3 to 3% , W: 0.5 to 3% of any one or more of the following, with the balance being Fe and unavoidable impurities, the metal honeycomb for a catalyst according to claim 1, wherein:
０１〜０．２％含み、更に Ｔｉ：０．０５〜０．５％、 Ｚｒ：０．０５〜０．５％、 Ｖ ：０．０３〜０．５％、 Ｍｏ：０．３〜３％、 Ｗ ：０．５〜３％のいずれか１種または２種以上 を含み、残部がＦｅおよび不可避不純物よりなることを
特徴とする請求項１記載の触媒用メタルハニカム。5. The chemical composition of the stainless steel foil is as follows: C: 0.2% or less, Si: 1% or less, Cr: 11 to 25%, Nb: 0.1 to 0.6%, Al: Impurity level: 0.8%, one or more rare earth elements including Y are added in a total amount of 0.
0.01 to 0.2%, Ti: 0.05 to 0.5%, Zr: 0.05 to 0.5%, V: 0.03 to 0.5%, Mo: 0.3 to 3% , W: 0.5 to 3% of any one or more of the following, with the balance being Fe and unavoidable impurities, the metal honeycomb for a catalyst according to claim 1, wherein:
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01270594A JP3238561B2 (en) | 1994-02-04 | 1994-02-04 | Metal honeycomb for catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP01270594A JP3238561B2 (en) | 1994-02-04 | 1994-02-04 | Metal honeycomb for catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH07213918A JPH07213918A (en) | 1995-08-15 |
| JP3238561B2 true JP3238561B2 (en) | 2001-12-17 |
Family
ID=11812834
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP01270594A Expired - Fee Related JP3238561B2 (en) | 1994-02-04 | 1994-02-04 | Metal honeycomb for catalyst |
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| Country | Link |
|---|---|
| JP (1) | JP3238561B2 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4963034B2 (en) * | 2006-04-11 | 2012-06-27 | 新日鉄マテリアルズ株式会社 | Metal substrate for catalyst support with excellent cold and heat resistance |
| MX346735B (en) | 2012-01-30 | 2017-03-30 | Jfe Steel Corp | Ferritic stainless steel foil. |
| JP5868241B2 (en) * | 2012-03-29 | 2016-02-24 | 日新製鋼株式会社 | Ferritic stainless steel for diffusion bonding and method for manufacturing diffusion bonding products |
| SG11201509040WA (en) | 2013-05-15 | 2015-12-30 | Nisshin Steel Co Ltd | Method for producing a stainless steel diffusion-bonded product |
| EP2987888B1 (en) | 2013-07-30 | 2018-02-28 | JFE Steel Corporation | Ferritic stainless steel foil |
| ES2901964T3 (en) | 2014-08-29 | 2022-03-24 | Jfe Steel Corp | Ferritic stainless steel sheet and production method thereof |
| JP6129140B2 (en) | 2014-11-05 | 2017-05-17 | 日新製鋼株式会社 | Stainless steel for diffusion bonding |
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1994
- 1994-02-04 JP JP01270594A patent/JP3238561B2/en not_active Expired - Fee Related
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| Publication number | Publication date |
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| JPH07213918A (en) | 1995-08-15 |
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