JPH108215A - Iron-chromium-aluminum alloy foil for catalyst support for exhaust gas cleaning - Google Patents
Iron-chromium-aluminum alloy foil for catalyst support for exhaust gas cleaningInfo
- Publication number
- JPH108215A JPH108215A JP15934296A JP15934296A JPH108215A JP H108215 A JPH108215 A JP H108215A JP 15934296 A JP15934296 A JP 15934296A JP 15934296 A JP15934296 A JP 15934296A JP H108215 A JPH108215 A JP H108215A
- Authority
- JP
- Japan
- Prior art keywords
- exhaust gas
- alloy foil
- rolling
- foil
- oxidation resistance
- 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
Landscapes
- Heat Treatment Of Steel (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、Fe−Cr−Al合金箔
に関し、とくに排ガス浄化触媒の担体に用いるFe−Cr−
Al合金箔に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an Fe--Cr--Al alloy foil, and more particularly to Fe--Cr--Al alloy foil used as a carrier for an exhaust gas purifying catalyst.
Related to Al alloy foil.
【０００２】[0002]
【従来の技術】大気汚染の発生源のひとつとして、自動
車等から排出される汚染物質が問題視され、それら汚染
物質の軽減のために触媒が使用されるようになった。排
ガス浄化用触媒コンバータは、自動車等で燃料と空気と
を混合し燃焼させたときに発生するNOX 、HC、COなどの
有害ガスを無害化するために使用されている。この触媒
を支える担体には、従来セラミックが用いられていた。
しかし、排ガス浄化効率を上げるために触媒をエンジン
に近い場所に搭載する必要が生じ、担体はより高温の排
ガスにさらされることになり、セラミック担体では構造
面から使用が困難となった。これに代わり、浄化特性向
上や通気抵抗低減が可能となる、Fe−Cr−Al合金箔を組
み立てた金属担体が使用されるようになってきている。2. Description of the Related Art As one of the sources of air pollution, pollutants emitted from automobiles and the like have been regarded as a problem, and catalysts have been used to reduce such pollutants. An exhaust gas purifying catalyst converter is used NO X generated when mixing the fuel and air is burned in an automobile or the like, HC, to detoxify harmful gases such as CO. Conventionally, ceramic has been used as a support for supporting the catalyst.
However, in order to increase the efficiency of exhaust gas purification, it is necessary to mount the catalyst near the engine, and the carrier is exposed to higher-temperature exhaust gas, making it difficult to use a ceramic carrier from the structural point of view. Instead, metal carriers assembled from Fe—Cr—Al alloy foil, which can improve purification characteristics and reduce airflow resistance, have been used.
【０００３】このような合金箔は通常50μm 程度の厚み
で使用されているが、最近では、特に自動車用触媒コン
バータに利用されるものについては、さらなる通気抵抗
低減と浄化特性向上を目的として、厚さ35μm 程度の極
薄箔の使用が検討されている。排ガス浄化用触媒コンバ
ータは、高温の排気ガスと触媒反応熱とにより加熱され
るため、使用する材料には優れた耐酸化性が要求され
る。このコンバータに用いられる担体用材料として、例
えば、特開昭64-11946号公報および特開平5-202449号公
報に、La、Zrを添加したFe−Cr−Al合金が提案されてい
る。[0003] Such alloy foils are usually used with a thickness of about 50 µm. Recently, however, especially for those used in catalytic converters for automobiles, the thickness of the alloy foil is reduced in order to further reduce the ventilation resistance and improve the purification characteristics. The use of ultra-thin foil of about 35 μm is under study. Since the exhaust gas purifying catalytic converter is heated by the high-temperature exhaust gas and the heat of catalytic reaction, the materials used are required to have excellent oxidation resistance. As a material for a carrier used in this converter, for example, Fe-Cr-Al alloys to which La and Zr are added have been proposed in JP-A-64-11946 and JP-A-5-202449.
【０００４】しかし、上記した材料は、50μm 程度の厚
さまでは何の支障もなく圧延ができるが、さらに薄い厚
みへの圧延は困難となる。例えば、厚みが40μm 程度よ
り薄くなると冷間圧延中に素材が破断し、それ以上の圧
延が困難となったり、圧延できても歩留りが低く少量の
製品しか得られないという問題があった。Fe−Cr−Al合
金は、熱間加工性が低く、熱延時に発生した微小割れが
原因で、ヘゲ等の表面欠陥が多発する。表面欠陥がある
熱延板を冷間圧延すると製品箔に穴が生じたり、また、
その穴が起点となって箔圧延時に素材が破断したりす
る。そのため、表面欠陥がある場合には、グラインダー
等で表面を研摩し、除去しなければならない。しかし、
このような研摩手入は、コストアップとなるうえ、研摩
量が多いと素材の形状が悪くなり、箔圧延時に素材が破
断しすく、箔の製造ができなくなる等の問題があった。However, the above-mentioned materials can be rolled without any trouble at a thickness of about 50 μm, but it is difficult to roll to a thinner thickness. For example, when the thickness is less than about 40 μm, there is a problem that the material is broken during cold rolling, and further rolling becomes difficult, and even if rolling can be performed, the yield is low and only a small amount of products can be obtained. The Fe—Cr—Al alloy has low hot workability, and causes many surface defects such as scabs due to minute cracks generated during hot rolling. Cold rolling of hot rolled sheet with surface defects may cause holes in product foil,
The hole serves as a starting point, and the material breaks during foil rolling. Therefore, if there is a surface defect, the surface must be polished and removed with a grinder or the like. But,
Such polishing treatments have a problem that the cost is increased, and that if the amount of polishing is large, the shape of the material is deteriorated, the material is easily broken at the time of foil rolling, and the foil cannot be manufactured.
【０００５】また、触媒担体の厚さを薄くすると、表面
積に対する体積比が減少し、より短時間で異常酸化を受
け担体が破壊されやすくなる。このため、極薄箔担体に
用いる材料は従来以上に耐酸化性が要求されている。さ
らに、浄化特性の向上、すなわち、触媒反応促進のため
には排ガス浄化用触媒コンバータは、エンジンに近い場
所に設置するのが好ましいが、エンジンに近づくほど担
体は高温に加熱される。そのため、担体が縮み、外筒と
の間に隙間を生じる。この隙間を通る排ガスは、浄化さ
れないため、有害物質の排出量が増加するという問題が
あった。[0005] When the thickness of the catalyst carrier is reduced, the volume ratio to the surface area is reduced, and the carrier is susceptible to abnormal oxidation in a shorter period of time, and the carrier is easily broken. For this reason, the material used for the ultra-thin foil carrier is required to have higher oxidation resistance than ever. Further, in order to improve the purification characteristics, that is, to promote the catalytic reaction, it is preferable to install the exhaust gas purifying catalytic converter near the engine, but the carrier is heated to a higher temperature as it approaches the engine. Therefore, the carrier shrinks, and a gap is formed between the carrier and the outer cylinder. Since the exhaust gas passing through this gap is not purified, there has been a problem that the emission amount of harmful substances increases.
【０００６】[0006]
【発明が解決しようとする課題】本発明は、上記問題点
を有利に解決し、加工性に優れ極薄箔とすることがで
き、また、極薄箔としても異常酸化を生ぜず耐酸化性に
優れ、かつ使用中縮みの少ない排ガス浄化触媒担体用Fe
−Cr−Al合金箔およびその製造方法を提案することを目
的とする。DISCLOSURE OF THE INVENTION The present invention advantageously solves the above-mentioned problems, and can be formed into an ultrathin foil having excellent workability. Fe for exhaust gas purifying catalyst carrier with excellent shrinkage during use
An object is to propose a Cr-Al alloy foil and a method for producing the same.
【０００７】[0007]
【課題を解決するための手段】本発明者らは、Fe−Cr−
Al合金箔の冷間圧延における破断が、素材中に存在する
析出物に起因することを突き止め、Fe−Cr−Al合金箔に
おける析出物の生成を抑える成分組成、製造条件を新規
に見いだし、さらに、排ガス浄化触媒コンバータで使用
中に発生する担体の縮みについて鋭意検討した結果、Ti
の添加が使用中縮みの減少には有効であることを新規に
知見し、本発明を構成した。Means for Solving the Problems The present inventors have proposed Fe-Cr-
Fracture in cold rolling of Al alloy foil was found to be caused by precipitates present in the material, component composition for suppressing the formation of precipitates in the Fe-Cr-Al alloy foil, and production conditions were newly found. Intensive study of carrier shrinkage during use in exhaust gas purification catalytic converters revealed that Ti
It was newly found that the addition of is effective in reducing shrinkage during use, and constituted the present invention.
【０００８】すなわち、本発明は、重量％で、Cr：15.0
〜25.0％、Al：4.0 〜6.5 ％、Zr：0.005 〜0.10％、T
i：0.005 〜0.05％を含み、かつ、Ti/Zr ：２以下で、
さらに、希土類元素のうちから選ばれた１種または２種
以上を合計で0.01〜0.20％含有し、残部がFeおよび不可
避的不純物からなる耐酸化性に優れた排ガス浄化触媒担
体用Fe−Cr−Al合金箔であり、また、本発明は、重量％
で、Cr：15.0〜25.0％、Al：4.0 〜6.5 ％、Zr：0.005
〜0.05％、Ti：0.005 〜0.05％を含み、かつ、Ti/Zr ：
0.2 〜２で、さらに、希土類元素のうちから選ばれた１
種または２種以上を合計で0.01〜0.20％含有し、残部が
Feおよび不可避的不純物からなることを特徴とする耐酸
化性・耐縮み性に優れた排ガス浄化触媒担体用Fe−Cr−
Al合金箔である。さらに、本発明は、重量％で、Cr：1
5.0〜25.0％、Al：4.0 〜6.5 ％、Zr：0.005 〜0.10
％、Ti：0.005 〜0.05％を含み、かつ、Ti/Zr ：２以下
で、さらに、希土類元素のうちから選ばれた１種または
２種以上を合計で0.01〜0.20％含有し、残部がFeおよび
不可避的不純物からなる素材を、1050℃超え1150℃未満
の温度範囲に加熱し熱間圧延したのち、焼鈍および冷間
圧延を施し合金箔とする耐酸化性に優れた排ガス浄化触
媒担体用Fe−Cr−Al合金箔の製造方法であり、前記熱間
圧延が、最初の３パスまでの少なくとも１パスの圧延を
圧下率：10％以下とするのが好ましく、また、前記素材
は、重量％で、Cr：15.0〜25.0％、Al：4.0〜6.5 ％、Z
r：0.005 〜0.05％、Ti：0.005 〜0.05％を含み、か
つ、Ti/Zr ：0.2 〜２で、さらに、希土類元素のうちか
ら選ばれた１種または２種以上を合計で0.01〜0.20％含
有し、残部がFeおよび不可避的不純物からなるのが好ま
しい。[0008] That is, the present invention relates to a method for producing Cr: 15.0% by weight.
~ 25.0%, Al: 4.0 ~ 6.5%, Zr: 0.005 ~ 0.10%, T
i: contains 0.005 to 0.05%, and Ti / Zr: 2 or less,
Furthermore, one or two or more selected from rare earth elements are contained in a total amount of 0.01 to 0.20%, and the balance is Fe-Cr- for an exhaust gas purifying catalyst carrier which is excellent in oxidation resistance and composed of Fe and unavoidable impurities. Al alloy foil and the present invention
And Cr: 15.0 to 25.0%, Al: 4.0 to 6.5%, Zr: 0.005
-0.05%, Ti: 0.005-0.05%, and Ti / Zr:
0.2 to 2, and 1 selected from rare earth elements
Contains 0.01 or 0.20% of seeds or two or more in total, with the balance being
Fe-Cr- for exhaust gas purifying catalyst carrier with excellent oxidation resistance and shrink resistance characterized by being composed of Fe and unavoidable impurities
Al alloy foil. In addition, the present invention provides a method for preparing a Cr: 1
5.0-25.0%, Al: 4.0-6.5%, Zr: 0.005-0.10
%, Ti: 0.005 to 0.05%, Ti / Zr: 2 or less, and one or more selected from rare earth elements in a total of 0.01 to 0.20%, with the balance being Fe After heating the material consisting of unavoidable impurities to a temperature range of more than 1050 ° C. and less than 1150 ° C., and then performing annealing and cold rolling to obtain an alloy foil, Fe for exhaust gas purifying catalyst carrier having excellent oxidation resistance. -A method for producing a Cr-Al alloy foil, wherein the hot rolling is preferably such that at least one pass rolling up to the first three passes is reduced to a rolling reduction of 10% or less, and the material is a weight% In, Cr: 15.0-25.0%, Al: 4.0-6.5%, Z
r: 0.005 to 0.05%, Ti: 0.005 to 0.05%, Ti / Zr: 0.2 to 2, and one or more selected from rare earth elements in a total of 0.01 to 0.20% It is preferable that the alloy contains Fe and the balance consists of Fe and inevitable impurities.
【０００９】[0009]
【発明の実施の形態】まず、本発明の限定理由について
説明する。 Cr：15.0〜25.0％ Crは、耐酸化性を向上させる元素であるが、15.0％未満
ではその効果が少なく、一方、25.0％を超えると靱性が
劣化し、冷間圧延が困難となる。このため、Crは 15.0
〜25.0％の範囲とする。なお、好ましくは、18.0〜22.0
％である。DESCRIPTION OF THE PREFERRED EMBODIMENTS First, the reasons for limiting the present invention will be described. Cr: 15.0 to 25.0% Cr is an element that improves the oxidation resistance. If Cr is less than 15.0%, its effect is small. On the other hand, if it exceeds 25.0%, toughness is deteriorated, and cold rolling becomes difficult. Therefore, Cr is 15.0
~ 25.0%. Incidentally, preferably, 18.0 ~ 22.0
%.
【００１０】Al：4.0 〜6.5 ％ Alは、合金箔表面に保護性の高いAl2O3 皮膜を形成し、
耐酸化性を向上する。しかし、 4.0％未満では、有効な
Al2O3 皮膜の形成が少なく耐酸化性が劣り、極薄箔の場
合には、短時間の酸化で消耗し異常酸化を生じ担体の破
壊を導くため、Al含有量の下限は 4.0％とした。また、
6.5 ％を超えると、靱性が劣化し、圧延が困難となるた
め、6.5 ％をAl含有量の上限とした。なお、好ましく
は、4.5 〜6.0 ％である。Al: 4.0-6.5% Al forms a highly protective Al 2 O 3 film on the alloy foil surface,
Improves oxidation resistance. However, less than 4.0% is effective
The formation of the Al 2 O 3 film is small and the oxidation resistance is inferior. In the case of ultra-thin foil, it is consumed in a short time of oxidation and abnormal oxidation occurs, leading to the destruction of the carrier, so the lower limit of the Al content is 4.0%. did. Also,
If it exceeds 6.5%, the toughness deteriorates and rolling becomes difficult. Therefore, the upper limit of the Al content is 6.5%. Preferably, the content is 4.5 to 6.0%.
【００１１】Zr：0.005 〜0.10％ Zrは、耐酸化性を向上させる元素であるが、0.005 ％未
満では、その効果が少なく、また、0.10％を超えると、
酸化速度を増加させ、かえって耐酸化性が低下するた
め、Zrは 0.005〜0.10％の範囲とした。なお、0.05％を
超えると、使用中縮みが大きくなり、Tiを添加しても縮
みを防止できなくなるため、使用中縮みを考慮する場合
には、Zrは 0.005〜0.05％の範囲が好ましい。さらに好
ましくは、0.01〜0.03％である。Zr: 0.005% to 0.10% Zr is an element which improves the oxidation resistance. If it is less than 0.005%, its effect is small.
Zr is set in the range of 0.005 to 0.10% because the oxidation rate is increased and the oxidation resistance is rather reduced. If the content exceeds 0.05%, the shrinkage during use increases, and it becomes impossible to prevent shrinkage even when Ti is added. Therefore, in consideration of shrinkage during use, Zr is preferably in the range of 0.005 to 0.05%. More preferably, it is 0.01 to 0.03%.
【００１２】Ti：0.005 〜0.05％ Tiは、合金中のＮ、Ｃを、TiN 、TiC として固定し、箔
圧延中に有害なZrN 、ZrC の析出を防ぐ。さらに、Ti
は、使用中に表面に生成するAl2O3 皮膜中に侵入し、使
用中に発生する縮みを防止する。0.005 ％未満では、こ
れらの効果が少なく、また、0.05％を超えると耐酸化性
を低下させるため、Tiは 0.005〜0.05％の範囲とした。
なお、好ましくは、0.01〜0.03％である。Ti: 0.005 to 0.05% Ti fixes N and C in the alloy as TiN and TiC, and prevents harmful precipitation of ZrN and ZrC during foil rolling. In addition, Ti
Penetrates into the Al 2 O 3 film formed on the surface during use and prevents shrinkage that occurs during use. If the content is less than 0.005%, these effects are small, and if it exceeds 0.05%, the oxidation resistance is reduced. Therefore, the content of Ti is set in the range of 0.005 to 0.05%.
In addition, Preferably, it is 0.01 to 0.03%.
【００１３】Ti/Zr ：２以下 本発明では、さらに、TiはZr含有量との関係で規制され
る。Ti/Zr が２を超えると、耐酸化性が低下するため、
Ti/Zr=２を上限とした。さらに、使用中の縮みを防止す
るために、Ti/Zr は0.2 以上が好ましい。なお、さらに
好ましくは、Ti/Zr は、0.5 以上1.5 以下である。Ti / Zr: 2 or less In the present invention, Ti is further restricted in relation to the Zr content. If Ti / Zr exceeds 2, the oxidation resistance decreases,
The upper limit was Ti / Zr = 2. Further, in order to prevent shrinkage during use, Ti / Zr is preferably 0.2 or more. Note that Ti / Zr is more preferably 0.5 or more and 1.5 or less.
【００１４】希土類元素の合計：0.01〜0.20％ 希土類元素は、本発明では、Ｙを含み、La、Ce、Pr、N
d、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Tm、Yb、Luをいう。
希土類元素群の中から選ばれた１種または２種以上を添
加できる。希土類元素は、耐酸化性を向上させる元素で
あり、その効果は、0.01％以上の添加で認められるが、
0.20％を超えると熱間加工性が劣化し、圧延時に耳割れ
が生じる。そのため、希土類元素は、0.01〜0.20％の範
囲とした。希土類元素を２種以上添加する場合には、そ
れら元素量の合計がこの範囲内であればよい。In the present invention, the rare earth element includes Y, La, Ce, Pr, N
d, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb, and Lu.
One or more selected from the group of rare earth elements can be added. Rare earth elements are elements that improve oxidation resistance, and their effects are observed when added at 0.01% or more.
If it exceeds 0.20%, hot workability deteriorates and ear cracks occur during rolling. Therefore, the content of the rare earth element is set in the range of 0.01 to 0.20%. When two or more rare earth elements are added, the sum of the amounts of these elements may be within this range.
【００１５】希土類元素群の中では、Laがもっとも好ま
しい。Ceは、熱間加工性の低下を著しく助長するため、
その添加は0.05％以下とするのが好ましい。なお、希土
類元素の添加量は、合計で0.05〜0.12％がより好まし
い。残部はFeであり、上記成分以外は不純物である。不
純物元素として、Ｃ、Si、Mn、Ｐ、Ｓ、Ｎは、それぞれ
Ｃ：0.02％以下、Si：1.0 ％以下、Mn：1.0 ％以下、
Ｐ：0.05％以下、Ｓ：0.01％以下、Ｎ：0.02％以下とす
る。Among the rare earth elements, La is most preferred. Ce significantly promotes the reduction of hot workability,
The addition is preferably set to 0.05% or less. It is more preferable that the total amount of the rare earth elements added is 0.05 to 0.12%. The balance is Fe, and impurities other than the above components are impurities. As impurity elements, C, Si, Mn, P, S, and N are respectively: C: 0.02% or less, Si: 1.0% or less, Mn: 1.0% or less,
P: 0.05% or less, S: 0.01% or less, N: 0.02% or less.
【００１６】また、HfはZr中に不純物として含有されて
いるため、Zrの添加とともに混入し、0.01〜0.05％程度
含有する場合がある。Hfは、耐酸化性を向上させる元素
であり、含有しても本発明の目的を害さない。上記組成
を有する素材は、通常の溶製方法、転炉、電気炉、ある
いは真空溶解炉等で溶製し、ＲＨ脱ガス法、ＡＯＤ法、
ＶＯＤ法などが好適である。鋳造法としては、生産性、
品質上から連鋳法が望ましいが、造塊法も適用できる。Further, since Hf is contained as an impurity in Zr, it may be mixed with the addition of Zr and contained in an amount of about 0.01 to 0.05%. Hf is an element that improves the oxidation resistance, and does not impair the purpose of the present invention even if Hf is contained. The material having the above composition is melted in a normal melting method, a converter, an electric furnace, a vacuum melting furnace, or the like, and is subjected to RH degassing, AOD,
The VOD method is suitable. As for the casting method, productivity,
Although a continuous casting method is desirable from the viewpoint of quality, an ingot casting method is also applicable.
【００１７】上記した方法で製造した素材を、熱間圧延
したのち、焼鈍、冷間圧延を施し、合金箔とする。熱間
圧延の加熱温度は、1050℃超え1150℃未満の温度範囲と
する。1050℃以下では、熱間圧延時に素材に割れが生じ
圧延が困難となり、また、1150℃以上では大型のZrC 、
ZrN が析出し、箔圧延時に素材が破断するため、熱間圧
延の加熱温度は、1050℃超え1150℃未満の温度範囲とし
た。なお、加熱時間は、長時間となるほど析出物の成長
が進むため１〜３hrが好ましい。After the material produced by the above method is hot-rolled, it is annealed and cold-rolled to obtain an alloy foil. The heating temperature of the hot rolling is in a temperature range of more than 1050 ° C and less than 1150 ° C. At 1050 ° C or lower, the material becomes cracked during hot rolling and rolling becomes difficult, and at 1150 ° C or higher, large ZrC,
Since ZrN precipitates and the material breaks during foil rolling, the heating temperature for hot rolling was set to a temperature range of more than 1050 ° C and less than 1150 ° C. The heating time is preferably 1 to 3 hours since the growth of the precipitate proceeds as the time becomes longer.
【００１８】熱間圧延の最初の３パスまでの少なくとも
１パスの圧延を圧下率：10％以下とする。最初の３パス
まで、すべてのパスのパスあたりの圧下量が10％を超え
ると、表面欠陥の原因となる微小割れが多発する。この
ような微小割れは、表面欠陥となり、冷間圧延時の素材
の破断を誘起する。最初の３パスまでの少なくとも１パ
スの圧延を圧下率：10％以下とすることにより、表面の
良好な熱延板を得ることができ、極薄箔圧延が可能とな
る。The rolling of at least one pass up to the first three passes of hot rolling is reduced to a rolling reduction of 10% or less. If the amount of reduction per pass of all the passes up to the first three passes exceeds 10%, minute cracks causing surface defects frequently occur. Such micro-cracks become surface defects and induce breakage of the material during cold rolling. By setting the rolling reduction of at least one pass up to the first three passes to a rolling reduction of 10% or less, a hot-rolled sheet having a good surface can be obtained, and ultrathin foil rolling becomes possible.
【００１９】[0019]
（実施例１）表１に示す組成のFe−Cr−Al合金を真空溶
解炉で溶製し、インゴットに鋳造したのち、表１に示す
熱間圧延条件で、熱間圧延した。その後、熱延板を焼
鈍、酸洗したのち、冷間圧延と焼鈍を繰り返し、35μm
厚さの箔とした。(Example 1) An Fe-Cr-Al alloy having the composition shown in Table 1 was melted in a vacuum melting furnace, cast into an ingot, and then hot-rolled under the hot rolling conditions shown in Table 1. Then, after annealing the hot-rolled sheet, pickling, repeated cold rolling and annealing, 35μm
The foil was thick.
【００２０】これらの箔について、（１）耐酸化性試
験、（２）耐縮み性試験を行い、耐酸化性と使用中の耐
縮み性を評価した。その結果を表１に併記する。これら
試験の試験方法を説明する。 （１）耐酸化性試験 箔から20×30mmの試験片を採取し、大気中で1150℃の温
度で72hrの酸化試験を行い、酸化試験前後の重量を測定
し、酸化増量を求めた。酸化増量が1.0mg/cm2以下の場
合を○、酸化増量が1.0mg/cm2 超え2.0mg/cm2 以下の場
合を△、酸化増量が2.0mg/cm2 超えの場合を×として評
価した。 （２）耐縮み性試験 箔から50×50mmの試験片を採取し、この試験片を図１に
示す形状（約５mmφの円筒状）で、圧延方向が円筒の長
手方向に一致するように約５mmφの大きさに巻き、端部
をスポット溶接により固定し、縮み測定試験片とした。
この縮み測定試験片を1100℃で100hr 保持し、長手方向
の縮み量（％）を測定した。異常酸化を生じ、測定でき
なかったものは、×印で示した。These foils were subjected to (1) oxidation resistance test and (2) shrink resistance test to evaluate the oxidation resistance and the shrink resistance during use. The results are also shown in Table 1. Test methods of these tests will be described. (1) Oxidation resistance test A 20 × 30 mm test piece was sampled from a foil and subjected to an oxidation test at 1150 ° C. for 72 hours in the air, and the weight before and after the oxidation test was measured to determine the oxidation weight gain. ○ where oxidation weight gain is less than 1.0 mg / cm 2, the case where oxidation weight gain is less than 1.0 mg / cm 2 than 2.0mg / cm 2 △, oxidized amount was evaluated as × in the case of exceeding 2.0 mg / cm 2 . (2) Shrink resistance test A test piece of 50 × 50 mm was sampled from the foil, and the test piece was shaped as shown in FIG. 1 (a cylindrical shape of about 5 mmφ) so that the rolling direction coincided with the longitudinal direction of the cylinder. It was wound into a size of 5 mmφ, and the end was fixed by spot welding to obtain a shrinkage measurement test piece.
This shrinkage measurement specimen was held at 1100 ° C. for 100 hours, and the amount of shrinkage (%) in the longitudinal direction was measured. Those which caused abnormal oxidation and could not be measured were indicated by x marks.
【００２１】[0021]
【表１】 [Table 1]
【００２２】表１から、本発明例のNo.1〜８は、酸化増
量が少なく良好な耐酸化性をしめすが、比較例のNo.9〜
17は、異常酸化を示し耐酸化性が劣化している。本発明
例の内、Zr含有量が0.05％以下に制限したNo.1〜５は、
縮み量が１％以下と良好な耐縮み性を示している。Zr含
有量が0.05％を超える本発明例および本発明範囲を外れ
る比較例は、縮み量が３〜８％と大きいか、あるいは異
常酸化を生じ縮み量が測定できないほど、耐縮み性が劣
化している。From Table 1, it can be seen that Nos. 1 to 8 of the examples of the present invention show good oxidation resistance with a small increase in oxidation, but Nos. 9 to 9 of the comparative examples.
No. 17 shows abnormal oxidation and oxidation resistance is deteriorated. Among the inventive examples, Nos. 1 to 5 in which the Zr content was limited to 0.05% or less,
The amount of shrinkage is 1% or less, indicating good shrink resistance. Examples of the present invention in which the Zr content exceeds 0.05% and comparative examples out of the range of the present invention show that the shrinkage is so large that the shrinkage is as large as 3 to 8% or the amount of shrinkage cannot be measured due to abnormal oxidation. ing.
【００２３】希土類元素の合計が0.20％を超えるNo.21
は、熱間加工性が劣化し、所定の厚みの箔とならなかっ
た。 （実施例２）表２に示す組成のFe−Cr−Al合金をＶＯＤ
炉で溶製し、連鋳によりスラブとした。これらスラブ
（200mm 厚×1000mm×7000mm) に表３に示す熱間圧延条
件で熱間圧延を施し、３mm厚の熱延コイルとした。表３
に示す熱間圧延条件のうち熱延圧下率は熱間圧延の最初
の３パスのそれぞれの圧下量を示す。つぎに、これら熱
延コイルを900 ℃で焼鈍し、酸洗し端部をトリミングし
たのち、冷間圧延し、100 μm 厚の冷延コイルとした。
さらに、これら冷延コイルを窒素ガス雰囲気中の850 ℃
で焼鈍した後、さらに端部をトリミングして冷間圧延を
行い、35μm 厚の箔とした。No. 21 wherein the total of the rare earth elements exceeds 0.20%
The hot workability deteriorated, and a foil having a predetermined thickness was not obtained. (Example 2) An Fe-Cr-Al alloy having the composition shown in Table 2 was VOD
It was melted in a furnace and slab was made by continuous casting. These slabs (200 mm thick × 1000 mm × 7000 mm) were subjected to hot rolling under the hot rolling conditions shown in Table 3 to obtain hot rolled coils having a thickness of 3 mm. Table 3
The hot rolling reduction among the hot rolling conditions shown in (1) indicates the amount of reduction in each of the first three passes of hot rolling. Next, these hot-rolled coils were annealed at 900 ° C., pickled, trimmed at their ends, and then cold-rolled into 100 μm-thick cold-rolled coils.
Further, these cold-rolled coils were heated at 850 ° C in a nitrogen gas atmosphere.
Then, the edge was further trimmed and cold-rolled to obtain a foil having a thickness of 35 μm.
【００２４】100 μm 厚の冷延コイルから35μm 厚の箔
への冷間圧延中に素材コイルが破断した回数を箔圧延性
とし、素材コイルの圧延性を評価した。その結果を表３
に示す。また、これら箔について、耐酸化性、耐縮み性
を実施例１と同様に行い、その結果を表３に示す。The number of times the material coil broke during cold rolling from a cold-rolled coil having a thickness of 100 μm to a foil having a thickness of 35 μm was defined as the foil rolling property, and the rolling property of the material coil was evaluated. Table 3 shows the results.
Shown in The oxidation resistance and shrinkage resistance of these foils were measured in the same manner as in Example 1, and the results are shown in Table 3.
【００２５】[0025]
【表２】 [Table 2]
【００２６】[0026]
【表３】 [Table 3]
【００２７】表３から本発明例のNo.1〜３は、熱延コイ
ルの表面状態は良好であり、箔圧延性、耐酸化性も良好
であった。一方、本発明の範囲を外れる比較例のNo.4、
No.5、No.7は、箔圧延性が５〜８と高く、極薄箔への圧
延中に破断が多発している。また、比較例のNo.5は熱間
圧延時の圧下率が高すぎ表面欠陥が多発し長時間のグラ
インダ研摩を必要とした。また、No.6はスラブ加熱温度
が低すぎ表面欠陥、耳割れが多発し、製品にすることが
できなかった。From Table 3, Nos. 1 to 3 of the examples of the present invention showed that the surface condition of the hot-rolled coil was good and that the foil rolling property and the oxidation resistance were also good. On the other hand, No. 4 of the comparative example out of the range of the present invention,
No. 5 and No. 7 have high foil rollability of 5 to 8, and breakage frequently occurs during rolling to ultra-thin foil. In Comparative Example No. 5, the rolling reduction at the time of hot rolling was too high, and many surface defects were generated, requiring long-time grinder polishing. In No. 6, the slab heating temperature was too low, and surface defects and edge cracks occurred frequently, and the product could not be manufactured.
【００２８】[0028]
【発明の効果】本発明によれば、排ガス浄化触媒担体に
用いて好適な耐酸化性に優れ、使用中の耐縮み性に優れ
た極薄のFe−Cr−Al合金箔が、コイル破断も少なく歩留
り良く製造でき、著しい産業上の効果が期待できる。According to the present invention, an ultra-thin Fe-Cr-Al alloy foil excellent in oxidation resistance suitable for use as an exhaust gas purifying catalyst carrier and excellent in shrinkage resistance during use can be used to prevent coil breakage. It can be manufactured with little yield and a significant industrial effect can be expected.
【図１】縮み測定試験片形状と製作方法を示す説明図で
ある。FIG. 1 is an explanatory view showing a shape of a shrinkage measurement test piece and a manufacturing method.
───────────────────────────────────────────────────── フロントページの続き (72)発明者 横田 毅 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所内 (72)発明者 佐藤 進 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所内 ──────────────────────────────────────────────────続 き Continuing on the front page (72) Inventor Takeshi Yokota 1 Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture Inside the Technical Research Institute of Kawasaki Steel Corp. (72) Susumu Sato Susumu 1 Kawasaki-cho, Chuo-ku, Chiba City, Chiba Prefecture Kawasaki Steel Research Institute
Claims (5)
計で0.01〜0.20％含有し、残部がFeおよび不可避的不純
物からなることを特徴とする耐酸化性に優れた排ガス浄
化触媒担体用Fe−Cr−Al合金箔。(1) In weight%, Cr: 15.0 to 25.0%, Al: 4.0 to 6.5%, Zr: 0.005 to 0.10%, Ti: 0.005 to 0.05%, and Ti / Zr: 2 or less, An exhaust gas purifying catalyst carrier having excellent oxidation resistance, characterized in that it contains one or more selected from rare earth elements in a total amount of 0.01 to 0.20%, with the balance being Fe and unavoidable impurities. Fe-Cr-Al alloy foil.
計で0.01〜0.20％含有し、残部がFeおよび不可避的不純
物からなることを特徴とする耐酸化性・耐縮み性に優れ
た排ガス浄化触媒担体用Fe−Cr−Al合金箔。2. The composition according to claim 1, wherein the composition contains Cr: 15.0 to 25.0%, Al: 4.0 to 6.5%, Zr: 0.005 to 0.05%, Ti: 0.005 to 0.05%, and Ti / Zr: 0.2 to 2, by weight%. Further, it contains one or more selected from rare earth elements in a total amount of 0.01 to 0.20%, with the balance being Fe and unavoidable impurities, and having excellent oxidation resistance and shrink resistance. Fe-Cr-Al alloy foil for exhaust gas purifying catalyst carrier.
計で0.01〜0.20％含有し、残部がFeおよび不可避的不純
物からなる素材を、1050℃超え1150℃未満の温度範囲に
加熱し熱間圧延したのち、焼鈍および冷間圧延を施し合
金箔とすることを特徴とする耐酸化性に優れた排ガス浄
化触媒担体用Fe−Cr−Al合金箔の製造方法。3% by weight: Cr: 15.0 to 25.0%, Al: 4.0 to 6.5%, Zr: 0.005 to 0.10%, Ti: 0.005 to 0.05%, and Ti / Zr: 2 or less. A material containing 0.01 to 0.20% in total of one or more selected from rare earth elements, with the balance being Fe and unavoidable impurities, heated to a temperature range of more than 1050 ° C. and less than 1150 ° C. A method for producing an Fe-Cr-Al alloy foil for an exhaust gas purifying catalyst carrier having excellent oxidation resistance, wherein an alloy foil is subjected to annealing and cold rolling after cold rolling.
なくとも1 パスの圧延を圧下率：10％以下とすることを
特徴とする請求項３記載の耐酸化性に優れた排ガス浄化
触媒担体用Fe−Cr−Al合金箔の製造方法。4. The exhaust gas purifying catalyst excellent in oxidation resistance according to claim 3, wherein the hot rolling is performed so that at least one pass of the first three passes is reduced to a rolling reduction of 10% or less. A method for producing an Fe-Cr-Al alloy foil for a carrier.
計で0.01〜0.20％含有し、残部がFeおよび不可避的不純
物からなることを特徴とする請求項３または４記載の耐
酸化性に優れた排ガス浄化触媒担体用Fe−Cr−Al合金箔
の製造方法。5. The material contains, by weight%, Cr: 15.0 to 25.0%, Al: 4.0 to 6.5%, Zr: 0.005 to 0.05%, Ti: 0.005 to 0.05%, and Ti / Zr: 0.2. 5. The method according to claim 3, further comprising 0.01 to 0.20% in total of one or more selected from rare earth elements, and the balance consisting of Fe and unavoidable impurities. A method for producing an Fe-Cr-Al alloy foil for an exhaust gas purifying catalyst carrier having excellent oxidation resistance.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15934296A JP3613891B2 (en) | 1996-06-20 | 1996-06-20 | Method for producing Fe-Cr-Al alloy foil for exhaust gas purification catalyst carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP15934296A JP3613891B2 (en) | 1996-06-20 | 1996-06-20 | Method for producing Fe-Cr-Al alloy foil for exhaust gas purification catalyst carrier |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH108215A true JPH108215A (en) | 1998-01-13 |
| JP3613891B2 JP3613891B2 (en) | 2005-01-26 |
Family
ID=15691751
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP15934296A Expired - Fee Related JP3613891B2 (en) | 1996-06-20 | 1996-06-20 | Method for producing Fe-Cr-Al alloy foil for exhaust gas purification catalyst carrier |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3613891B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007538157A (en) * | 2004-05-19 | 2007-12-27 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | Heat resistant steel |
| JP2011032524A (en) * | 2009-07-31 | 2011-02-17 | Jfe Steel Corp | Stainless steel foil and method for producing the same |
| CN108479386A (en) * | 2018-05-31 | 2018-09-04 | 深圳市中金岭南科技有限公司 | A kind of device and processing method of selectivity heatable catalytic processing exhaust gas |
-
1996
- 1996-06-20 JP JP15934296A patent/JP3613891B2/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007538157A (en) * | 2004-05-19 | 2007-12-27 | サンドビック インテレクチュアル プロパティー アクティエボラーグ | Heat resistant steel |
| JP2011032524A (en) * | 2009-07-31 | 2011-02-17 | Jfe Steel Corp | Stainless steel foil and method for producing the same |
| CN108479386A (en) * | 2018-05-31 | 2018-09-04 | 深圳市中金岭南科技有限公司 | A kind of device and processing method of selectivity heatable catalytic processing exhaust gas |
| CN108479386B (en) * | 2018-05-31 | 2023-12-19 | 深圳市中金岭南科技有限公司 | Device and method for selectively heating and catalyzing waste gas |
Also Published As
| Publication number | Publication date |
|---|---|
| JP3613891B2 (en) | 2005-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5522330B2 (en) | Ferritic stainless steel foil | |
| EP2554700B1 (en) | Stainless steel foil and catalyst carrier for exhaust gas purification device using the foil | |
| EP3527683B1 (en) | Stainless steel sheet and stainless steel foil | |
| EP2695962B1 (en) | Stainless steel foil and catalyst carrier for exhaust emission control system using said foil | |
| US5045404A (en) | Heat-resistant stainless steel foil for catalyst-carrier of combustion exhaust gas purifiers | |
| JP3247162B2 (en) | Fe-Cr-Al-based alloy excellent in oxidation resistance and foil thereof | |
| JP4941320B2 (en) | Catalyst support for exhaust gas purification device and Fe-Cr-Al alloy foil used therefor | |
| EP0625585B1 (en) | Fe-Cr-Al alloy foil having high oxidation resistance for a substrate of a catalytic converter and method of manufacturing same | |
| JPH108215A (en) | Iron-chromium-aluminum alloy foil for catalyst support for exhaust gas cleaning | |
| JP3200160B2 (en) | Fe-Cr-Al alloy excellent in oxidation resistance and high-temperature embrittlement resistance, catalyst carrier using the same, and method for producing alloy foil | |
| WO2002002836A1 (en) | Fe-cr-al based alloy foil and method for producing the same | |
| JPH08299808A (en) | Production of metal carrier for catalyst excellent in oxidation resistance and durability | |
| JPH03170642A (en) | Heat-resistant ferritic stainless steel foil excellent in acid resistance in combustion exhaust gas | |
| JP3491334B2 (en) | Fe-Cr-Al alloy for catalytic converter carrier excellent in oxidation resistance and method for producing alloy foil using the same | |
| JPH07252608A (en) | Ferritic stainless steel alloy amenable to hot working | |
| JP3901224B2 (en) | Catalyst metal carrier | |
| EP4446441A1 (en) | Ferritic stainless steel and method for manufacturing same | |
| JP3633518B2 (en) | Ultrathin Fe-Cr-Al alloy foil and method for producing the same | |
| JPH1161348A (en) | Fe-cr-al-w base quenched alloy foil | |
| JPH06220587A (en) | Fe-cr-al alloy excellent in oxidation resistance and minimal in electric resistance reduction rate | |
| JP2579393B2 (en) | Fe-Cr-Al-based quenched alloy foil with excellent oxidation resistance | |
| JPH06108268A (en) | Ferritic stainless steel foil and its production | |
| JP4222217B2 (en) | Steel material for exhaust gas purification systems with excellent deformation resistance. | |
| JPH06104879B2 (en) | Heat-resistant stainless steel foil for combustion exhaust gas purification catalyst carrier | |
| JPH06248395A (en) | Ferritic stainless steel for automotive catalytic carrier excellent in oxidation resistance |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20040205 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20040224 |
|
| A521 | Written amendment |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20040419 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20041012 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20041025 |
|
| R150 | Certificate of patent (=grant) or registration of utility model |
Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20071112 Year of fee payment: 3 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20081112 Year of fee payment: 4 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20091112 Year of fee payment: 5 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20101112 Year of fee payment: 6 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111112 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20111112 Year of fee payment: 7 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20121112 Year of fee payment: 8 |
|
| FPAY | Renewal fee payment (prs date is renewal date of database) |
Free format text: PAYMENT UNTIL: 20131112 Year of fee payment: 9 |
|
| LAPS | Cancellation because of no payment of annual fees |