JPH06116686A - Fe-cr-al alloy excellent in oxidation resistance and foil thereof - Google Patents
Fe-cr-al alloy excellent in oxidation resistance and foil thereofInfo
- Publication number
- JPH06116686A JPH06116686A JP4267642A JP26764292A JPH06116686A JP H06116686 A JPH06116686 A JP H06116686A JP 4267642 A JP4267642 A JP 4267642A JP 26764292 A JP26764292 A JP 26764292A JP H06116686 A JPH06116686 A JP H06116686A
- Authority
- JP
- Japan
- Prior art keywords
- weight
- oxidation resistance
- alloy
- less
- foil
- 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.)
- Granted
Links
- 230000003647 oxidation Effects 0.000 title claims abstract description 58
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 58
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 title claims abstract description 17
- 239000011888 foil Substances 0.000 title claims abstract description 17
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 31
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 25
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 15
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 13
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 10
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 7
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910045601 alloy Inorganic materials 0.000 claims description 31
- 239000000956 alloy Substances 0.000 claims description 31
- 229910052735 hafnium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910000838 Al alloy Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000005096 rolling process Methods 0.000 claims description 2
- 229910017112 Fe—C Inorganic materials 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 abstract description 9
- 229910052748 manganese Inorganic materials 0.000 abstract description 8
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 230000000694 effects Effects 0.000 description 24
- 239000000463 material Substances 0.000 description 18
- 239000007789 gas Substances 0.000 description 8
- 238000000137 annealing Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000006104 solid solution Substances 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- 229910000851 Alloy steel Inorganic materials 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000002159 abnormal effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 150000004767 nitrides Chemical class 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 239000007769 metal material Substances 0.000 description 2
- 229910052761 rare earth metal Inorganic materials 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- 229910001122 Mischmetal Inorganic materials 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 210000001787 dendrite Anatomy 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000003779 heat-resistant material Substances 0.000 description 1
- 238000005098 hot rolling Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000001247 metal acetylides Chemical class 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
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
Abstract
Description
【０００１】[0001]
【産業上の利用分野】本発明は、排ガスコンバーターな
どの触媒担体用金属材料を代表とする耐酸化性合金鋼お
よびその箔に係る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an oxidation resistant alloy steel represented by a metal material for a catalyst carrier such as an exhaust gas converter and a foil thereof.
【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。2. Description of the Related Art An exhaust gas purifying catalytic converter produces NO x , HC and C produced 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 converter temperature rises. Recently, in order to improve the efficiency of the catalytic reaction, there are many cases where a converter is installed near the combustion environment to cause the catalytic reaction in high-temperature exhaust gas. Due to repeated cooling, it receives a very large thermal shock.
【０００３】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。As a material for catalytic converters used under such extremely severe conditions, since ceramics are vulnerable to thermal shock and cannot withstand use, Fe is excellent in oxidation resistance.
A metal material such as -Cr-Al alloy is used.
【０００４】Ｆｅ−Ｃｒ−Ａｌ合金としては特開昭４８
−４１９１８号、特開昭５８−１７７４３７号、特公平
２−５８３４０号、特公昭６２−１４６２６号、特開昭
６３−２１８２５３号、特開昭６３−２４８４４７号、
特開昭６４−１１９４６号、特開昭６４−３０６５３
号、特開平１−１１５４５５号、特開平２−３０３６０
５号、特開平３−３６２４１号等が開示されている。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４８−４１９１８号、特開昭５８−１７７４
３７号および特公平２−５８３４０号では十分な耐酸化
性が得られない。特開昭６３−２１８２５３号、特開昭
６３−２４８４４７号、特開平２−３０３６０５号、特
公昭６２−１４６２６号、特開昭６４−３０６５３号お
よび特開平１−１１５４５５号は、ＲＥＭとしてＣｅを
含有したミッシュメタルを主に添加しており、これらの
材料は耐酸化性が十分でない。A Fe-Cr-Al alloy is disclosed in Japanese Patent Application Laid-Open No. 48
-41918, JP-A-58-177437, JP-B-2-58340, JP-B-62-14626, JP-A-63-218253, JP-A-63-248447,
JP-A-64-11946, JP-A-64-30653
JP-A-1-115455, JP-A-2-30360
No. 5, JP-A-3-36241 and the like are disclosed. However, the materials shown therein have the following problems. JP-A-48-41918, JP-A-58-1774
In No. 37 and Japanese Patent Publication No. 2-58340, sufficient oxidation resistance cannot be obtained. In JP-A-63-218253, JP-A-63-248447, JP-A-2-303605, JP-B-62-14626, JP-A-64-30653 and JP-A-1-115455, Ce is used as REM. The contained misch metal is mainly added, and these materials have insufficient oxidation resistance.
【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メタルハニカム材とし
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てメタルハニカムは破損してしま
う。Therefore, when these materials are used as a metal honeycomb material for a catalytic converter as a foil having a plate thickness of 0.2 mm or less, the oxidation resistance is insufficient and abnormal oxidation occurs in a short time to cause a metal honeycomb. Will be damaged.
【０００６】[0006]
【発明が解決しようとする課題】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が不充分であり、材料全体が酸化物
に変化する、いわゆる異常酸化を起こすなど使用に耐え
ないのが実情である。本発明は、上述した従来技術の欠
点を解消した高温での耐酸化性に優れたＦｅ−Ｃｒ−Ａ
ｌ系合金および板厚が０．２ｍｍ以下とした合金箔を提
供することを目的としている。As described above, the conventional Fe-Cr-Al alloy has a high temperature of 0.2 mm at a high temperature.
As a material for the catalytic converter used as the following alloy foil, the oxidation resistance is insufficient, and the fact is that it cannot withstand use such as the entire material being converted into an oxide, so-called abnormal oxidation. The present invention solves the above-mentioned drawbacks of the prior art and is excellent in oxidation resistance at high temperature Fe-Cr-A.
It is an object of the present invention to provide an l-based alloy and an alloy foil having a plate thickness of 0.2 mm or less.
【０００７】[0007]
【課題を解決されるための手段】すなわち、本発明によ
れば、Ｃ：０．０５重量％以下、 Ｎ：０．０２重量
％以下、Ｓｉ：１．０重量％以下、 Ｍｎ：１．５重
量％以下、Ｓ：０．０１重量％以下、 Ｔｉ，Ｎｂ：
合計で０．０５重量％以下、Ｃｅ：０．０１重量％以
下、 Ｃｒ：１０〜２８重量％Ａｌ：１〜６重量％、
Ｃａ：０．０００３〜０．０３重量％を含有し、
さらにＬａおよびＺｒがＬａ：０．０１〜０．２０重量
％、 Ｚｒ：０．０１〜１．０重量％ ０．１≦〔Ｚｒ重量％〕／〔Ｌａ重量％」≦２０ ………（Ａ） で、かつ（Ａ）式を満足し、残部Ｆｅおよび不可避的不
純物よりなる、耐酸化性に優れたＦｅ−Ｃｒ−Ａｌ系合
金が提供される。That is, according to the present invention, C: 0.05 wt% or less, N: 0.02 wt% or less, Si: 1.0 wt% or less, Mn: 1.5 Wt% or less, S: 0.01 wt% or less, Ti, Nb:
0.05% by weight or less in total, Ce: 0.01% by weight or less, Cr: 10 to 28% by weight Al: 1 to 6% by weight,
Ca: contains 0.0003 to 0.03% by weight,
Further, La and Zr are La: 0.01 to 0.20 wt%, Zr: 0.01 to 1.0 wt% 0.1 ≦ [Zr wt%] / [La wt% ”≦ 20 ... (A ) And satisfying the formula (A), and comprising the balance Fe and unavoidable impurities and having excellent oxidation resistance, an Fe-Cr-Al-based alloy is provided.
【０００８】本発明の合金は、上記成分に加えて、Ａ１
Ｎの形成の阻止および耐酸化性向上の目的でＶ，Ｔａお
よびＨｆのうち１種または２種以上を合計で１．０重量
％以下含有させてもよい。In addition to the above components, the alloy of the present invention has A1
For the purpose of preventing the formation of N and improving the oxidation resistance, one or more of V, Ta and Hf may be contained in a total amount of 1.0 wt% or less.
【０００９】また本発明の合金は、上記成分に加えて耐
酸化性向上の目的でさらにＹを０．５重量％以下含有し
てもよい。In addition to the above components, the alloy of the present invention may further contain Y in an amount of 0.5% by weight or less for the purpose of improving oxidation resistance.
【００１０】さらに本発明の合金は、上記成分に加えて
耐酸化性向上の目的でＭｇを０．０００５〜０．０３重
量％含有させてもよい。In addition to the above components, the alloy of the present invention may contain 0.0005 to 0.03% by weight of Mg for the purpose of improving oxidation resistance.
【００１１】さらに、上記の合金を０．２ｍｍ以下の箔
とすることにより優れた耐酸化性の効果はより顕著に発
揮される。Further, when the above alloy is a foil having a thickness of 0.2 mm or less, the effect of excellent oxidation resistance is more remarkably exhibited.
【００１２】[0012]
【作用】以下に本発明をさらに詳細に説明する。まず、
本発明で非常に重要な要件である、耐酸化性を向上させ
る（Ａ）式で表されるＬａとＺｒの複合含有およびＣａ
の含有、さらに耐酸化性を劣化されるＴｉ，Ｎｂ，Ｃｅ
の含有について述べる。The present invention will be described in more detail below. First,
A compound of La and Zr represented by the formula (A) for improving the oxidation resistance, which is a very important requirement in the present invention, and Ca.
Content of Ti, Nb, Ce
The inclusion of is described.
【００１３】はじめに本発明者らは、１２００℃での高
温におけるＦｅ−Ｃｒ−Ａｌ系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，Ｈｆ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。First, the present inventors investigated the effect of elements on the oxidation resistance of the Fe-Cr-Al alloy foil at a high temperature of 1200 ° C. As a result, it has been clarified that the combined content of La and Zr has the effect of improving the oxidation resistance, which cannot be achieved by the single inclusion of the elements such as the lanthanoid, which is a rare earth element, Y, and Hf which have been clarified hitherto. became.
【００１４】図１は、重量比にして０．００５％Ｃ，
０．１５％Ｓｉ，０．２％Ｍｎ，２０％Ｃｒ，５％Ａ
ｌ，０．００２％Ｎ，Ｔｉ，Ｎｂ合計で０．０１％未
満，Ｃｅ０．００５％未満で残部Ｆｅおよび不可避的不
純物より成る合金を基本組成とし、さらに、Ｚｒを単独
で０．０７２％含有する合金、Ｌａを単独で０．０９１
％含有する合金、Ｌａ：０．０９１％とＺｒ：０．０７
５％を複合含有する合金、Ｌａ：０．０８９％，Ｚｒ：
０．０７６％，Ｃａ：０．００４２％を複合含有する合
金の、板厚５０μｍの箔に対しての１２００℃、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。ま
た、図中には、実施例の項で定義される耐酸化寿命比の
値も合せて示した。図１より、Ｌａ単独含有、Ｚｒ単独
含有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の複合含有ではそれぞ
れの単独含有で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、単にＬａとＺｒを複合含有
させたとしても双方の耐酸化性改善効果の和になるとす
る従来の考え方を逸脱する新たな発見がある。FIG. 1 shows a weight ratio of 0.005% C,
0.15% Si, 0.2% Mn, 20% Cr, 5% A
1, 0.002% N, Ti, Nb total less than 0.01%, Ce less than 0.005%, the basic composition is an alloy consisting of balance Fe and unavoidable impurities, and further contains 0.072% Zr alone. Alloy, La alone 0.091
% Alloy containing, La: 0.091% and Zr: 0.07
Alloy containing 5% in combination, La: 0.089%, Zr:
It shows the weight change of an alloy containing 0.076% and Ca: 0.0042% in combination with respect to a foil having a plate thickness of 50 μm at 1200 ° C. in the atmosphere for oxidation time. Further, in the figure, the value of the oxidation resistance life ratio defined in the section of Examples is also shown. From FIG. 1, it can be seen that the content of La alone and the content of Zr alone cause a weight increase due to abnormal oxidation in a short time, whereas the composite content of La and Zr causes the increase in the life of each single content by 2%. It can be seen that it has a life more than twice as long. This is a new discovery that deviates from the conventional idea that even if La and Zr are contained in combination, the effect of improving both oxidation resistance is the sum.
【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なった結果、ＬａとＺｒの複
合含有の効果を十分に発揮させるためには含有量を制限
する必要があることがわかった。これは図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の耐
酸化性しか得られないため、ＬａとＺｒの含有量の比は
一定の範囲内にある必要がある。図２は、重量比にし
て、０．００５％Ｃ，０．１５％Ｓｉ，０．２％Ｍｎ，
２０％Ｃｒ，５％Ａｌ，０．００２％Ｎ，０．００１〜
０．００４％Ｃａ，Ｔｉ，Ｎｂ合計で０．０１％未満，
Ｃｅ：０．００５％未満で、さらにＬａ：０．０１〜
０．２％，Ｚｒ０．０１〜１．０％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〕／〔Ｌ
ａ含有量〕の値）の影響を、Ｌａ：０．０１〜０．２重
量％、Ｚｒ：０．０１〜１．０重量％の範囲で調査した
結果である。図２に示すように、ＬａとＺｒの含有量の
間に（Ａ）式の関係がある時に優れた耐酸化性が得られ
ることが判明した。 ０．１≦〔Ｚｒ重量％〕／〔Ｌａ重量％〕≦２０ ………（Ａ）As a result of further detailed investigation on the composite content of La and Zr, the present inventors have found that it is necessary to limit the content in order to fully exert the effect of the composite content of La and Zr. I understood. As can be inferred from FIG. 1, when the content of one of La and Zr is extremely small with respect to the content of the other, only the same oxidation resistance as in the case of single content is obtained. The ratio of the contents of the must be within a certain range. FIG. 2 shows a weight ratio of 0.005% C, 0.15% Si, 0.2% Mn,
20% Cr, 5% Al, 0.002% N, 0.001
0.004% Ca, Ti, Nb total less than 0.01%,
Ce: less than 0.005%, and further La: 0.01-
Effect of Zr on the oxidation resistance life ratio (defined in Examples described later) of a foil having a plate thickness of 50 μm of an alloy containing 0.2% and 0.01 to 1.0% Zr and consisting of balance Fe and unavoidable impurities Ratio of content to La content ([Zr content] / [L
This is the result of investigating the influence of the value of [a content] in the range of La: 0.01 to 0.2% by weight and Zr: 0.01 to 1.0% by weight. As shown in FIG. 2, it was found that excellent oxidation resistance was obtained when the relationship of the formula (A) was found between the contents of La and Zr. 0.1 ≦ [Zr weight%] / [La weight%] ≦ 20 (A)
【００１６】本発明では、耐酸化性に関して（Ａ）式が
最も重量な関係である。すなわち、ＬａとＺｒを含有し
たＦｅ−Ｃｒ−Ａｌ系合金において（Ａ）式を満足する
ことが高温における耐酸化性を改善する画期的な方法で
ある。In the present invention, the formula (A) has the most weight relation with respect to the oxidation resistance. That is, satisfying the formula (A) in the Fe-Cr-Al alloy containing La and Zr is an epoch-making method for improving the oxidation resistance at high temperature.
【００１７】ＬａとＺｒは、（Ａ）式を満足しても含有
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０．０１重量％以上の含有
量で（Ａ）式を満足させればその効果が十分発揮させる
ことができるが、Ｌａは固溶限が小さく、それを越えて
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
間での加工性が著しく劣化させるので、含有量の上限を
０．２０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、逆に耐酸化性が劣化したり熱
間および冷間での加工性を逸するので、含有量の上限を
１．０重量％に限定する必要がある。Even if La and Zr satisfy the formula (A), if the contents are too small, sufficient effects cannot be exhibited. For that purpose, both La and Zr must 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 formula (A) is satisfied, the effect can be sufficiently exerted, but La has a small solid solubility limit, and La is contained beyond the range. Since the metal La and the metal La precipitate at the grain boundaries, the oxidation resistance corresponding to the content cannot be obtained, and the hot and cold workability is significantly deteriorated. Therefore, the upper limit of the content is 0.20% by weight. Need to be limited to. Zr is
If it is contained excessively, an intermetallic compound such as Fe 2 Zr or Fe 3 Zr is formed, so that the oxidation resistance is deteriorated and the workability in hot and cold is lost, so the upper limit of the content is set. It should be limited to 1.0% by weight.
【００１８】さらに本発明者らは、ＬａとＺｒの複合添
加の効果と第３元素の共存の影響を調査した。その結
果、Ｃａの添加が効果があること、Ｔｉ，Ｎｂ，Ｃｅが
きわめて有害であることが判明した。図１より、Ｌａ，
Ｚｒ複合添加鋼に対しさらにＣａを０．００４２％含有
させることにより耐酸化寿命はさらに延び、耐酸化寿命
比にして３．６となっており、Ｃａ添加によって、寿命
が１．６倍延びたことが分かる。Ｃａの共存によるＬ
ａ，Ｚｒ複合添加効果の向上機構については明らかでな
いが、耐酸化性に対してきわめて有害であるＳを無害化
するためと推察される。従って、Ｃａを有効にはたらか
せるためには有害元素Ｓを低い値に抑えることが望まし
い。具体的には、Ｓを０．０１重量％以下に抑えた上に
Ｓ固定のためＣａを最低限０．０００３重量％以上含有
させる必要がある。願わくば、Ｃａの含有量は重量％に
してＳの１．５倍以上が理想的である。しかし、０．０
３重量％を超えて含有させると、デンドライト粒間に偏
析して粒界強度を低下させ、熱間加工性を著しく劣化さ
せるため上限を０．０３重量％ととし、範囲を０．００
０３〜０．０３重量％に限定した。Further, the present inventors investigated the effect of the combined addition of La and Zr and the effect of the coexistence of the third element. As a result, it was found that the addition of Ca was effective and Ti, Nb and Ce were extremely harmful. From FIG. 1, La,
By adding 0.0042% of Ca to the Zr composite-added steel, the oxidation resistance life was further extended, and the oxidation resistance life ratio was 3.6. The addition of Ca extended the life 1.6 times. I understand. L due to the coexistence of Ca
Although the mechanism for improving the effect of the combined addition of a and Zr is not clear, it is presumed that it is for detoxifying S, which is extremely harmful to the oxidation resistance. Therefore, it is desirable to suppress the harmful element S to a low value in order to effectively actuate Ca. Specifically, it is necessary to suppress S to 0.01% by weight or less and to contain Ca at least 0.0003% by weight or more for fixing S. Hopefully, the Ca content is ideally 1.5 times or more of S in weight%. But 0.0
If it is contained in excess of 3% by weight, it segregates between the dendrite grains to lower the grain boundary strength and significantly deteriorate the hot workability, so the upper limit is made 0.03% by weight, and the range is 0.00
It was limited to 03 to 0.03% by weight.
【００１９】また、機構については明らかでないがＴ
ｉ，Ｎｂ，ＣｅはＬａ，Ｚｒ複合添加効果を減少させて
しまう。従って、これらの元素をＬａ，Ｚｒ複合添加の
効果が損なわれない程度に低く抑える必要がある。具体
的には、ＴｉとＮｂは合計で０．０５重量％以下、願わ
くば０．０３重量％以下、Ｃｅは０．０１重量％以下に
抑える必要がある。Although the mechanism is not clear, T
i, Nb and Ce reduce the combined effect of La and Zr. Therefore, it is necessary to suppress these elements to such a low level that the effect of the combined addition of La and Zr is not impaired. Specifically, it is necessary to suppress the total of Ti and Nb to 0.05% by weight or less, preferably 0.03% by weight or less, and Ce to 0.01% by weight or less.
【００２０】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。 Ｃｒ：Ｃｒは、Ａｌの耐酸化性を向上させる効果を助け
る役割を持つばかりでなく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、そ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％を越えて含有させると、靱性およ
び延性が低下し製造性を逸するので範囲を１０〜２８重
量％に限定した。The functions of other alloying elements and the reasons for limiting numerical values will be described below. Cr: Cr is an element that not only plays a role of assisting the effect of improving the oxidation resistance of Al, but also Cr itself has the effect of improving the oxidation resistance, and 10% by weight is sufficient to fully exert those effects. The above contents are required. Cr
The effect of improving the oxidation resistance of increases with the increase of the content,
Particularly, if the content is 18% by weight or more, excellent oxidation resistance can be obtained, but if the content exceeds 28% by weight, toughness and ductility are deteriorated and manufacturability is lost, so the range is limited to 10 to 28% by weight. did.
【００２１】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。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。しかし、１０重量％を越えて含有させる
と、合金鋼の靱性が著しく低くなり冷間圧延で割れを生
じるため上限を１０重量％とし、範囲を１〜１０重量％
とした。Al: Al is an indispensable element for maintaining the oxidation resistance, and becomes a material that can withstand long-term use at high temperature as its content increases. In order to bring out the effect sufficiently, it is necessary to contain at least 1% by weight. However, if the content exceeds 10% by weight, the toughness of the alloy steel is remarkably lowered and cracking occurs in cold rolling, so the upper limit is set to 10% by weight, and the range is 1 to 10% by weight.
And
【００２２】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 a small solid solution limit in ferritic stainless steels and mainly precipitate as carbides and nitrides to deteriorate corrosion resistance.
It significantly reduces the toughness and ductility of the steel sheet. Especially N is A
Not only does it reduce the effective Al (solid solution Al) by forming a nitride with l, but also a huge nitride causes defects during foil production and significantly deteriorates the yield. The upper limits were set to C: 0.05% by weight and N: 0.02% by weight in consideration of the economical and economical melting technique.
【００２３】Ｓｉ，Ｍｎ：ＳｉとＭｎは、Ａｌ脱酸の予
備脱酸材として添加された場合合金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１．０重量％以下、Ｍｎは１．５重量
％以下に限定した。Si, Mn: Si and Mn may remain in the alloy when added as a preliminary deoxidizer for Al deoxidation, but Si reduces the flaking resistance of oxide scale,
Further, since Mn deteriorates the oxidation resistance and the corrosion resistance, it is preferable that both are small, but in view of industrial and economical melting manufacturing technology, Si is 1.0 wt% or less and Mn is 1.5 wt% or less. Limited
【００２４】Ｖ，Ｔａ，Ｈｆ：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。V, Ta, Hf: These elements are AlN
Has the effect of detoxifying N which forms Al and consumes Al and deteriorates oxidation resistance. However, when it is contained in excess, the solid solution amount of these elements increases and conversely deteriorates oxidation resistance and Also, since the workability in cold is deteriorated, the upper limit of the total content is set to 1.0% by weight.
【００２５】Ｙ：Ｙ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。これらの元素はその
効果のために多い方が望ましいが、Ｆｅ−Ｃｒ−Ａｌ合
金に対する固溶限が小さい上に固溶限を越えて含有させ
ると、粒界に析出して加工性を劣化させるため、上限を
０．５０重量％とした。Y: Y has the effect of improving the oxidation resistance by improving the adhesion of the oxide film formed on the Fe-Cr-Al alloy at high temperature. It is desirable that the amount of these elements is large for their effect, but if the solid solution limit to the Fe-Cr-Al alloy is small and if it is contained beyond the solid solution limit, it precipitates at grain boundaries and deteriorates the workability. Therefore, the upper limit is set to 0.50% by weight.
【００２６】Ｍｇ：Ｍｇは、０．０００５重量％以上含
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、０．０３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０．０３重量％とした。Mg: Mg is an element which, when contained in an amount of 0.0005% by weight or more, forms a very dense Al 2 O 3 scale to improve the oxidation resistance, but if it exceeds 0.03% by weight. When it is contained, the manufacturability such as hot ductility is remarkably reduced, so the upper limit was made 0.03% by weight.
【００２７】本発明合金鋼は、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５
０％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。The alloy steel of the present invention is melted by a normal converter method, the composition is adjusted in a molten state, cast into a steel ingot or a slab, and the rolling reduction is 5 within a temperature range of 500 to 1300 ° C.
After hot rolling of 0% or more, annealing is performed, and then cold rolling and annealing are repeatedly performed to manufacture a coil or a cut plate having a required thickness.
【００２８】圧延された材料は、圧延ままの状態で使用
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 annealing, 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Ａｌ2 Ｏ3 スケー
ルを形成して合金中のＡｌを消費し、かつＡｌ2 Ｏ3 ス
ケールがハニカムの加工性を逸するためである。The rolled material can be used as it is rolled, but in the case of producing an annealed final product, it is bright under an inert gas atmosphere or a reducing gas atmosphere having a low oxygen partial pressure. Bright annealing (BA) is performed. The reason for this is that when annealing is performed in an oxidizing gas atmosphere, Al in the alloy is preferentially oxidized and Al 2 O 3 scale is formed to consume Al in the alloy, and Al 2 O 3 scale becomes honeycomb. This is because the workability of is lost.
【００２９】上記合金は、特に板圧０．２ｍｍ以下とし
た場合に従来材に比較し優れた耐酸化性が得られ排ガス
コンバータ用のメタルハニカムとして最適な材料とな
る。The above alloy has excellent oxidation resistance as compared with the conventional material especially when the plate pressure is 0.2 mm or less, and is an optimum material as a metal honeycomb for an exhaust gas converter.
【００３０】[0030]
【実施例】つぎに実施例に基づいて、本発明を具体的に
説明する。 （実施例）表１および表２に示す組成の合金を溶製し、
還元ガス雰囲気で光輝焼鈍し、圧延して箔とし、供試材
を得た。表１に示すのは本発明合金であり、表２に示す
のは比較合金である。以上の供試材について以下の試験
を行なった。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およびＣａ添加の効果によっ
て寿命が延びたことを確認する観点と、Ｔｉ，Ｎｂ，Ｃ
ｅがＬａ，Ｚｒ複合添加の効果を劣化させる観点から、
Ｌａ，Ｚｒ，Ｃａ，Ｔｉ，Ｎｂ，Ｃｅ以外の成分を同一
とし、Ｌａ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Ｌａ，Ｚ
ｒ，Ｃａ複合含有でさらに必要に応じてＴｉ，Ｎｂ，Ｃ
ｅを含有させた材料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。ここで、耐酸化寿命とは、各
供試材の板厚５０μｍのＢＡ箔を１２００℃、大気開放
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。表３お
よび表４にそれぞれ本発明合金と比較合金の耐酸化寿命
比および備考欄に製造性を示した。EXAMPLES Next, the present invention will be specifically described based on examples. (Example) An alloy having the composition shown in Table 1 and Table 2 was melted,
Bright annealing was performed in a reducing gas atmosphere, and the foil was rolled to obtain a test material. Table 1 shows the alloys of the present invention, and Table 2 shows the comparative alloys. The following tests were performed on the above test materials. The oxidation resistance life of the test materials was evaluated by La and Zr.
From the viewpoint of confirming that the life is extended by the synergistic effect of the combined inclusion of Ca and the effect of Ca addition, and Ti, Nb, C
From the viewpoint that e deteriorates the effect of the combined addition of La and Zr,
A comparative material containing La or Zr, Ca, Ti, Nb, and Ce with the same components other than La, Zr, and Ce alone was manufactured, and the oxidation resistance life was measured.
Contains r, Ca, and if necessary, Ti, Nb, C
The oxidation resistance life ratio was evaluated by multiplying the life of the material containing e. Here, the oxidation resistance life is obtained by obtaining the relationship between the oxidation time and the weight change of the BA foil with a plate thickness of 50 μm of each test material at 1200 ° C. and open to the atmosphere.
It was defined as the total oxidation time when it reached 0 mg / cm 2 . Tables 3 and 4 show the oxidation-resistant life ratios of the alloys of the present invention and the comparative alloys, and the manufacturability in the remarks column.
【００３１】[0031]
【表１】 [Table 1]
【００３２】[0032]
【表２】 [Table 2]
【００３３】 [0033]
【００３４】[0034]
【発明の効果】本発明は、Ｆｅ−Ｃｒ−Ａｌ系合金のＬ
ａ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
を実現させるとともにＬａ，Ｚｒ複合添加の効果を向上
させるＣａを適量含有させ、その効果を減少させるＴ
ｉ，Ｎｂ，Ｃｅを限定することにより高温での耐酸化性
を飛躍的に向上させたＦｅ−Ｃｒ−Ａｌ系合金およびそ
の合金箔を提供する。本発明は、自動車をなどの触媒コ
ンパーター用材料をはじめとした、耐熱用材料として最
適な合金である。INDUSTRIAL APPLICABILITY The present invention is an alloy of Fe--Cr--Al alloy.
By limiting the ratio of the a and Zr contents, it is possible to realize an oxidation resistance life not less than the sum of the respective lifespans rather than the simple sum of the oxidation resistance lifespans of La or Zr alone, which has been considered in the past. , Which contains the appropriate amount of Ca to improve the effect of Zr / Zr compound addition, and reduces the effect of T
Provided are a Fe-Cr-Al-based alloy and its alloy foil in which oxidation resistance at high temperature is dramatically improved by limiting i, Nb, and Ce. INDUSTRIAL APPLICABILITY The present invention is an optimal alloy as a heat-resistant material, including a material for a catalyst separator for automobiles and the like.
【図１】 重量比にして、０．００５％Ｃ，０．１５％
Ｓｉ，０．２％Ｍｎ，２０％Ｃｒ，５％Ａｌ，０．００
２％Ｎ，Ｔｉ，Ｎｂの合計で０．０１未満，Ｃｅ０．０
０５％未満で、残部Ｆｅおよび不可避的不純物より成り
合金を基本組成とし、Ｚｒ単独含有、Ｌａ単独含有、Ｌ
ａとＺｒの複合含有、Ｌａ，Ｚｒ，Ｃａの複合含有の４
種の合金の板厚５０μｍの箔の酸化時間に対する重量変
化を示す図である。1 is a weight ratio of 0.005% C, 0.15%
Si, 0.2% Mn, 20% Cr, 5% Al, 0.00
2% N, Ti, Nb total less than 0.01, Ce0.0
If less than 05%, the basic composition is an alloy consisting of balance Fe and inevitable impurities, Zr alone contained, La alone contained, L
4 of composite inclusion of a and Zr, composite inclusion of La, Zr, Ca
It is a figure which shows the weight change with respect to the oxidation time of the foil of 50-micrometer board | plate thickness of a kind alloy.
【図２】 重量比にして、０．００５％Ｃ，０．１５％
Ｓｉ，０．２％Ｍｎ，２０％Ｃｒ，５％Ａｌ，０．００
２％Ｎ，０．００１〜０．００４％Ｃａ，Ｔｉ，Ｎｂ合
計で０．０１％未満，Ｃｅ０．００５％未満で、さらに
Ｌａ：０．０１〜０．２％，Ｚｒ０．０１〜１．０％を
含有し、残部Ｆｅおよび不可避的不純物より成る合金の
板厚５０μｍの箔の耐酸化寿命比と〔Ｚｒ重量％〕／
〔Ｌａ重量％〕の値の関係を示す図である。FIG. 2: 0.005% C, 0.15% by weight
Si, 0.2% Mn, 20% Cr, 5% Al, 0.00
2% N, 0.001-0.004% Ca, Ti, Nb total less than 0.01%, Ce less than 0.005%, La: 0.01-0.2%, Zr 0.01-1. Oxidation resistance ratio and [Zr weight%] of a 50 μm-thick foil of an alloy containing 0% and the balance Fe and unavoidable impurities
It is a figure which shows the relationship of the value of [La weight%].
Claims (5)
２重量％以下、 Ｓｉ：１．０重量％以下、 Ｍｎ：１．５重量％以
下、 Ｓ：０．０１重量％以下、 Ｔｉ，Ｎｂ：合計で０．
０５重量％以下、 Ｃｅ：０．０１重量％以下、 Ｃｒ：１０〜２８重量％ Ａｌ：１〜６重量％、 Ｃａ：０．０００３〜
０．０３重量％を含有し、さらにＬａおよびＺｒが Ｌａ：０．０１〜０．２０重量％、 Ｚｒ：０．０１〜
１．０重量％ ０．１≦〔Ｚｒ重量％〕／〔Ｌａ重量％〕≦２０ ………（Ａ） で、かつ（Ａ）式を満足し、残部Ｆｅおよび不可避的不
純物よりなる、耐酸化性に優れたＦｅ−Ｃｒ−Ａｌ系合
金。1. C: 0.05% by weight or less, N: 0.0
2% by weight or less, Si: 1.0% by weight or less, Mn: 1.5% by weight or less, S: 0.01% by weight or less, Ti, Nb: 0.
05 wt% or less, Ce: 0.01 wt% or less, Cr: 10 to 28 wt% Al: 1 to 6 wt%, Ca: 0.0003 to
0.03% by weight, and La and Zr are La: 0.01 to 0.20% by weight, Zr: 0.01 to
1.0 wt% 0.1 ≦ [Zr wt%] / [La wt%] ≦ 20 (A) and satisfies the formula (A), the balance consisting of Fe and unavoidable impurities, oxidation resistance Fe-Cr-Al alloy with excellent properties.
種以上を合計で１．０重量％以下含有する請求項１に記
載のＦｅ−Ｃｒ−Ａｌ系合金。2. One or two of V, Ta and Hf.
The Fe-Cr-Al-based alloy according to claim 1, which contains 1.0% by weight or less in total of at least one kind.
または２に記載のＦｅ−Ｃｒ−Ａｌ系合金。3. Y: 0.5 wt% or less is contained.
Alternatively, the Fe-Cr-Al alloy described in 2.
する請求項１〜３のいずれかに記載のＦｅ−Ｃｒ−Ａｌ
系合金。4. Fe-Cr-Al according to claim 1, which contains Mg in an amount of 0.0005 to 0.03% by weight.
Series alloy.
ｒ−Ａｌ系合金を圧延により作製した０．２ｍｍ以下の
箔。5. Fe-C according to claim 1.
A foil of 0.2 mm or less produced by rolling an r-Al alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26764292A JP3247162B2 (en) | 1992-10-06 | 1992-10-06 | Fe-Cr-Al-based alloy excellent in oxidation resistance and foil thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP26764292A JP3247162B2 (en) | 1992-10-06 | 1992-10-06 | Fe-Cr-Al-based alloy excellent in oxidation resistance and foil thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH06116686A true JPH06116686A (en) | 1994-04-26 |
| JP3247162B2 JP3247162B2 (en) | 2002-01-15 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP26764292A Expired - Lifetime JP3247162B2 (en) | 1992-10-06 | 1992-10-06 | Fe-Cr-Al-based alloy excellent in oxidation resistance and foil thereof |
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