JP2587413B2 - Fe-Cr-Al alloy foil for catalyst converter for automobile exhaust gas purification with excellent oxidation resistance - Google Patents
Fe-Cr-Al alloy foil for catalyst converter for automobile exhaust gas purification with excellent oxidation resistanceInfo
- Publication number
- JP2587413B2 JP2587413B2 JP61268838A JP26883886A JP2587413B2 JP 2587413 B2 JP2587413 B2 JP 2587413B2 JP 61268838 A JP61268838 A JP 61268838A JP 26883886 A JP26883886 A JP 26883886A JP 2587413 B2 JP2587413 B2 JP 2587413B2
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- oxidation resistance
- exhaust gas
- oxidation
- 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.)
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- Exhaust Gas Treatment By Means Of Catalyst (AREA)
Description
【発明の詳細な説明】 〔産業上の利用分野〕 本発明は、耐酸化性に優れたFe−Cr−Al系合金箔に関
し、高温酸化性雰囲気下で激しい酸化を受ける自動車排
ガス浄化用触媒コンバータに好適である。Description: FIELD OF THE INVENTION The present invention relates to Fe-Cr-Al-based alloy foils having excellent oxidation resistance and relates to a catalytic converter for purifying automobile exhaust gas which is subject to severe oxidation in a high-temperature oxidizing atmosphere. It is suitable for.
従来、自動車排ガス浄化用触媒コンバータには、コー
ディエライト（2MgO・2Al2O3・5SiO2）の押出焼成ハニ
カムにγ−アルミナ微粒子を触媒担体としてコーティン
グした後、Ptなどの触媒をつけたものが用いられてい
る。Conventionally, catalytic converters for purifying automotive exhaust gas have been prepared by coating γ-alumina fine particles as a catalyst carrier on an extruded and fired honeycomb of cordierite (2MgO.2Al 2 O 3 .5SiO 2 ) and then attaching a catalyst such as Pt. Is used.
特開昭56−96726号公報に示されているように、この
コーディエライト製ハニカムを耐酸化ステンレス箔を組
みたてて製作した金属製ハニカムにすると、コンバータ
の小型化、エンジン性能の向上など、種々の利点があ
る。前記引用公報では耐酸化ステンレス箔としてイット
リウム（Ｙ）を添加したFe−Cr−Al系合金（Cr:15〜25
重量％、Al:3〜６重量％、Y:0.3〜1.0重量％）を提案し
ているが、Ｙが希少金属であるため非常に高価となり、
かつ供給量にも不安があり、一般の自動車に用いるのは
経済性の点で困難であった。As shown in JP-A-56-96726, if this cordierite honeycomb is made into a metal honeycomb made by assembling oxidation-resistant stainless steel foil, the converter can be downsized and the engine performance can be improved. There are various advantages. In the cited publication, a Fe-Cr-Al-based alloy (Cr: 15 to 25) to which yttrium (Y) is added as an oxidation-resistant stainless steel foil is disclosed.
%, Al: 3 to 6% by weight, Y: 0.3 to 1.0% by weight), but very expensive because Y is a rare metal,
In addition, there is concern about the supply amount, and it has been difficult to use it for ordinary vehicles in terms of economy.
これに対し、特開昭58−177437号公報ではCr:8〜25重
量％、Al:3〜８重量％、全希土類元素が0.06重量％まで
で、0.002〜0.05重量％のCe、La、Ndなどを添加した合
金（以下これをFe−Cr−Al−REM合金と呼ぶ）の使用を
提案している。これは稀土類元素の添加によってスケー
ルの剥離を防いだFe−Cr−Al系合金で、電熱線などには
古くから用いられていたものである。On the other hand, Japanese Patent Application Laid-Open No. 58-177437 discloses that Cr: 8 to 25% by weight, Al: 3 to 8% by weight, the total rare earth element is up to 0.06% by weight, and 0.002 to 0.05% by weight of Ce, La, Nd. It has been proposed to use an alloy to which an alloy is added (hereinafter, this is referred to as an Fe-Cr-Al-REM alloy). This is an Fe-Cr-Al-based alloy in which exfoliation of scale is prevented by the addition of rare earth elements, and has been used for a long time for heating wires and the like.
一般にFe−Cr−Al系合金を製造性の面から見ると、Al
含有量３％程度ならば通常のステンレス製造工程で製造
可能であるが、Al含有量が５％程度になると、熱延時に
表面欠陥が多発しその除去に表面研磨を繰り返したり、
冷間圧延時に板が破断しやすいため、低速、低圧下で圧
延しなければならないなど、生産能率が大幅に低下し、
非常に高価なものになる。Generally, from the viewpoint of manufacturability, Fe-Cr-Al alloys
If the content is about 3%, it can be manufactured in a normal stainless steel manufacturing process. However, if the Al content is about 5%, surface defects occur frequently during hot rolling, and surface polishing is repeated to remove them.
Since the plate is easily broken at the time of cold rolling, it must be rolled at low speed and low pressure.
It will be very expensive.
前出のFe−Cr−Al−REM合金では一般用途の燃焼機器
用途では３％Al含有で十分な耐酸化性を持っているが、
自動車の排気ガス浄化用触媒コンバータのように30〜50
μｍといった極薄の材料が過酷な高温酸化を受ける場
合、３％Alでは耐酸化性が不足しており、高価な５％Al
材を使用しなければならなかった。The Fe-Cr-Al-REM alloy mentioned above has sufficient oxidation resistance with 3% Al content for combustion equipment for general use,
30 ~ 50 like catalytic converter for automotive exhaust gas purification
When extremely thin materials such as μm are subjected to severe high-temperature oxidation, oxidation resistance is insufficient with 3% Al, and expensive 5% Al
Wood had to be used.
このFe−Cr−Al−REM合金では「全希土類の合計が0.0
6重量％である少なくとも0.002重量％そして0.05重量％
までのセリウムおよびランタン、ネオジムおよびプラセ
オジムよりなる群からの添加物」として、Ceを必須と
し、La、Nd等を区別していない。In this Fe-Cr-Al-REM alloy, "the total of all rare earth elements is 0.0
6% by weight at least 0.002% by weight and 0.05% by weight
As an additive from the group consisting of cerium and lanthanum, neodymium and praseodymium, Ce is essential and La, Nd, etc. are not distinguished.
しかし、本発明者らの研究によると、希土類元素とし
てCeを除いたLa、Ndのランタノイドを添加すれば、耐酸
化性が大幅に向上することを発見し、さきに特願昭61−
09185号において、『Cr:13〜27％、Al:3.5〜８％、Ceを
除くランタノイド:0.05〜0.20％を含むFe−Cr−Al−合
金』を出願した。However, according to the study of the present inventors, it has been discovered that the addition of La and Nd lanthanoids excluding Ce as a rare earth element significantly improves the oxidation resistance.
No. 09185, filed an application for "Fe-Cr-Al-alloy containing 13-27% Cr, 3.5-8% Al, and lanthanoids other than Ce: 0.05-0.20%".
その後、自動車排ガス浄化用触媒コンバータの改良が
進み、エンジン型式、触媒取付け位置等の条件によって
は、高温酸化腐食条件が緩やかにすることができる部分
も生じた。After that, the improvement of the catalytic converter for purifying automobile exhaust gas has progressed, and depending on the conditions such as the type of engine and the position where the catalyst is mounted, there are some parts where the conditions for high-temperature oxidation corrosion can be moderated.
本発明は触媒コンバータの中で酸化条件が緩やかな場
合に、好適に用いることのできる安価なFe−Cr−Al系合
金箔を製造することを目的としたものである。An object of the present invention is to produce an inexpensive Fe-Cr-Al-based alloy foil that can be suitably used when oxidation conditions are mild in a catalytic converter.
〔問題点を解決するための手段〕 本発明の第１の発明は、 C:0.02重量％未満 Si:1.0重量％以下 Cr:12重量％以上21重量％以下 Al:2.5重量％以上3.5重量％未満 La:0.05重量％以上0.20重量％以下 Ti:C重量％の５倍以上でかつ0.10重量％未満 を含み、残分がFeと不可避不純物よりなることを特徴と
する耐酸化性に優れた自動車の排気ガス浄化用触媒コン
バータ用Fe−Cr−Al系合金箔である。[Means for Solving the Problems] In the first invention of the present invention, C: less than 0.02% by weight Si: 1.0% by weight or less Cr: 12% by weight or more and 21% by weight or less Al: 2.5% by weight or more and 3.5% by weight Less than La: 0.05 wt% or more and 0.20 wt% or less Ti: Contains at least 5 times the weight of C and less than 0.10 wt%, with the balance being Fe and inevitable impurities, the automobile having excellent oxidation resistance. And a Fe-Cr-Al alloy foil for a catalytic converter for purifying exhaust gas.
また本発明の第２の発明は上記第１の発明のLaに代り
La＋Nd:0.05重量％以上0.20重量％以下を含むことを特
徴とする耐酸化性に優れた自動車の排気ガス浄化用触媒
コンバータ用Fe−Cr−Al系合金箔である。The second invention of the present invention is an alternative to La of the first invention.
La + Nd: Fe-Cr-Al-based alloy foil for catalytic converter for purifying exhaust gas of automobiles having excellent oxidation resistance, characterized by containing not less than 0.05% by weight and not more than 0.20% by weight.
本発明合金は安価な３％Al合金であるFe−Cr−Alをベ
ースとするものであって、Ti及びLaを含み、安価でかつ
耐酸化性にすぐれた合金である。The alloy of the present invention is based on Fe-Cr-Al, which is an inexpensive 3% Al alloy, and contains Ti and La, and is an alloy which is inexpensive and has excellent oxidation resistance.
以下、本発明の各成分の作用とその限定理由について
述べる。Hereinafter, the action of each component of the present invention and the reason for the limitation will be described.
ランタノイド： ランタノイドはLa、Ce、Ndその他原子番号51〜71まで
の15種の金属元素である。Ceを除くLa、Ndのランタノイ
ドは耐酸化性及び酸化スケールの耐剥離性向上に対し顕
著な効果がある。ただし、含有量が0.05重量％未満では
厚さ30〜50μｍ程度の箔での耐酸化性及び酸化スケール
の耐剥離性を確保することはできず、0.20重量％を超え
ると熱間圧延が不可能になるので、0.05重量％以上0.20
重量％以下とした。Ceは熱間加工性、耐酸化性を悪化さ
せるので除外される。Lanthanoids: Lanthanoids are La, Ce, Nd and other 15 metal elements with atomic numbers 51-71. La and Nd lanthanoids other than Ce have a remarkable effect on the improvement of oxidation resistance and the peeling resistance of oxide scale. However, if the content is less than 0.05% by weight, it is not possible to secure the oxidation resistance and the peeling resistance of the oxide scale in a foil with a thickness of about 30 to 50 μm, and if it exceeds 0.20% by weight, hot rolling cannot be performed. Becomes 0.050% by weight or more and 0.20
% By weight or less. Ce is excluded because it deteriorates hot workability and oxidation resistance.
Cr: Crは12重量％未満では耐熱化性が確保できず、21重量
％を超えると靭性が低下し、冷間圧延の生産性が低下す
るので12〜21重量％とした。Cr: When Cr is less than 12% by weight, heat resistance cannot be secured, and when it exceeds 21% by weight, toughness is reduced and productivity of cold rolling is reduced.
Al: 2.5重量％未満では耐酸化性が確保できず、3.5重量％
以下では熱間圧延中に表面欠陥が発生し、その除去に多
大の手数が掛ることと、靭性、延性が低下し、冷間圧延
の生産性が低下するので2.5重量％以上〜3.5重量％未満
とした。Al: If less than 2.5% by weight, oxidation resistance cannot be secured, and 3.5% by weight
In the following, surface defects are generated during hot rolling, and removal of the surface takes a lot of trouble, and toughness and ductility are reduced, and productivity of cold rolling is reduced, so that 2.5% by weight or more and less than 3.5% by weight And
Si: 耐酸化性向上に有効であるが1.0重量％を超えると加
工性を低下させるので1.0重量％以下とした。Si: Effective for improving oxidation resistance, but if it exceeds 1.0% by weight, the workability is reduced.
C: 過剰になると靭性を低下させ、冷間圧延性、加工性を
悪化させるのでC:0.02重量％未満にする必要がある。C: An excessive amount lowers the toughness and deteriorates the cold rolling property and the workability. Therefore, it is necessary to make C: less than 0.02% by weight.
Ti: Tiを添加するとTiが炭化物となってＣを固定して靭性
を改善する。TiはＣ濃度の５倍以上添加しないとその改
善効果が表れないが、0.1重量％以上添加すると耐酸化
性を低下させるので、Ｃ重量％の５倍〜0.10重量％未満
とする。Ti: When Ti is added, Ti becomes carbide and fixes C to improve toughness. If Ti is not added at least 5 times the C concentration, the improvement effect will not be exhibited, but if added at 0.1% by weight or more, the oxidation resistance will be reduced.
第１表に本発明の実施例の化学成分を示し、第２表に
比較例の合金成分を示す。Table 1 shows the chemical components of Examples of the present invention, and Table 2 shows the alloy components of Comparative Examples.
実施例および比較例はそれぞれ10kgインゴットに溶製
造塊した後、1200℃で板厚3mmまで熱間圧延した。この
段階でLa濃度が0.25重量％のＢ−１は熱間圧延時に鋼塊
が割れたので、その後の試験は行っていない。In each of Examples and Comparative Examples, after being melt-produced into 10 kg ingots, each was hot-rolled at 1200 ° C. to a thickness of 3 mm. At this stage, B-1 having a La concentration of 0.25% by weight cracked the steel ingot at the time of hot rolling, and thus no subsequent test was performed.
Ｂ−１以外は焼鈍−酸洗−冷延を繰返し厚さ30μｍの
箔にした。これから板厚30μｍ、幅20mm、長さ30mmの試
験片を採取して、1100℃大気中雰囲気で酸化試験を行っ
た。Except for B-1, annealing, pickling and cold rolling were repeated to form a foil having a thickness of 30 μm. From this, a test piece having a thickness of 30 μm, a width of 20 mm and a length of 30 mm was sampled and subjected to an oxidation test at 1100 ° C. in the atmosphere.
酸化試験は24時間おきに試験片を取り出して重量を測
定する方法である。The oxidation test is a method of taking out a test piece every 24 hours and measuring the weight.
比較鋼中Ｂ−３、Ｂ−５、Ｂ−６は１日目で酸化増量
4mg/cm2で内部まで完全に酸化し、金属部分は残ってい
なかった。残りの比較鋼中Ｂ−２、Ｂ−３は１日目の酸
化増量は0.4mg/cm2であったが、２日目には4mg/cm2にな
り、内部まで完全に酸化消耗していた。これに対し、本
発明による実施鋼Ａ−１〜Ａ−３は１日目に酸化増量が
0.4mg/cm2になった後は２日目までは酸化増の変化はな
く、健全な状態であった。その後、３日目以後、端部等
から異常酸化が徐々に進行し、酸化消耗していった。B-3, B-5 and B-6 in the comparative steels increased in oxidation on the first day
It was completely oxidized to the inside at 4 mg / cm 2 , and no metal part remained. The remaining comparative steels in B-2, B-3 is oxidized amounts of day 1 was 0.4 mg / cm 2, on the second day would 4 mg / cm 2, fully oxidized and consumed the interior Was. On the other hand, the steels A-1 to A-3 according to the present invention showed an increase in oxidation on the first day.
After reaching 0.4 mg / cm 2 , there was no change in oxidation increase until the second day, and the condition was healthy. Thereafter, after the third day, abnormal oxidation gradually progressed from the end portion and the like, and oxidation was consumed.
このように同じ18重量％Cr3重量％Al鋼であってもLa
又はLaとNdを十分に添加してないものは短時間で鋼中の
AlをAl2O3として消耗した後は酸化皮膜の保護性が失わ
れ、酸化が急激に進行してしまうのに対し、La、Ndを添
加したものはAlを消耗した後も十分な耐酸化性を維持し
ている。Thus, even with the same 18 wt% Cr 3 wt% Al steel, La
Or, if La and Nd are not sufficiently added,
After Al was consumed as Al 2 O 3 , the protective properties of the oxide film were lost and oxidation proceeded rapidly, whereas those with La and Nd added had sufficient oxidation resistance even after Al was consumed. Maintain their sexuality.
従って、自動車排ガス浄化用触媒コンバータの中で高
温腐食環境が緩やかな部分であっても、従来のFe−Cr−
Al−REM系合金での３％Al含有鋼では耐久性が不足して
おり、高価な５％Al含有鋼を使用しなければならない。
それに対し、本発明鋼ならば安価な３％Al含有鋼で十分
な耐久性があり、使用可能であり、経済的利益は大き
い。Therefore, even if the high-temperature corrosive environment is moderate in the automotive exhaust gas purifying catalytic converter, the conventional Fe-Cr-
The durability of the 3% Al-containing steel in the Al-REM alloy is insufficient, and expensive 5% Al-containing steel must be used.
On the other hand, in the case of the steel of the present invention, an inexpensive steel containing 3% Al has sufficient durability, can be used, and has a great economic advantage.
また、前述の特開昭56−96726号公報では特殊な熱処
理で表面に長さ数μｍのAl2O3ウィスカーを生成した上
に、触媒のコーティングを行っている。本発明鋼もこれ
と同一の熱処理を行った場合、良好なAl2O3ウィスカー
が生成するので、この製造方法による触媒コンバータに
も好適である。In the above-mentioned Japanese Patent Application Laid-Open No. 56-96726, Al 2 O 3 whiskers having a length of several μm are formed on the surface by a special heat treatment, and a catalyst is coated. When the steel of the present invention is also subjected to the same heat treatment, good Al 2 O 3 whiskers are generated, and thus the steel is also suitable for a catalytic converter according to this production method.
〔発明の効果〕 本発明によれば３％AlのFe−Cr−Al酸化条件のやや緩
やかな場合に好適に使用することのできる安価な３％Al
のFe−Cr−Al系合金箔を製造することができ、産業上寄
与するところが極めて大きい。 [Effects of the Invention] According to the present invention, inexpensive 3% Al which can be suitably used in the case of slightly mild Fe-Cr-Al oxidation conditions of 3% Al.
Fe-Cr-Al-based alloy foils can be produced, which greatly contributes to the industry.
フロントページの続き (56)参考文献 特開 昭49−115927（ＪＰ，Ａ) 特公 昭55−31824（ＪＰ，Ｂ２)Continuation of front page (56) References JP-A-49-115927 (JP, A) JP-B-55-31824 (JP, B2)
Claims (2)
する耐酸化性に優れた自動車の排気ガス浄化用触媒コン
バータ用Fe−Cr−Al系合金箔。1. C: less than 0.02% by weight Si: 1.0% by weight or less Cr: 12% by weight to 21% by weight Al: 2.5% by weight to less than 3.5% by weight La: 0.05% by weight to 0.20% by weight Ti: C Fe-Cr-Al-based catalyst converter for exhaust gas purification of automobiles with excellent oxidation resistance, characterized by containing not less than 5% by weight and less than 0.10% by weight, with the balance being Fe and inevitable impurities. Alloy foil.
する耐酸化性に優れた自動車の排気ガス浄化用触媒コン
バータ用Fe−Cr−Al系合金箔。2. C: less than 0.02% by weight Si: 1.0% by weight or less Cr: 12% by weight to 21% by weight Al: 2.5% by weight to less than 3.5% by weight La + Nd: 0.05% by weight to 0.20% by weight Ti: C Fe-Cr-Al-based catalyst converter for exhaust gas purification of automobiles with excellent oxidation resistance, characterized by containing not less than 5% by weight and less than 0.10% by weight, with the balance being Fe and inevitable impurities. Alloy foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61268838A JP2587413B2 (en) | 1986-11-12 | 1986-11-12 | Fe-Cr-Al alloy foil for catalyst converter for automobile exhaust gas purification with excellent oxidation resistance |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP61268838A JP2587413B2 (en) | 1986-11-12 | 1986-11-12 | Fe-Cr-Al alloy foil for catalyst converter for automobile exhaust gas purification with excellent oxidation resistance |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63125641A JPS63125641A (en) | 1988-05-28 |
| JP2587413B2 true JP2587413B2 (en) | 1997-03-05 |
Family
ID=17463966
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP61268838A Expired - Lifetime JP2587413B2 (en) | 1986-11-12 | 1986-11-12 | Fe-Cr-Al alloy foil for catalyst converter for automobile exhaust gas purification with excellent oxidation resistance |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2587413B2 (en) |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49115927A (en) * | 1973-03-10 | 1974-11-06 | ||
| JPS5531824A (en) * | 1978-08-25 | 1980-03-06 | Taiyo Oil & Fat Mfg | Oil and fat purifying method |
-
1986
- 1986-11-12 JP JP61268838A patent/JP2587413B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63125641A (en) | 1988-05-28 |
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