JP3200160B2 - Fe-Cr-Al alloy excellent in oxidation resistance and high-temperature embrittlement resistance, catalyst carrier using the same, and method for producing alloy foil - Google Patents
Fe-Cr-Al alloy excellent in oxidation resistance and high-temperature embrittlement resistance, catalyst carrier using the same, and method for producing alloy foilInfo
- Publication number
- JP3200160B2 JP3200160B2 JP13883092A JP13883092A JP3200160B2 JP 3200160 B2 JP3200160 B2 JP 3200160B2 JP 13883092 A JP13883092 A JP 13883092A JP 13883092 A JP13883092 A JP 13883092A JP 3200160 B2 JP3200160 B2 JP 3200160B2
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Links
- 230000003647 oxidation Effects 0.000 title claims description 72
- 238000007254 oxidation reaction Methods 0.000 title claims description 72
- 229910045601 alloy Inorganic materials 0.000 title claims description 47
- 239000000956 alloy Substances 0.000 title claims description 47
- 239000011888 foil Substances 0.000 title claims description 32
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 title claims description 27
- 238000004519 manufacturing process Methods 0.000 title claims description 25
- 239000003054 catalyst Substances 0.000 title claims description 9
- 238000000137 annealing Methods 0.000 claims description 36
- 238000005097 cold rolling Methods 0.000 claims description 22
- 230000009467 reduction Effects 0.000 claims description 18
- 238000005096 rolling process Methods 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 14
- 238000005098 hot rolling Methods 0.000 claims description 11
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 8
- 229910000838 Al alloy Inorganic materials 0.000 claims description 7
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 7
- 150000002602 lanthanoids Chemical class 0.000 claims description 7
- 229910017112 Fe—C Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910017060 Fe Cr Inorganic materials 0.000 claims description 2
- 229910002544 Fe-Cr Inorganic materials 0.000 claims description 2
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000758 substrate Substances 0.000 claims 1
- 239000000463 material Substances 0.000 description 42
- 238000012360 testing method Methods 0.000 description 30
- 230000000694 effects Effects 0.000 description 28
- 229910052726 zirconium Inorganic materials 0.000 description 25
- 229910052746 lanthanum Inorganic materials 0.000 description 22
- 229910000831 Steel Inorganic materials 0.000 description 16
- 239000010959 steel Substances 0.000 description 16
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- 238000002844 melting Methods 0.000 description 11
- 230000008018 melting Effects 0.000 description 11
- 230000035939 shock Effects 0.000 description 11
- 229910052748 manganese Inorganic materials 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052804 chromium Inorganic materials 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 229910000851 Alloy steel Inorganic materials 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000013078 crystal Substances 0.000 description 6
- 238000011156 evaluation Methods 0.000 description 6
- 230000002159 abnormal effect Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 230000006872 improvement Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 238000005219 brazing Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 229910052727 yttrium Inorganic materials 0.000 description 3
- 102220479482 Puromycin-sensitive aminopeptidase-like protein_C21D_mutation Human genes 0.000 description 2
- 230000003064 anti-oxidating effect Effects 0.000 description 2
- 239000002131 composite material Substances 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
- 230000007423 decrease Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 230000001747 exhibiting effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910052735 hafnium Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000001953 recrystallisation Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- 229910017108 Fe—Fe Inorganic materials 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 239000003779 heat-resistant material 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
- 229910052742 iron Inorganic materials 0.000 description 1
- 238000005339 levitation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Landscapes
- Metal Rolling (AREA)
- Catalysts (AREA)
- Heat Treatment Of Steel (AREA)
- Heat Treatment Of Sheet Steel (AREA)
Description
【０００１】[0001]
【産業上の利用分野】本発明は、排ガス浄化触媒コンバ
ーターにおける触媒担体として代表的に使用される耐酸
化性合金鋼に係り、特に高温での耐久性に優れたＦｅ−
Ｃｒ−Ａｌ合金およびそれを用いた排ガス浄化触媒コン
バーターの触媒担体ならびに合金箔の製造方法に関す
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxidation-resistant alloy steel typically used as a catalyst carrier in an exhaust gas purifying catalytic converter, and particularly to Fe-Fe alloys having excellent durability at high temperatures.
The present invention relates to a Cr-Al alloy, a catalyst carrier for an exhaust gas purifying catalytic converter using the same, and a method for producing an alloy foil.
【０００２】[0002]
【従来の技術】排ガス浄化触媒コンバーターは、燃料と
空気を混合し燃焼させた時に生成するＮＯｘ、ＨＣ、Ｃ
Ｏなどの有害ガスを無害化するために使用される。この
触媒反応は発熱反応であるためコンバーターの温度は上
昇する。また最近では、触媒反応の効率向上のためコン
バーターを燃焼環境に近い位置に設置し高温の排ガス中
で触媒反応を起こさせる例が多く見られ、高温環境にさ
らされるばかりでなく、急加熱と急冷却が繰り返される
ため非常に大きい熱衝撃を受ける。このような非常に厳
しい条件下で使用される触媒コンバーター用材料として
は、セラミックスが熱衝撃に弱く使用に耐えないため、
耐酸化性に優れるＦｅ−Ｃｒ−Ａｌ合金などの金属材料
が使用される。Ｆｅ−Ｃｒ−Ａｌ合金としては特開昭４
８−４１９１８号、特開昭５８−１７７４３７号、特公
平２−５８３４０号、特公昭６２−１４６２６号、特開
昭６４−３０６５３号、特開平１−１１５４５５号、特
開平２−３０３６０５号等が開示されている。2. Description of the Related Art Exhaust gas purifying catalytic converters are composed of NOx, HC and C generated when fuel and air are mixed and burned.
Used to detoxify harmful gases such as O. Since this catalytic reaction is an exothermic reaction, the temperature of the converter rises. Recently, there have been many cases where a converter is installed close to the combustion environment in order to improve the efficiency of the catalytic reaction, causing a catalytic reaction in high-temperature exhaust gas. Due to repeated cooling, it receives a very large thermal shock. As a material for catalytic converters used under such extremely severe conditions, ceramics are vulnerable to thermal shock and cannot withstand use.
A metal material such as an Fe-Cr-Al alloy having excellent oxidation resistance is used. As an Fe-Cr-Al alloy, Japanese Unexamined Patent Publication No.
JP-A-8-41918, JP-A-58-177337, JP-B-2-58340, JP-B-62-14626, JP-A-64-30653, JP-A-1-115455, JP-A-2-303605, and the like. It has been disclosed.
【０００３】[0003]
【発明が解決しようとする課題】しかし、これらに示さ
れている材料には以下の問題がある。特開昭４８−４１
９１８号では、ＬａとＺｒを複合含有しかつＢを添加し
ているが、結晶粒粗大防止のためＴｉを必須添加とし量
的に多く添加している。本発明によれば、Ｂは耐高温脆
化性を向上させる効果がきわめて大きく、耐破損性を必
要とする触媒コンバーター用のメタルハニカム材には適
量含有が必要であることが確認された。しかし、Ｔｉは
少量の含有によってもＢの耐高温脆化性向上効果を無効
とする作用が強いためハニカム箔は高温脆化を招き、エ
ンジンに近い位置に設置される触媒コンバーター用のメ
タルハニカム材とした場合、厳しい熱衝撃のためハニカ
ムが容易に破損してしまう。従って、特開昭４８−４１
９１８号におけるＴｉの多量含有は上述のメタルハニカ
ム材として致命的な欠陥を招く。However, these materials have the following problems. JP-A-48-41
In No. 918, La and Zr are compounded and B is added, but Ti is indispensably added to prevent crystal grain coarsening, and a large amount is added. According to the present invention, B has an extremely large effect of improving high-temperature embrittlement resistance, and it has been confirmed that a metal honeycomb material for a catalytic converter requiring breakage resistance needs to contain an appropriate amount. However, even if a small amount of Ti is contained, the effect of negating the effect of improving the high-temperature embrittlement resistance of B is strong, so that the honeycomb foil causes high-temperature embrittlement, and a metal honeycomb material for a catalytic converter installed near the engine is provided. In this case, the honeycomb is easily broken due to severe thermal shock. Accordingly, JP-A-48-41
The high content of Ti in No. 918 causes a fatal defect as the above-mentioned metal honeycomb material.
【０００４】特開昭５８−１７７４３７号および特公平
２−５８３４０号ではＬａとＺｒを複合含有している
が、Ｌａの含有量を０．０５重量％以下としているので
複合含有の効果が発揮されず、十分な耐酸化性が得られ
ないうえに、Ｂを含有していないので高温脆化を招く。
特公昭６２−１４６２６号、特開昭６４−３０６５３
号、特開平１−１１５４５５号および特開平２−３０３
６０５号では、同じくＢを含有していないので高温脆化
を招く。In Japanese Patent Application Laid-Open Nos. 58-177737 and 2-58340, La and Zr are compounded. However, since the content of La is set to 0.05% by weight or less, the effect of compounding is exhibited. In addition, sufficient oxidation resistance cannot be obtained, and high temperature embrittlement is caused because B is not contained.
JP-B-62-14626, JP-A-64-30653
, JP-A-1-115455 and JP-A-2-303
No. 605 also does not contain B, which causes high-temperature embrittlement.
【０００５】従って、これらの材料を板厚０．２ｍｍ以
下の箔として触媒コンバーター用ハニカム材として使用
した場合には、耐酸化性が不十分であるため短時間で異
常酸化を生じたり、ハニカムの箔が高温脆化を招いたり
してメタルハニカムは破損してしまう。なお、ここで板
厚０．２ｍｍ以下の箔を特に取り上げたのは、自動車エ
ンジンの排ガス用の触媒担体として、排気抵抗を下げる
ために箔の厚みが薄いことが望まれているという事情か
らである。Accordingly, when these materials are used as a honeycomb material for a catalytic converter as a foil having a plate thickness of 0.2 mm or less, the oxidation resistance is insufficient, so that abnormal oxidation occurs in a short time, The metal honeycomb is broken due to the high temperature embrittlement of the foil. The reason why the foil having a plate thickness of 0.2 mm or less is particularly taken into consideration here is that, as a catalyst carrier for an exhaust gas of an automobile engine, it is desired that the foil has a small thickness in order to reduce exhaust resistance. is there.
【０００６】以上のように、従来のＦｅ−Ｃｒ−Ａｌ合
金では高温下で、しかも０．２ｍｍ以下の合金箔として
使用される触媒コンバーター用の材料としては耐酸化性
およびハニカム破損に対する耐久性が不十分であり、材
料全体が酸化物に変化する、いわゆる異常酸化を起こし
たり、ハニカム箔が高温で脆化し破損するなど、使用に
耐えないのが実情である。As described above, the conventional Fe-Cr-Al alloy has a high oxidation resistance and a high durability against honeycomb breakage as a material for a catalytic converter used as an alloy foil of 0.2 mm or less at a high temperature. It is inadequate and does not withstand use, for example, the entire material changes into oxides, so-called abnormal oxidation, and the honeycomb foil becomes brittle and breaks at high temperatures.
【０００７】従って、上述した従来技術の欠点を解消し
た耐酸化性および耐高温脆化性に優れたＦｅ−Ｃｒ−Ａ
ｌ合金、より具体的には、Ａｌ含有量が４重量％未満の
材料に対しては９００℃までの温度、またＡｌ含有量が
４重量％以上の材料に対しては１１００℃までの温度に
繰り返し加熱される条件下で長時間使用しても異常酸化
あるいは高温脆化を生じない、板厚が０．２ｍｍ以下の
箔用に最適なＦｅ−Ｃｒ−Ａｌ合金およびそれを用いた
排ガス浄化触媒コンバーターにおける触媒担体ならびに
Ｆｅ−Ｃｒ−Ａｌ合金箔の製造方法を提供することを目
的としている。Accordingly, Fe-Cr-A which is excellent in oxidation resistance and high-temperature embrittlement resistance which has solved the above-mentioned disadvantages of the prior art.
alloys, more specifically at temperatures up to 900 ° C. for materials with an Al content of less than 4% by weight and up to 1100 ° C. for materials with an Al content of 4% by weight or more. Fe-Cr-Al alloy that does not cause abnormal oxidation or high-temperature embrittlement even if used for a long time under conditions of repeated heating and is optimal for foils with a thickness of 0.2 mm or less, and an exhaust gas purification catalyst using the same It is an object of the present invention to provide a method for producing a catalyst carrier and an Fe—Cr—Al alloy foil in a converter.
【０００８】[0008]
【課題を解決するための手段】すなわち、本発明は、
Ｃ：０．０５重量％以下、Ｎ：０．０２重量％以下、Ｓ
ｉ：０．５重量％以下、Ｍｎ：１．０重量％以下、Ｃ
ｒ：１０〜２８重量％、Ａｌ：１〜１０重量％、Ｂ：
０．０００３〜０．０１０重量％を含有し、さらに Ｌａ：０．０１〜０．２０重量％、 Ｚｒ：０．０１〜１．０重量％ を含有し、かつ（Ｉ）式を満足し、 ０．１≦〔Ｚｒ重量％〕／〔Ｌａ重量％〕≦２０………（Ｉ） 残部Ｆｅおよび不可避的不純物よりなる、耐酸化性およ
び耐高温脆化性に優れたＦｅ−Ｃｒ−Ａｌ合金を提供す
るものである。ここで、本発明のＦｅ−Ｃｒ−Ａｌ合金
は、下記〜を選択的に１つ以上含有していてもよ
い。 Ｔｉを０．０５重量％未満、 Ｃａ、Ｍｇのうち１種以上をそれぞれ０．０５重量％
以下、 Ｌａを除くランタノイド：０．２重量％以下、 Ｙ：０．５重量％以下、 Ｈｆ：０．３重量％以下 から選ばれた１種以上、 Ｎｂ、Ｖ、Ｔａから選ばれた１種以上を合計で１．０
重量％以下That is, the present invention provides:
C: 0.05% by weight or less, N: 0.02% by weight or less, S
i: 0.5% by weight or less, Mn: 1.0% by weight or less, C
r: 10 to 28% by weight, Al: 1 to 10% by weight, B:
0.0003 to 0.010% by weight, La: 0.01 to 0.20% by weight, Zr: 0.01 to 1.0% by weight and satisfying the formula (I), 0.1 ≦ [Zr wt%] / [La wt%] ≦ 20 (I) Fe—Cr—Al alloy consisting of balance of Fe and unavoidable impurities and having excellent oxidation resistance and high temperature embrittlement resistance Is provided. Here, the Fe—Cr—Al alloy of the present invention may selectively contain one or more of the following. Less than 0.05% by weight of Ti, 0.05% by weight of at least one of Ca and Mg
Hereinafter, lanthanoids excluding La: 0.2 wt% or less, Y: 0.5 wt% or less, Hf: 0.3 wt% or less, one or more selected from Nb, V, Ta The above is a total of 1.0
Weight% or less
【０００９】また、本発明は、Ｆｅ−Ｃｒ−Ａｌ合金を
圧延した０．２ｍｍ以下の箔を用いて組み立てられた排
ガス浄化触媒コンバーター用触媒担体を提供する。[0009] The present invention also provides a catalyst carrier for an exhaust gas purifying catalytic converter assembled using a foil of 0.2 mm or less obtained by rolling an Fe-Cr-Al alloy.
【００１０】さらに、本発明は、Ｆｅ−Ｃｒ−Ａｌ合金
のスラブに熱間圧延を行った後で焼鈍を行い、さらに圧
下率３０％以上の冷間圧延と８００〜１２００℃の温度
での焼鈍を１回以上行うことを特徴とする耐酸化性およ
び耐高温脆化性に優れたＦｅ−Ｃｒ−Ａｌ合金箔の製造
方法を提供する。[0010] Further, the present invention is to perform annealing after performing hot rolling on a slab of an Fe-Cr-Al alloy, and further perform cold rolling at a rolling reduction of 30% or more and annealing at a temperature of 800 to 1200 ° C. Is carried out at least once, and a method for producing an Fe—Cr—Al alloy foil excellent in oxidation resistance and high-temperature embrittlement resistance is provided.
【００１１】さらに、本発明は、Ｆｅ−Ｃｒ合金または
Ｆｅ−Ｃｒ−Ａｌ合金よりなる素地板に、Ａｌまたはさ
らに所定の元素を含有するＡｌ合金を表面に付着させ、
不活性あるいは還元性雰囲気内で加熱して、前記付着成
分を前記素地板中に拡散させて、請求項１〜５に記載の
合金組成とした合金板に、さらに圧下率３０％以上の冷
間圧延と８００〜１２００℃の温度での焼鈍を１回以上
行うことを特徴とする耐酸化性および耐高温脆化性に優
れたＦｅ−Ｃｒ−Ａｌ合金箔の製造方法を提供する。Further, the present invention provides a base plate made of an Fe—Cr alloy or an Fe—Cr—Al alloy, wherein Al or an Al alloy containing a predetermined element is adhered to the surface,
Heating in an inert or reducing atmosphere to diffuse the adhering component into the base plate, and further to a cold plate having a rolling reduction of 30% or more on the alloy plate having the alloy composition according to claim 1. A method for producing an Fe—Cr—Al alloy foil having excellent oxidation resistance and high-temperature embrittlement resistance, characterized by performing rolling and annealing at a temperature of 800 to 1200 ° C. at least once.
【００１２】[0012]
【作用】以下に本発明をさらに詳細に説明する。まず、
本発明の基礎となった実験を説明する。はじめに本発明
者らは、１２００℃、大気中での高温におけるＦｅ−Ｃ
ｒ−Ａｌ合金箔の耐酸化性について元素の影響を調査し
た。その結果、ＬａとＺｒの複合含有が、従来より明ら
かにされている希土類元素であるランタノイド、Ｙ、Ｈ
ｆなどの元素の単独の含有では実現不可能な耐酸化性改
善効果を有することが明らかとなった。The present invention will be described below in more detail. First,
The experiment on which the present invention is based will be described. First, the present inventors have found that Fe-C
The influence of elements on the oxidation resistance of the r-Al alloy foil was investigated. As a result, the complex content of La and Zr was found to be a rare earth element lanthanoid, Y, H
It has been clarified that a single element such as f has an oxidation resistance improving effect that cannot be realized.
【００１３】図１は、０．００５ｗｔ％Ｃ、０．００５
ｗｔ％Ｎ、２０ｗｔ％Ｃｒ、５ｗｔ％Ａｌ、０．１ｗｔ
％Ｓｉ、０．２ｗｔ％Ｍｎ、０．００２ｗｔ％Ｂを含有
し、残部Ｆｅおよび不可避的不純物よりなる合金に対し
て、Ｌａを単独で０．０７２重量％含有させた合金、Ｚ
ｒを単独で０．０７８重量％含有させた合金、およびＬ
ａとＺｒをそれぞれ０．０５３重量％、０．０８３重量
％複合含有させた合金の板厚５０μｍの箔に対しての１
２００℃、大気中での酸化時間に対する重量変化を示し
たものである。FIG. 1 shows 0.005 wt% C, 0.005 wt% C,
wt% N, 20wt% Cr, 5wt% Al, 0.1wt
%, An alloy containing 0.2 wt% Mn and 0.002 wt% B, and an alloy containing 0.072 wt% of La alone with respect to the balance of Fe and inevitable impurities.
an alloy containing 0.078% by weight of r alone;
a and Zr in an alloy containing 0.053% by weight and 0.083% by weight, respectively, of a 50 μm-thick foil.
It shows a change in weight with respect to the oxidation time in the air at 200 ° C.
【００１４】図１より、Ｌａを単独含有させた合金、Ｚ
ｒを単独含有させた合金のそれぞれが短時間で異常酸化
により重量増加を起こしているのに対し、ＬａとＺｒを
複合含有させた合金では、上記単独含有させた合金のそ
れぞれの寿命の和に対して２倍以上の寿命を有すること
がわかる。これは、ＬａとＺｒを複合させた場合の耐酸
化性改善効果は、Ｌａ、Ｚｒを単独含有させた場合のそ
れぞれの耐酸化性改善効果の和になるとする従来の考え
方を超える新たな発見である。FIG. 1 shows that the alloy containing only La, Z
While each of the alloys containing r alone caused an increase in weight due to abnormal oxidation in a short period of time, the alloy containing La and Zr compositely contained the sum of the life of each of the alloys containing only r. It can be seen that the life is more than twice as long. This is a new discovery that goes beyond the conventional idea that the oxidation resistance improvement effect when La and Zr are combined is the sum of the respective oxidation resistance improvement effects when La and Zr are solely contained. is there.
【００１５】本発明者らは、ＬａとＺｒの複合含有につ
いてさらに詳細な調査を行った結果、ＬａとＺｒの複合
含有の効果を十分に発揮させるためには、ＬａとＺｒの
含有量の比が所定の範囲内にあることが必要なことを見
出した。The present inventors have conducted a more detailed study on the complex content of La and Zr. As a result, in order to sufficiently exert the effect of the complex content of La and Zr, the ratio of the content of La and Zr was determined. Has to be within a predetermined range.
【００１６】すなわち、図１からも推察されるように、
Ｌａ、Ｚｒの一方の含有量に対し他方の含有量が極端に
少なくなると、単独含有の場合と同様に耐酸化性が著し
く劣化するため、ＬａとＺｒの含有量の比は一定の範囲
内にある必要があることを見出した。That is, as inferred from FIG.
When the content of one of La and Zr is extremely small with respect to the other, oxidation resistance is significantly deteriorated as in the case of single content, so that the ratio of the content of La and Zr is within a certain range. I found that there was a need.
【００１７】本発明者らは、０．００５ｗｔ％Ｃ、０．
００５ｗｔ％Ｎ、２０ｗｔ％Ｃｒ、５ｗｔ％Ａｌ、０．
１ｗｔ％Ｓｉ、０．２ｗｔ％Ｍｎ、０．００２ｗｔ％Ｂ
を含有し、残部Ｆｅおよび不可避的不純物よりなる合金
の、板厚５０μｍの箔の耐酸化寿命比（後述する実施例
で定義される）に及ぼすＺｒ含有量とＬａ含有量の比
（〔Ｚｒ含有量〕／〔Ｌａ含有量〕の値）の影響を、Ｌ
ａ：０．０１〜０．２重量％、Ｚｒ：０．０１〜１．０
重量％の範囲で調査した結果、図２に示すように、Ｌａ
とＺｒの含有量の間に（Ｉ）式の関係がある時に優れた
耐酸化性が得られることを見出した。 ０．１≦〔Ｚｒ重量％〕／〔Ｌａ重量％〕≦２０………（Ｉ）[0017] The present inventors have found that 0.005 wt% C, 0.
005 wt% N, 20 wt% Cr, 5 wt% Al, 0.1 wt%
1 wt% Si, 0.2 wt% Mn, 0.002 wt% B
And the ratio of the Zr content to the La content of the alloy consisting of the balance of Fe and unavoidable impurities on the oxidation life ratio (defined in Examples described later) of a 50-μm-thick foil ([Zr content Amount] / [value of [La content])
a: 0.01 to 0.2% by weight, Zr: 0.01 to 1.0
As a result of investigation in the range of weight%, as shown in FIG.
It has been found that excellent oxidation resistance can be obtained when there is a relationship of the formula (I) between the content of Zr and Zr. 0.1 ≦ [Zr weight%] / [La weight%] ≦ 20 (I)
【００１８】本発明では、耐酸化性の改善に関して
（Ｉ）式が最も重要な関係である。すなわち、ＬａとＺ
ｒを含有したＦｅ−Ｃｒ−Ａｌ合金において（Ｉ）式を
満足することが高温における耐酸化性を改善するための
最も重要な関係である。ただし、（Ｉ）式を満足しても
Ｌａ、Ｚｒの単独含有量が少なすぎると十分な効果が発
揮されない。そのためにはＬａ、Ｚｒともに０．０１重
量％以上の含有が必要である。また、ＬａとＺｒはそれ
ぞれ０．０１重量％以上の含有量で（Ｉ）式を満足させ
ればその効果が十分発揮させることができる。しかし、
Ｌａは固溶限が小さく、０．２０ｗｔ％を超えて含有さ
せると金属Ｌａが粒界に析出するため、含有量に見合っ
た耐酸化性が得られなくなるほか、熱間および冷間での
加工性を著しく劣化させるので、含有量の上限を０．２
０重量％に限定する必要がある。また、Ｚｒは、過剰に
含有させるとＦｅ2 ＺｒやＦｅ3 Ｚｒなどの金属間化合
物を形成するため、逆に耐酸化性を劣化したり熱間およ
び冷間での加工性を劣化するので、含有量の上限を１．
０重量％に限定する必要がある。In the present invention, the formula (I) is the most important relationship with respect to the improvement of oxidation resistance. That is, La and Z
Satisfying the formula (I) in the Fe-Cr-Al alloy containing r is the most important relationship for improving the oxidation resistance at high temperatures. However, even if the formula (I) is satisfied, if the single content of La and Zr is too small, a sufficient effect is not exhibited. For this purpose, La and Zr must both be contained in an amount of 0.01% by weight or more. Further, if the content of La and Zr is 0.01% by weight or more and the expression (I) is satisfied, the effect can be sufficiently exhibited. But,
La has a small solid solubility limit, and if contained in excess of 0.20 wt%, metal La precipitates at the grain boundaries, so that oxidation resistance commensurate with the content cannot be obtained, and hot and cold working is performed. Content, the upper limit of the content is 0.2
It must be limited to 0% by weight. In addition, Zr, when contained excessively, forms an intermetallic compound such as Fe 2 Zr or Fe 3 Zr, and conversely deteriorates oxidation resistance or deteriorates hot and cold workability. The upper limit of the content is 1.
It must be limited to 0% by weight.
【００１９】次に本発明者らは、Ｆｅ−Ｃｒ−Ａｌ合金
について、耐高温脆化性について検討を行った。その結
果、Ｆｅ−Ｃｒ−Ａｌ合金に対しては特にＢの添加が有
効であることがわかった。本発明者らは、０．００５ｗ
ｔ％Ｃ、０．００５ｗｔ％Ｎ、２０ｗｔ％Ｃｒ、５ｗｔ
％Ａｌ、０．１ｗｔ％Ｌａ、０．１ｗｔ％Ｚｒ、０．２
５ｗｔ％Ｓｉ、０．４ｗｔ％Ｍｎを含有し、残部Ｆｅお
よび不可避的不純物よりなる組成を基準とし、Ｂの含有
量を変化させた合金の板厚５０μｍ箔を加工してハニカ
ム状とし、後述する大気中での繰り返し酸化試験を行っ
た。Next, the present inventors examined the high-temperature embrittlement resistance of the Fe—Cr—Al alloy. As a result, it was found that the addition of B was particularly effective for the Fe—Cr—Al alloy. We have 0.005w
t% C, 0.005wt% N, 20wt% Cr, 5wt
% Al, 0.1 wt% La, 0.1 wt% Zr, 0.2
A 50 μm-thick foil of an alloy containing 5 wt% Si and 0.4 wt% Mn and having the B content changed based on the composition of the balance of Fe and unavoidable impurities is processed into a honeycomb shape, which will be described later. A repeated oxidation test in the atmosphere was performed.
【００２０】耐高温脆化性の評価は、繰り返し酸化試験
に対して破損を生じた繰り返し回数を各供試材について
求め、Ｂを含有させていない合金に対する比をとり、こ
れを耐高温脆化性比と定義し、この値の比較により行っ
た。図３に、上記繰り返し試験を行った場合の供試材の
耐高温脆化性比とＢ含有量の関係を示す。図３より、Ｂ
を０．０００３〜０．０１重量％含有することで高温で
のハニカムの破損を防止できることがわかる。The evaluation of high-temperature embrittlement resistance was performed by obtaining the number of repetitions at which damage occurred in the repeated oxidation test for each test material, taking the ratio to the alloy containing no B, and calculating the ratio. The ratio was defined as the sex ratio, and this value was compared. FIG. 3 shows the relationship between the high-temperature embrittlement resistance ratio and the B content of the test material when the above-mentioned repetition test was performed. According to FIG.
Contains 0.0003 to 0.01% by weight, it is possible to prevent honeycomb breakage at high temperatures.
【００２１】この機構は必ずしも明らかではないが、以
下のように考えられる。すなわち、Ｂを微量含有した場
合は粒界に偏析したＢが粒界のエネルギーを低下させて
粒界を析出サイトとする化合物の析出を防止し、粒界強
度を上げるため脆化が防止できる。一方、多量に含有し
た場合にはＢ自身の粒界のエネルギーを低下させる効果
によって粒界の強度が低下して脆化してしまうと考えら
れる。以上のように、メタルハニカムの高温での脆化を
防止するためには、Ｂを含有することが必要である。Although this mechanism is not always clear, it is considered as follows. That is, when a small amount of B is contained, B segregated at the grain boundary lowers the energy of the grain boundary to prevent precipitation of a compound having the grain boundary as a precipitation site, and increases the strength of the grain boundary, so that embrittlement can be prevented. On the other hand, when contained in a large amount, it is considered that the effect of lowering the energy of the grain boundaries of B itself lowers the strength of the grain boundaries and causes embrittlement. As described above, it is necessary to contain B in order to prevent embrittlement of a metal honeycomb at a high temperature.
【００２２】さらに本発明者らは、Ｂの耐高温脆化性改
善効果について詳細を調査した結果、より厳しい熱衝撃
を受ける試験条件下ではＴｉの存在によりＢの耐高温脆
化性の向上効果が無効となることが明らかとなった。す
なわち、図３の実験に用いた試料の合金成分に対し、Ｔ
ｉを０．０５重量％以上含有させた合金の板厚５０μｍ
の箔で作製したメタルハニカムに対して後述する熱衝撃
試験を行った場合、供試材の耐高温脆化性比はすべての
合金で１．０となってしまった。すなわち、Ｔｉの０．
０５重量％以上の含有によりＢの耐高温脆化性向上効果
が無効となることを示している。この事実は、後述する
実施例において示される。この理由については明らかで
はないが、ＴｉＣなどが粒界に優先析出して上述したＢ
の粒界のエネルギーを低下させる効果をなくすためと思
われる。従って、Ｂの耐高温脆化性を向上させる効果を
発揮させるためには、Ｔｉを含有させないか、あるいは
含有させるとしても、Ｔｉ含有量を０．０５重量％未
満、好ましくは０．０３重量％以下に抑えることが必要
である。The present inventors have further investigated the effect of improving the high-temperature embrittlement resistance of B. As a result, under the test conditions subjected to severer thermal shock, the presence of Ti caused the effect of improving the high-temperature embrittlement resistance of B. Became invalid. That is, the alloy component of the sample used in the experiment of FIG.
50 μm thickness of alloy containing 0.05% by weight or more of i
When a later-described thermal shock test was performed on a metal honeycomb made of the above-mentioned foil, the high-temperature embrittlement resistance ratio of the test material was 1.0 for all alloys. That is, the Ti.
This indicates that the effect of improving the high-temperature embrittlement resistance of B becomes ineffective when the content is 05% by weight or more. This fact will be shown in the examples described later. Although the reason for this is not clear, TiC or the like preferentially precipitates at the grain boundaries and the above-mentioned B
This seems to eliminate the effect of lowering the energy of the grain boundaries. Therefore, in order to exhibit the effect of improving the high-temperature embrittlement resistance of B, Ti is not contained, or even if it is contained, the Ti content is less than 0.05% by weight, preferably 0.03% by weight. It is necessary to keep it below.
【００２３】以下に、その他の合金元素の作用および数
値限定理由について説明する。The functions of other alloying elements and the reasons for limiting the numerical values will be described below.
【００２４】Ｃｒ：Ｃｒは、Ａｌの耐酸化性を向上させ
る効果を助ける役割を待つばかりでなくＣｒ自体が耐酸
化性を向上させる効果を有する元素であり、これらの効
果を十分発揮させるために１０重量％以上の含有が必要
である。Ｃｒの耐酸化性向上効果は、含有量の増加に伴
って増加し、特に１８重量％以上含有することで優れた
耐酸化性が得られるが、２８重量％を超えて含有させる
と、靱性および延性が低下し製造性が低下するので範囲
を１０〜２８重量％に限定する。Cr: Cr is an element that not only waits for the role of assisting the effect of improving the oxidation resistance of Al but also has the effect of improving the oxidation resistance of Cr itself. A content of 10% by weight or more is required. The effect of improving the oxidation resistance of Cr increases with an increase in the content. In particular, when the content is 18% by weight or more, excellent oxidation resistance is obtained. However, when the content exceeds 28% by weight, the toughness and The range is limited to 10 to 28% by weight because the ductility is reduced and the productivity is reduced.
【００２５】Ａｌ：Ａｌは、耐酸化性を維持するために
必要不可欠な元素であり、含有量の増加に伴って高温で
かつ長時間の使用に耐え得る材料となる。触媒コンバー
ターとして実際に使用される温度が最高９００℃であれ
ば４重量％未満のＡｌ含有量、それ以上の温度で使用す
る場合は４重量％以上が必要であるが、その効果を十分
発揮させるためには、最低でも１重量％以上の含有が必
要である。Al: Al is an indispensable element for maintaining oxidation resistance, and becomes a material that can withstand high temperature and long-term use as its content increases. When the temperature actually used as a catalytic converter is 900 ° C. at the maximum, the Al content is less than 4% by weight, and when it is used at a temperature higher than 4% by weight, the effect is sufficiently exhibited. For this purpose, the content must be at least 1% by weight or more.
【００２６】ここで、Ａｌ含有量が６重量％以上の合金
を溶製する場合は靱性が低く製造しにくいため、板厚
０．２ｍｍ程度に圧延加工が可能な適当な組成の合金に
メッキなどの方法によりＡｌを付着させ、熱処理により
Ａｌを拡散させて合金鋼の成分を調整してもよい。しか
し、１０重量％を超えて含有させると、合金鋼の靱性が
著しく低くなり、たとえＡｌメッキ法を用いたとしても
Ａｌメッキ層の拡散処理後に行われる箔圧延で割れを生
じるため上限を１０重量％とし、範囲を１〜１０重量％
とした。Here, when an alloy having an Al content of 6% by weight or more is produced by melting, the toughness is low and it is difficult to produce the alloy. Al may be adhered by the method described above, and the component of the alloy steel may be adjusted by diffusing Al by heat treatment. However, when the content exceeds 10% by weight, the toughness of the alloy steel is remarkably lowered, and even if an Al plating method is used, a crack is generated in the foil rolling performed after the diffusion treatment of the Al plating layer. % And the range is 1 to 10% by weight
And
【００２７】ＣおよびＮ：ＣおよびＮは、フェライト系
ステンレス鋼においては共に固溶限が小さく、主として
炭化物、窒化物として析出し耐食性を劣化させるほか、
鋼板の靱性および延性を著しく低下させる。特にＮはＡ
ｌと窒化物を形成し有効Ａｌ（固溶Ａｌ）を減少させる
ばかりでなく、巨大な窒化物が箔製造時の欠陥の原因と
なり歩止りを著しく劣化させるので、できるだけ少ない
方が望ましいが、工業的、経済的な溶製技術を考慮して
上限をＣ：０．０５重量％、Ｎ：０．０２重量％とし
た。C and N: C and N both have small solid solubility limits in ferritic stainless steel, and precipitate mainly as carbides and nitrides to deteriorate corrosion resistance.
It significantly reduces the toughness and ductility of the steel sheet. Especially N is A
In addition to forming a nitride with l to reduce the effective Al (solid solution Al), a large nitride causes defects during the production of the foil and significantly deteriorates the yield. The upper limits were set to 0.05% by weight of C and 0.02% by weight of N in consideration of a cost-effective and economical smelting technique.
【００２８】ＳｉおよびＭｎ：ＳｉおよびＭｎは、Ａｌ
脱酸の予備脱酸剤として添加された場合鋼中に残存する
ことがあるが、Ｓｉは酸化スケールの耐はくり性を低下
させ、またＭｎは耐酸化性および耐食性を劣化させるの
でともに少ない方がよいが工業的および経済的な溶製造
技術を考慮して、Ｓｉは０．５重量％以下、Ｍｎは１．
０重量％以下に限定した。Si and Mn: Si and Mn are Al
If added as a preliminary deoxidizing agent for deoxidation, it may remain in the steel, but Si reduces the peeling resistance of the oxide scale, and Mn deteriorates the oxidation resistance and corrosion resistance. However, considering industrial and economical solution production technology, Si is 0.5% by weight or less and Mn is 1.
It was limited to 0% by weight or less.
【００２９】本発明は、上記元素を実質的な基本成分と
する鋼に、下記元素群から必要に応じて１種または２種
以上が添加される。According to the present invention, one or more of the following elements may be added to steel containing the above elements as a substantial basic component, if necessary.
【００３０】Ｃａ：Ｃａは、鋼中のＳを固定して鋼を清
浄にし耐酸化性および靱性を向上させる元素であり、ま
たＡｌ2 Ｏ3 の融点を下げて精練時に生成したＡｌ2 Ｏ
3 の浮上を促進して鋼中の介在物を少なくして靱性を向
上させる元素であるが、鋼中に０．０５重量％を超えて
存在すると逆に耐酸化性が低下するために、その上限を
０．０５重量％とした。Ca: Ca is an element that fixes S in steel, cleans the steel and improves oxidation resistance and toughness, and lowers the melting point of Al 2 O 3 to form Al 2 O generated during refining.
3 is an element that promotes the levitation and reduces inclusions in the steel to improve toughness. However, if it exceeds 0.05% by weight in the steel, on the contrary, the oxidation resistance decreases. The upper limit was 0.05% by weight.
【００３１】Ｍｇ：Ｍｇは、微量含有した場合には非常
に緻密なＡｌ2 Ｏ3 スケールを生成させ耐酸化性を向上
させる元素であるが、０．０５重量％を超えて含有する
と熱延性等の製造性が著しく低下するためにその上限を
０．０５重量％とした。Mg: Mg is an element that forms a very dense Al 2 O 3 scale and improves oxidation resistance when contained in a trace amount, but contains more than 0.05% by weight, such as hot ductility. The upper limit was set to 0.05% by weight because of the remarkable decrease in productivity.
【００３２】Ｌａを除くランタノイド、Ｙ、Ｈｆ：Ｌａ
を除くＮｄ、Ｓｍ等のランタノイド、ＹおよびＨｆは、
Ｆｅ−Ｃｒ−Ａｌ合金に高温で生成する酸化皮膜の密着
性を向上させることを通じて耐酸化性を向上させる効果
を有する。しかし、Ｆｅ−Ｃｒ−Ａｌ合金に対する固溶
限が小さい上に固溶限を超えて含有させると、粒界に析
出して加工性を劣化させるため、それぞれ、上限をＬａ
を除くランタノイド：０．２０重量％、Ｙ：０．５０重
量％、Ｈｆ：０．３０重量％とした。ここで、タンタノ
イドであるＣｅは耐酸化性向上効果が小さく、また多量
に添加した場合にはＬａの耐酸化性向上効果を減ずるこ
とがあるので、含有させない方が望ましい。Lanthanoid except La, Y, Hf: La
Lanthanoids such as Nd, Sm, etc., except for
It has the effect of improving the oxidation resistance by improving the adhesion of the oxide film formed at a high temperature to the Fe-Cr-Al alloy. However, when the solid solubility limit of Fe—Cr—Al alloy is small and the content exceeds the solid solubility limit, precipitation at grain boundaries deteriorates workability.
Lanthanoid except for: 0.20% by weight, Y: 0.50% by weight, and Hf: 0.30% by weight. Here, Ce, which is a tantanoid, has a small effect of improving the oxidation resistance, and when added in a large amount, the effect of improving the oxidation resistance of La may be reduced.
【００３３】Ｎｂ，Ｔａ，Ｖ：これらの元素は、ＡｌＮ
を形成してＡｌを消耗し耐酸化性を劣化させるＮを無害
化する効果を有するが、過剰に含有させると、これら元
素の固溶量が増大し逆に耐酸化性を劣化させたり熱間お
よび冷間での加工性を低下させるので上限を含有量の合
計で１．０重量％とした。Nb, Ta, V: These elements are AlN
Has the effect of detoxifying N, which consumes Al and degrades oxidation resistance. However, if it is contained excessively, the solid solution amount of these elements increases, conversely deteriorating oxidation resistance or reducing hot work. Further, since the workability in the cold state is lowered, the upper limit is set to 1.0% by weight in total of the contents.
【００３４】次に、本発明の合金箔の製造方法について
説明する。本発明合金は、大体の目安としてＡｌ含有量
が６重量％までは、通常の転炉法により溶製され溶融状
態で成分調整を行い、鋼塊あるいはスラブに鋳込まれ、
５００〜１３００℃の温度範囲内で圧下率５０％以上の
熱間圧延を行った後で焼鈍を行い、さらに冷間圧延と焼
鈍を繰り返し行って、必要な厚さのコイルあるいは切板
として製造される。Next, the method for producing the alloy foil of the present invention will be described. The alloy of the present invention is, as a rough guide, up to an Al content of 6% by weight, is melted by a normal converter method, is subjected to component adjustment in a molten state, and is cast into a steel ingot or slab.
After performing hot rolling at a reduction rate of 50% or more in a temperature range of 500 to 1300 ° C., annealing is performed, and then cold rolling and annealing are repeatedly performed to produce a coil or a cut plate having a required thickness. You.
【００３５】また、特にＡｌ含有量が６重量％を越える
場合などは、上述の製造方法でコイルあるいは切板を製
造すると冷間での靱性が著しく低いため、歩止りが悪く
大量生産には向かない。このような場合には、適当な組
成の合金のコイルまたは切板を上記製造方法にて作製
し、その表面にスパッタリング法やメッキ法、クラッド
法などによりＡｌあるいはさらに必要元素を含有するＡ
ｌ合金を付着させたものを適切な熱処理によって元素を
拡散させ均質とした後に冷間圧延と焼鈍を行って、本発
明に規定される合金組成を有するコイルあるいは切板と
して製造する方法が採用される。In particular, when the Al content exceeds 6% by weight, when the coil or the cut plate is manufactured by the above-described manufacturing method, the toughness in the cold state is extremely low. No In such a case, a coil or a cut plate of an alloy having an appropriate composition is prepared by the above-described manufacturing method, and the surface thereof is formed by sputtering, plating, cladding, or the like containing Al or a necessary element.
(1) A method of producing a coil or a cut plate having the alloy composition specified in the present invention by performing cold rolling and annealing after diffusing the element by appropriate heat treatment to homogenize the element to which the alloy is adhered, and then performing cold rolling and annealing. You.
【００３６】いずれの製造方法においても、圧延したま
まの状態で使用することができるが、焼鈍された最終製
品を製造する場合には、低酸素分圧の不活性ガス雰囲気
下あるいは還元ガス雰囲気下で光輝焼鈍（Bright annea
ling, BA）を行う。この理由は、酸化性ガス雰囲気下で
焼鈍を行うと、合金中のＡｌが優先的に酸化されＡｌ 2
Ｏ3 スケールを形成して合金中のＡｌを消費し、かつハ
ニカムの加工性が悪化するためである。In any of the manufacturing methods,
Can be used as is, but annealed final product
When manufacturing products, use an inert gas atmosphere with a low oxygen partial pressure.
Bright annealed under a reducing gas atmosphere
ling, BA). The reason is that in an oxidizing gas atmosphere
When annealing is performed, Al in the alloy is preferentially oxidized and Al Two
OThreeForming scale and consuming Al in the alloy;
This is because the workability of the honeycomb deteriorates.
【００３７】また、上記２種類の製造方法において、冷
間圧延の圧下率を３０％以上とし、かつ冷間圧延後の焼
鈍を８００〜１２００℃の範囲で行うと、Ｂの耐高温脆
化性向上の特性がより発揮される。なお、後者の製造方
法においては、この製造条件は、Ａｌまたはさらに必要
元素を含有するＡｌ合金を付着させる前のコイルまたは
切板に対する冷間圧延およびこの冷間圧延後の焼鈍に対
しても適用される。In the above two types of manufacturing methods, when the rolling reduction of the cold rolling is set to 30% or more and the annealing after the cold rolling is performed in the range of 800 to 1200 ° C., the high temperature embrittlement resistance of B The improved characteristics are exhibited more. In the latter manufacturing method, this manufacturing condition is also applied to cold rolling on a coil or a cut plate before attaching Al or an Al alloy further containing a necessary element, and annealing after this cold rolling. Is done.
【００３８】これは、冷間圧延において圧下率を３０％
以上とすることにより材料内に十分な歪みを蓄積させ、
さらに８００℃以上の温度で焼鈍を行うことによりＢの
均一分散が図れるとともに再結晶時の結晶粒径を比較的
細かくかつ均一とするためである。Ｂは上述のように粒
界のエネルギーを減少させて耐高温脆化性を向上させる
と考えられるため、粒界に均一に偏析していることが望
ましい。そのためにも上記の冷間圧延および焼鈍条件で
製造することはＢの効果を発揮させるためにも役立つ。This is because the rolling reduction is 30% in cold rolling.
By doing so, sufficient strain is accumulated in the material,
Further, by performing annealing at a temperature of 800 ° C. or more, uniform dispersion of B can be achieved, and the crystal grain size during recrystallization is made relatively fine and uniform. B is considered to improve the high-temperature embrittlement resistance by reducing the energy of the grain boundaries as described above, and therefore it is desirable that B is uniformly segregated at the grain boundaries. For this reason, manufacturing under the above-described cold rolling and annealing conditions is also useful for exhibiting the effect of B.
【００３９】このような効果は熱間圧延と焼鈍の組み合
わせでは実現しにくい。その理由は、熱間圧延の焼鈍組
織には集合組織の集積が顕著であるため、均一な組織が
得られにくいためである。この種の合金鋼の場合、再結
晶時の結晶粒径は保持時間によらず保持温度でほぼ決定
される。１２００℃超の高温で焼鈍を行った場合、結晶
粒は約３００μｍ以上に粗大化する。粗大化した結晶粒
は、そのままでは粒界面積が小さくなるため高温脆化が
おこりやすくなる。また、たとえさらに冷間圧延を施し
たとしても再結晶組織に悪影響を与え均一な組織となり
にくい。結晶粒径が不均一な部分では、Ｂの粒界偏析の
程度が偏るため、高温脆化に対しては弱い部分が生じ
る。従って、焼鈍温度は１２００℃以下とすべきであ
る。Such an effect is difficult to realize by a combination of hot rolling and annealing. The reason is that since the texture of the annealed structure of hot rolling is remarkably accumulated, it is difficult to obtain a uniform structure. In the case of this type of alloy steel, the crystal grain size during recrystallization is substantially determined by the holding temperature regardless of the holding time. When annealing is performed at a high temperature of more than 1200 ° C., the crystal grains are coarsened to about 300 μm or more. The coarsened crystal grains have a small grain boundary area as they are, so that high-temperature embrittlement is likely to occur. Further, even if further cold rolling is performed, the recrystallized structure is adversely affected and a uniform structure is hardly obtained. In a portion where the crystal grain size is not uniform, the degree of grain boundary segregation of B is uneven, so that a portion weak against high-temperature embrittlement occurs. Therefore, the annealing temperature should be 1200 ° C. or less.
【００４０】上記の製造条件は、最終圧延において圧下
率３０％以上の冷間圧延を施して作製された圧延したま
まの材料をハニカム加工した場合でも、その後のＮｉろ
う付けにおいて８００〜１２００℃で１秒以上の熱処理
が施される場合にも、同様の効果を有する。上記合金
は、特に板厚０．２ｍｍ以下とした場合に従来材に比較
し優れた耐酸化性と耐高温脆化性が得られ、排ガスコン
バーター用のメタルハニカムとして最適な材料となる。[0040] The above manufacturing conditions are such that even if the as-rolled material produced by performing cold rolling at a rolling reduction of 30% or more in the final rolling is subjected to honeycomb processing, the subsequent Ni brazing is performed at 800 to 1200 ° C. The same effect is obtained when heat treatment is performed for one second or longer. The above alloy has excellent oxidation resistance and high-temperature embrittlement resistance as compared with conventional materials especially when the thickness is 0.2 mm or less, and is an optimal material as a metal honeycomb for an exhaust gas converter.
【００４１】[0041]
【実施例】つぎに、本発明を実施例に基づいて具体的に
説明する。Next, the present invention will be specifically described based on examples.
【００４２】（実施例１）第１表に本発明鋼と比較鋼
の、板厚方向の平均化学成分を示す。(Example 1) Table 1 shows the average chemical composition in the thickness direction of the steel of the present invention and the comparative steel.
【００４３】本発明合金１４、１８と比較合金８、１０
は、適切な組成のＦｅ−Ｃｒ−Ａｌ合金板にＡｌをメッ
キし、不活性ガス中で拡散処理することにより第１表に
示す目標組成の合金板を得、圧延率５０％の冷間圧延を
行って板厚５０μｍとし、９５０℃で１分の光輝焼鈍を
行って製造した。上記４種以外の合金は、真空溶解によ
り溶製され、１２００〜９００℃の温度域で圧下率の合
計が８０％の熱間圧延、９５０℃での焼鈍、圧延率８８
％の冷間圧延後、９５０℃、３０秒の焼鈍を行い、さら
に冷間圧延と焼鈍を繰り返して板厚５０μｍにしたあと
９５０℃で１分の光輝焼鈍を行って製造した。The alloys 14 and 18 of the present invention and the comparative alloys 8 and 10
Means that an Fe-Cr-Al alloy plate having an appropriate composition is plated with Al and subjected to a diffusion treatment in an inert gas to obtain an alloy plate having a target composition shown in Table 1. To a plate thickness of 50 μm, and subjected to bright annealing at 950 ° C. for 1 minute. Alloys other than the above four types are melted by vacuum melting, and hot-rolled with a total reduction of 80% in a temperature range of 1200 to 900 ° C, annealing at 950 ° C, and a rolling rate of 88.
%, Cold annealing was performed at 950 ° C. for 30 seconds, cold rolling and annealing were repeated to obtain a sheet thickness of 50 μm, and then bright annealing was performed at 950 ° C. for 1 minute.
【００４４】以上の供試材について以下の試験を行っ
た。供試材の耐酸化寿命の評価は、ＬａとＺｒの複合含
有による相乗効果によって寿命が延びたことを確認する
意味を含め、Ｌａ、Ｚｒ以外の成分をそのままにしてＬ
ａまたはＺｒを単独含有した比較材を製造して耐酸化寿
命を測定し、その寿命の和に対して複合含有材の寿命が
何倍になっているかを耐酸化寿命比として評価した。The following tests were conducted on the above test materials. The evaluation of the oxidation resistance life of the test material was carried out by including the components other than La and Zr as they were, including the purpose of confirming that the life was extended by the synergistic effect of the composite inclusion of La and Zr.
A comparative material containing only a or Zr was manufactured, and the oxidation resistance life was measured, and how many times the life of the composite-containing material was longer than the sum of the life was evaluated as an oxidation life resistance ratio.
【００４５】ここで、耐酸化寿命とは、前記の板厚５０
μｍのＢＡ箔を１２００℃、大気解放下で酸化時間と重
量変化の関係を求め、重量変化が２．０mg/cm2となった
時点の総酸化時間で定義した。Here, the oxidation resistance life is defined as the thickness 50
The relationship between the oxidation time and the weight change of the BA foil of μm at 1200 ° C. and in the atmosphere was determined, and defined as the total oxidation time when the weight change reached 2.0 mg / cm 2 .
【００４６】また、Ａｌ含有量が４重量％未満の供試材
については、０．００５ｗｔ％Ｃ、０．００５ｗｔ％
Ｎ、１８ｗｔ％Ｃｒ、３ｗｔ％Ａｌ、０．０８ｗｔ％Ｌ
ａ、０．０６ｗｔ％Ｔｉ、０．１ｗｔ％Ｓｉ、０．１ｗ
ｔ％Ｍｎを含有し残部Ｆｅおよび不可避的不純物よりな
る合金鋼の耐酸化寿命を基準とした場合の供試材の耐酸
化寿命比を絶対耐酸化寿命比と定義した。For the test material having an Al content of less than 4% by weight, 0.005 wt% C, 0.005 wt%
N, 18 wt% Cr, 3 wt% Al, 0.08 wt% L
a, 0.06 wt% Ti, 0.1 wt% Si, 0.1 w
The ratio of the oxidation life of the test sample to the oxidation life of the alloy steel containing t% Mn and the balance of Fe and inevitable impurities was defined as the absolute oxidation life ratio.
【００４７】Ａｌ含有量が４重量％以上の供試材につい
ては、０．００５ｗｔ％Ｃ、０．００５ｗｔ％Ｎ、２０
ｗｔ％Ｃｒ、５ｗｔ％Ａｌ、０．０８ｗｔ％Ｌａ、０．
０６ｗｔ％Ｔｉ、０．１ｗｔ％Ｓｉ、０．２ｗｔ％Ｍｎ
を含有し残部Ｆｅおよび不可避的不純物よりなる合金鋼
の耐酸化寿命を、基準とした場合の供試材の耐酸化寿命
比を絶対耐酸化寿命比と定義し、評価の指標とした。For the test material having an Al content of 4% by weight or more, 0.005 wt% C, 0.005 wt% N, 20 wt%
wt% Cr, 5 wt% Al, 0.08 wt% La, 0.1 wt%
06 wt% Ti, 0.1 wt% Si, 0.2 wt% Mn
The ratio of the oxidation life of the test material with respect to the oxidation life of the alloy steel containing Fe and the balance of Fe and unavoidable impurities was defined as an absolute oxidation life ratio, which was used as an evaluation index.
【００４８】耐高温脆化性は、大気中での繰り返し酸化
試験とエンジンベンチによる熱衝撃試験の２種類の試験
方法で評価した。大気中での繰り返し酸化試験は材料の
スクリーニングを行うために、またエンジンベンチによ
る熱衝撃試験はさらに材料の厳しい評価を行うために実
施した。The high-temperature embrittlement resistance was evaluated by two types of test methods: a repeated oxidation test in the atmosphere and a thermal shock test using an engine bench. The repeated oxidation test in the atmosphere was performed to screen the material, and the thermal shock test using the engine bench was performed to perform a more severe evaluation of the material.
【００４９】大気中での繰り返し酸化試験には、各供試
材の板厚５０μｍ箔で製造した平板と波板を巻きあげて
Ｎｉろう付けを施して作製したハニカムを用いた。そし
て、Ａｌ含有量が４重量％以上の供試材に対しては１１
００℃までの昇温と常温までの降温を、またＡｌ含有量
が４重量％未満の供試材に対しては９００℃までの昇温
と常温までの降温を繰り返して行った。For the repeated oxidation test in the atmosphere, a honeycomb prepared by winding a flat plate and a corrugated plate made of a 50 μm-thick foil of each test material and subjecting it to Ni brazing was used. And, for a test material having an Al content of 4% by weight or more, 11
The temperature was raised to 00 ° C. and lowered to room temperature, and for the test material having an Al content of less than 4% by weight, the temperature was raised to 900 ° C. and the temperature was lowered to room temperature.
【００５０】また、エンジンベンチによる熱衝撃試験に
は、同じくろう付けまで完了したハニカムに、さらにγ
−Ａｌ2 Ｏ3 と触媒金属を担持させたものを用いた。そ
して、エンジンのマニホールド位置にハニカムを設置し
て、ハニカムの中心で測温した場合に、Ａｌ含有量が４
重量％以上の供試材に対しては最高１１００℃、またＡ
ｌ含有量が４重量％未満の供試材に対しては最高９００
℃とし、最低３００℃の短時間サイクルを繰り返すこと
により行った。このとき、高温から３００℃までの冷却
過程は、エンジンブレーキ状態としてハニカムが短時間
で急速に冷却されるように調整した。Further, in a thermal shock test using an engine bench, a honeycomb which was also completed up to brazing, and γ
A material carrying -Al 2 O 3 and a catalyst metal was used. When the honeycomb was installed at the manifold position of the engine and the temperature was measured at the center of the honeycomb, the Al content was 4%.
1100 ° C max.
up to 900 for test material with l content less than 4% by weight
C. and a short cycle of at least 300.degree. C. was repeated. At this time, the cooling process from the high temperature to 300 ° C. was adjusted so that the honeycomb was rapidly cooled in a short time in an engine braking state.
【００５１】耐高温脆化性の評価は、上記２種類の試験
において従来材が割れを生じた繰り返し回数の２倍の回
数まで試験を行い、試験後の解体調査によりハニカム箔
の割れの有無により○×で評価した。さらに、耐高温脆
化性の向上をより定量的に評価するために、上記２種類
の試験を数回行い、破損を生じるまでの平均繰り返し回
数を求め、耐酸化性の評価の基準として用いた１８Ｃｒ
−３Ａｌ合金鋼と２０Ｃｒ−５Ａｌ合金を、供試材のＡ
ｌ含有量に応じて割れを生じた平均繰り返し回数との比
をとって耐高温脆化性比とした。The evaluation of high-temperature embrittlement resistance was carried out up to twice the number of repetitions in which the conventional material cracked in the above two types of tests. ×× was evaluated. Furthermore, in order to more quantitatively evaluate the improvement in high-temperature embrittlement resistance, the above two types of tests were performed several times, and the average number of repetitions until breakage was obtained was used as a standard for evaluation of oxidation resistance. 18Cr
-3Al alloy steel and 20Cr-5Al alloy, A
The ratio to the average number of repetitions at which cracks occurred according to the 1 content was taken as the high-temperature embrittlement resistance ratio.
【００５２】第２表に本発明例と比較例の耐酸化寿命
比、絶対耐酸化寿命比、耐高温脆化性評価のために行っ
た２種類の試験の試験後のハニカム破損の有無、耐高温
脆化性比、そして備考欄に製造性を示した。Table 2 shows the ratio of oxidation life resistance, the ratio of absolute oxidation life resistance, and the existence or non-existence of honeycomb breakage after the two types of tests performed to evaluate the resistance to oxidation life and the resistance to high temperature embrittlement. The high temperature embrittlement ratio and the remarks column indicate the manufacturability.
【００５３】第３表の比較鋼において、アンダーライン
は本発明の範囲外を示す。In the comparative steels shown in Table 3, the underlines are outside the scope of the present invention.
【００５４】比較鋼のうち、Ｎｏ．５はＬａ含有量、Ｎ
ｏ．６はＬａ含有量およびＺｒ含有量、Ｎｏ．７はＣｒ
含有量、Ｎｏ．８はＡｌ含有量がそれぞれ本発明の範囲
を超えているために熱間圧延ができず、箔まで加工でき
なかったものである。Among the comparative steels, No. 5 is La content, N
o. No. 6 is La content and Zr content. 7 is Cr
Content, No. In No. 8, hot rolling could not be performed because the Al content exceeded the range of the present invention, and foil could not be processed.
【００５５】また、比較鋼のうち、Ｎｏ．１６はＬａを
除くランタノイド含有量、Ｎｏ．１７はＹ含有量、Ｎ
ｏ．１８はＨｆ含有量、Ｎｏ．１９はＴｉ含有量がそれ
ぞれ本発明の範囲を超えているために熱間圧延ができ
ず、箔まで加工できなかったものである。Further, among the comparative steels, No. No. 16 is a lanthanoid content excluding La; 17 is Y content, N
o. No. 18 is the Hf content. In No. 19, hot rolling could not be performed and Ti could not be processed because the Ti content exceeded the range of the present invention.
【００５６】また、比較鋼１〜４と９〜１５、２０〜２
２はエンジンベンチの熱衝撃試験において耐酸化性が十
分でないために異常酸化を起こしたり高温脆化したりし
てハニカムが破損している。Comparative steels 1-4 and 9-15, 20-2
In No. 2, the honeycomb was damaged due to abnormal oxidation or high-temperature embrittlement due to insufficient oxidation resistance in a thermal shock test of an engine bench.
【００５７】さらに、比較鋼２３〜２５はＢを含有して
はいるが同時にＴｉを本発明範囲を超えて含有している
ため耐高温脆化性に劣り、より厳しいエンジンベンチに
よる熱衝撃試験ではハニカムが破損している。Furthermore, the comparative steels 23 to 25 contain B, but at the same time, contain Ti exceeding the scope of the present invention, so that they are inferior in high-temperature embrittlement resistance. Honeycomb is damaged.
【００５８】これに対し本発明鋼は、より厳しいベンジ
ンベンチによる熱衝撃試験でもハニカムの破損がなく、
かつ耐酸化寿命比および絶対耐酸化寿命比がすべて２．
０以上であり、耐久性に優れた触媒コンバーター用材料
であることがわかる。On the other hand, the steel of the present invention has no honeycomb breakage even in a more severe thermal shock test using a benzene bench.
In addition, the oxidation life ratio and the absolute oxidation life ratio are all 2.
0 or more, indicating that the material is a catalytic converter material having excellent durability.
【００５９】[0059]
【表１】 [Table 1]
【００６０】[0060]
【表２】 [Table 2]
【００６１】[0061]
【表３】 [Table 3]
【００６２】[0062]
【表４】 [Table 4]
【００６３】[0063]
【表５】 [Table 5]
【００６４】[0064]
【表６】 [Table 6]
【００６５】（実施例２）第３表に示す本発明の合金
Ａ、Ｂ、Ｃについて、耐高温脆化性に及ぼす製造条件の
影響を明らかとするために、次に示すＩ〜IVの４種類の
製造条件で箔を作製した。Example 2 For the alloys A, B, and C of the present invention shown in Table 3, in order to clarify the influence of the manufacturing conditions on the high-temperature embrittlement resistance, Foil was produced under various manufacturing conditions.
【００６６】＜製造条件＞ Ｉ）真空溶解により溶製し、１２００〜９００℃の温度
域で圧下率の合計が８０％の熱間圧延、９５０℃での焼
鈍、圧下率８８％の冷間圧延後、９５０℃、１分の焼鈍
を行い、さらに冷間圧延と同じ９５０℃の焼鈍を繰り返
して板厚５０μｍにしたＢＡ材。これは本発明の製造方
法である。 II）真空溶解により溶製し、１２００〜９００℃の温度
域で圧下率の合計が８０％の熱間圧延、９５０℃での焼
鈍を行った後、研削と電解研磨によって板厚６５μｍと
し、圧延率２３％の冷間圧延焼鈍と９５０℃、１分の光
輝焼鈍を行って板厚５０μｍとしたＢＡ材。これは圧下
率が本発明の範囲より小である。 III ）真空溶解により溶製し、１２００〜９００℃の温
度域で圧下率の合計が８０％の熱間圧延、９５０℃での
焼鈍、圧下率８８％の冷間圧延後、７５０℃、１分の焼
鈍を行い、さらに冷間圧延と同じ７５０℃の焼鈍を繰り
返して板厚５０μｍにしたＢＡ材。これは焼鈍温度が本
発明の範囲より小である。 IV）真空溶解により溶製し、１２００〜９００℃の温度
域で圧下率の合計が８０％の熱間圧延、９５０℃での焼
鈍、圧下率８８％の冷間圧延後、１２５０℃、１分の焼
鈍を行い、さらに冷間圧延と同じ１２５０℃の焼鈍を繰
り返して板厚５０μｍにしたＢＡ材。これは焼鈍温度が
本発明の範囲より大である。<Manufacturing Conditions> I) Melting by vacuum melting, hot rolling with a total reduction of 80% in a temperature range of 1200 to 900 ° C., annealing at 950 ° C., cold rolling with a reduction of 88% Thereafter, annealing is performed at 950 ° C. for 1 minute, and annealing at 950 ° C., which is the same as that of cold rolling, is repeated to obtain a BA material having a thickness of 50 μm. This is the manufacturing method of the present invention. II) Melting by vacuum melting, hot rolling with a total reduction of 80% in a temperature range of 1200 to 900 ° C., annealing at 950 ° C., and grinding and electrolytic polishing to a plate thickness of 65 μm. A BA material having a thickness of 50 μm by performing cold rolling annealing at a rate of 23% and bright annealing at 950 ° C. for 1 minute. This means that the rolling reduction is smaller than the scope of the present invention. III) Melting by vacuum melting, hot rolling at a total reduction of 80% in a temperature range of 1200 to 900 ° C, annealing at 950 ° C, cold rolling at a rolling reduction of 88%, 750 ° C for 1 minute BA material obtained by performing annealing at 750 ° C., which is the same as cold rolling, to obtain a sheet thickness of 50 μm. This is because the annealing temperature is lower than the scope of the present invention. IV) Melting by vacuum melting, hot rolling with a total reduction of 80% in a temperature range of 1200 to 900 ° C, annealing at 950 ° C, cold rolling with a rolling reduction of 88%, 1250 ° C for 1 minute BA material obtained by performing annealing at 1250 ° C., which is the same as cold rolling, to obtain a sheet thickness of 50 μm. This is because the annealing temperature is higher than the scope of the present invention.
【００６７】第４表に、耐高温脆化性に及ぼす各製造条
件の影響を調査した結果を示した。第４表より、製造工
程において、圧下率３０％以上の冷間圧延を施したのち
８００〜１２００℃の範囲で焼鈍を行った本発明例Ｉ
は、耐高温脆化比が５以上になっているが、この条件を
満たさないII、III 、IVの場合には、４．５以下となっ
ている。従って、本発明の方法によりＢの耐高温脆化性
をより発揮させることができることがわかる。Table 4 shows the results of investigating the influence of each manufacturing condition on the high-temperature embrittlement resistance. As shown in Table 4, in the manufacturing process, the present invention example I was subjected to cold rolling at a rolling reduction of 30% or more and then annealing at 800 to 1200 ° C.
Has a high-temperature embrittlement resistance of 5 or more, but in the case of II, III and IV that do not satisfy this condition, it has a value of 4.5 or less. Therefore, it is understood that the high temperature embrittlement resistance of B can be further exhibited by the method of the present invention.
【００６８】[0068]
【表７】 [Table 7]
【００６９】[0069]
【表８】 [Table 8]
【００７０】[0070]
【発明の効果】本発明は、Ｆｅ−Ｃｒ−Ａｌ合金のＬａ
とＺｒ含有量の比を限定することにより、従来考えられ
ていたＬａあるいはＺｒの単独含有の耐酸化寿命の単純
な和ではなく、それぞれの寿命の和以上の耐酸化寿命を
実現させることができるとともに、Ｂを適量含有させる
ことにより、厳しい熱衝撃によっても破損しない触媒コ
ンバーター用メタルハニカムを提供することができる。
また、本発明により、特に９００℃を超える高温で優れ
た耐酸化性と耐久性を示す材料を提供できる。本発明の
合金は、自動車などの触媒コンバーター用材料をはじめ
とした、耐熱用材料としての最適な合金であり、特に
０．２ｍｍ以下の箔として優れた性能を示す。According to the present invention, the La-Fe-Cr-Al alloy
By limiting the ratio of the Zr content to the Zr content, it is possible to realize not only the simple sum of the anti-oxidation life of La or Zr alone contained conventionally, but also the anti-oxidation life which is equal to or longer than the sum of the respective life. In addition, by containing an appropriate amount of B, it is possible to provide a metal honeycomb for a catalytic converter that is not damaged by severe thermal shock.
Further, according to the present invention, a material exhibiting excellent oxidation resistance and durability especially at a high temperature exceeding 900 ° C. can be provided. The alloy of the present invention is an optimal alloy as a heat-resistant material including a material for a catalytic converter of an automobile or the like, and particularly exhibits excellent performance as a foil of 0.2 mm or less.
【図１】 ０．００５ｗｔ％Ｃ、０．００５ｗｔ％Ｎ、
２０ｗｔ％Ｃｒ、５ｗｔ％Ａｌ、０．２ｗｔ％Ｓｉ、
０．２ｗｔ％Ｍｎ、残部Ｆｅ、Ｌａ、Ｚｒおよび不可避
的不純物よりなる合金においてＬａ単独含有、Ｚｒ単独
含有およびＬａとＺｒの複合含有した場合の１２００
℃、大気中における５０μｍ箔の酸化時間に対する重量
変化を示したグラフである。FIG. 1: 0.005 wt% C, 0.005 wt% N,
20 wt% Cr, 5 wt% Al, 0.2 wt% Si,
An alloy containing 0.2 wt% Mn, the balance Fe, La, Zr, and unavoidable impurities, when containing only La, containing only Zr, and containing a complex of La and Zr.
It is a graph which showed the weight change with respect to the oxidation time of 50 micrometers foil in air | atmosphere and the air.
【図２】 ０．００５ｗｔ％Ｃ、０．００５ｗｔ％Ｎ、
２０ｗｔ％Ｃｒ、５ｗｔ％Ａｌ、０．２ｗｔ％Ｓｉ、
０．２ｗｔ％Ｍｎ、残部Ｆｅおよび不可避的不純物より
なる合金の板厚５０μｍの箔の耐酸化寿命比と〔Ｚｒ重
量％〕／〔Ｌａ重量％〕の値との関係を、Ｌａ：０．０
１〜０．２重量％、Ｚｒ：０．０１〜１．０重量％の範
囲で示したグラフである。FIG. 2 shows 0.005 wt% C, 0.005 wt% N,
20 wt% Cr, 5 wt% Al, 0.2 wt% Si,
The relation between the oxidation resistance life ratio of the foil having a thickness of 50 μm and the value of [Zr wt%] / [La wt%] of 0.2 wt% Mn, the balance of Fe and inevitable impurities was La: 0.0
It is the graph shown in the range of 1-0.2 weight% and Zr: 0.01-1.0 weight%.
【図３】 ０．００５ｗｔ％Ｃ、０．００５ｗｔ％Ｎ、
２０ｗｔ％Ｃｒ、５ｗｔ％Ａｌ、０．１ｗｔ％Ｌａ、
０．１ｗｔ％Ｚｒ、０．２５ｗｔ％Ｓｉ、０．４ｗｔ％
Ｍｎ、残部Ｆｅおよび不可避的不純物よりなる合金に、
Ｂを含有させた時の耐高温脆化性比に及ぼすＢ含有量の
影響を示したグラフである。FIG. 3 shows 0.005 wt% C, 0.005 wt% N,
20 wt% Cr, 5 wt% Al, 0.1 wt% La,
0.1 wt% Zr, 0.25 wt% Si, 0.4 wt%
An alloy consisting of Mn, balance Fe and inevitable impurities,
4 is a graph showing the effect of the B content on the high-temperature embrittlement resistance ratio when B is contained.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ Ｃ２２Ｃ 38/18 Ｃ２２Ｃ 38/18 (72)発明者 冨 樫 房 夫 千葉県千葉市中央区川崎町１番地 川崎 製鉄株式会社技術研究本部内 (56)参考文献 特開 平４−350148（ＪＰ，Ａ) 特開 平４−235255（ＪＰ，Ａ) 特開 平２−192801（ＪＰ，Ａ) (58)調査した分野(Int.Cl.7，ＤＢ名) C22C 38/00 - 38/60 B01J 32/00 B01J 35/04 301 C21D 8/02 C21D 9/46 ──────────────────────────────────────────────────続 き Continuing on the front page (51) Int.Cl. 7 Identification code FI C22C 38/18 C22C 38/18 (72) Inventor Fusao Togashi 1 Kawasaki-cho, Chuo-ku, Chiba-shi, Chiba Kawasaki Steel Engineering Co., Ltd. (56) References JP-A-4-350148 (JP, A) JP-A-4-235255 (JP, A) JP-A-2-192801 (JP, A) (58) Fields studied (Int. Cl 7, DB name) C22C 38/00 -. 38/60 B01J 32/00 B01J 35/04 301 C21D 8/02 C21D 9/46
Claims (8)
び耐高温脆化性に優れたＦｅ−Ｃｒ−Ａｌ合金。1. C: 0.05% by weight or less, N: 0.02% by weight or less, Si: 0.5% by weight or less, Mn: 1.0% by weight or less, Cr: 10 to 28% by weight, Al 1 to 10% by weight, B: 0.0003 to 0.010% by weight, La: 0.01 to 0.20% by weight, Zr: 0.01 to 1.0% by weight, And satisfying the formula (I), 0.1 ≦ [Zr wt%] / [La wt%] ≦ 20 (I) Oxidation resistance and high temperature embrittlement resistance consisting of the balance of Fe and unavoidable impurities Excellent Fe-Cr-Al alloy.
る請求項１に記載のＦｅ−Ｃｒ−Ａｌ合金。2. The Fe—Cr—Al alloy according to claim 1, further comprising less than 0.05% by weight of Ti.
れ０．０５重量％以下含有する請求項１または２に記載
のＦｅ−Ｃｒ−Ａｌ合金。3. The Fe—Cr—Al alloy according to claim 1, wherein one or two of Ca and Mg are contained in an amount of 0.05% by weight or less, respectively.
３のいずれかに記載のＦｅ−Ｃｒ−Ａｌ合金。4. A lanthanoid excluding La: 0.2% by weight or less Y: 0.5% by weight or less Hf: 0.3% by weight or less
3. The Fe—Cr—Al alloy according to any one of 3.
種以上を合計で１．０重量％以下含有する請求項１〜４
のいずれかに記載のＦｅ−Ｃｒ−Ａｌ合金。5. One or two selected from Nb, V and Ta
A total of 1.0% by weight or less of at least one species.
The Fe-Cr-Al alloy according to any one of the above.
ｒ−Ａｌ合金を圧延した０．２ｍｍ以下の箔を用いて組
み立てられた排ガス浄化触媒コンバーター用触媒担体。6. The Fe—C according to claim 1, wherein
A catalyst carrier for an exhaust gas purifying catalytic converter assembled using a foil of 0.2 mm or less obtained by rolling an r-Al alloy.
ｒ−Ａｌ合金のスラブに熱間圧延を行った後で焼鈍を行
い、さらに圧下率３０％以上の冷間圧延と８００〜１２
００℃の温度での焼鈍を１回以上行うことを特徴とする
耐酸化性および耐高温脆化性に優れたＦｅ−Ｃｒ−Ａｌ
合金箔の製造方法。7. The Fe—C according to claim 1, wherein
After hot rolling is performed on the slab of the r-Al alloy, annealing is performed, and cold rolling with a reduction ratio of 30% or more and 800 to 12 are performed.
Fe-Cr-Al excellent in oxidation resistance and high-temperature embrittlement resistance, wherein annealing at a temperature of 00C is performed at least once.
Manufacturing method of alloy foil.
金よりなる素地板に、Ａｌまたはさらに所定の元素を含
有するＡｌ合金を表面に付着させ、不活性あるいは還元
性雰囲気内で加熱して、前記付着成分を前記素地板中に
拡散させて、請求項１〜５に記載の合金組成とした合金
板に、さらに圧下率３０％以上の冷間圧延と８００〜１
２００℃の温度での焼鈍を１回以上行うことを特徴とす
る耐酸化性および耐高温脆化性に優れたＦｅ−Ｃｒ−Ａ
ｌ合金箔の製造方法。8. A substrate made of an Fe—Cr alloy or an Fe—Cr—Al alloy, wherein Al or an Al alloy containing a predetermined element is adhered to the surface and heated in an inert or reducing atmosphere. An alloy sheet having the alloy composition according to any one of claims 1 to 5, wherein the adhesion component is diffused into the base sheet, and further cold-rolled at a rolling reduction of 30% or more to 800-1.
Fe-Cr-A excellent in oxidation resistance and high-temperature embrittlement resistance, characterized in that annealing at a temperature of 200 ° C is performed at least once.
1 Manufacturing method of alloy foil.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP13883092A JP3200160B2 (en) | 1991-05-29 | 1992-05-29 | Fe-Cr-Al alloy excellent in oxidation resistance and high-temperature embrittlement resistance, catalyst carrier using the same, and method for producing alloy foil |
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP12436391 | 1991-05-29 | ||
| JP12436191 | 1991-05-29 | ||
| JP3-124363 | 1991-10-31 | ||
| JP3-286071 | 1991-10-31 | ||
| JP3-124361 | 1991-10-31 | ||
| JP28607191 | 1991-10-31 | ||
| JP13883092A JP3200160B2 (en) | 1991-05-29 | 1992-05-29 | Fe-Cr-Al alloy excellent in oxidation resistance and high-temperature embrittlement resistance, catalyst carrier using the same, and method for producing alloy foil |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH05202449A JPH05202449A (en) | 1993-08-10 |
| JP3200160B2 true JP3200160B2 (en) | 2001-08-20 |
Family
ID=27471028
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP13883092A Expired - Lifetime JP3200160B2 (en) | 1991-05-29 | 1992-05-29 | Fe-Cr-Al alloy excellent in oxidation resistance and high-temperature embrittlement resistance, catalyst carrier using the same, and method for producing alloy foil |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3200160B2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9028625B2 (en) | 2004-10-21 | 2015-05-12 | Nippon Steel Materials Co., Ltd. | High Al-content steel sheet excellent in workability and method of production of same |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4604446B2 (en) * | 2000-06-30 | 2011-01-05 | Ｊｆｅスチール株式会社 | Fe-Cr-Al alloy foil and method for producing the same |
| CN101985130A (en) * | 2010-11-16 | 2011-03-16 | 苏州有色金属研究院有限公司 | Method for casting and rolling 1235-alloy aluminum foil blank |
| CN104870675B (en) * | 2012-12-17 | 2017-10-03 | 杰富意钢铁株式会社 | Stainless steel plate and stainless steel foil |
| AU2015359265B2 (en) | 2014-12-11 | 2021-01-21 | Sandvik Intellectual Property Ab | A ferritic alloy |
| JP6504973B6 (en) * | 2015-08-28 | 2019-05-29 | 日鉄ステンレス株式会社 | Al-containing ferritic stainless steel excellent in sulfide corrosion resistance and method for producing the same |
| CN107385307B (en) * | 2017-06-13 | 2019-07-16 | 东北大学 | A kind of preparation method of the Fe-Cr-Al electrothermal alloy cold-reduced sheet containing yttrium |
-
1992
- 1992-05-29 JP JP13883092A patent/JP3200160B2/en not_active Expired - Lifetime
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9028625B2 (en) | 2004-10-21 | 2015-05-12 | Nippon Steel Materials Co., Ltd. | High Al-content steel sheet excellent in workability and method of production of same |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH05202449A (en) | 1993-08-10 |
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