JPH01255648A - Fe-cr-al alloy excellent in oxidation resistance and resistance to high temperature embrittlement - Google Patents
Fe-cr-al alloy excellent in oxidation resistance and resistance to high temperature embrittlementInfo
- Publication number
- JPH01255648A JPH01255648A JP8221688A JP8221688A JPH01255648A JP H01255648 A JPH01255648 A JP H01255648A JP 8221688 A JP8221688 A JP 8221688A JP 8221688 A JP8221688 A JP 8221688A JP H01255648 A JPH01255648 A JP H01255648A
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- Prior art keywords
- alloy
- resistance
- weight
- high temperature
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- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 230000003647 oxidation Effects 0.000 title claims abstract description 30
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 30
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 title abstract 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 31
- 239000000956 alloy Substances 0.000 claims abstract description 31
- 229910052747 lanthanoid Inorganic materials 0.000 claims abstract description 8
- 150000002602 lanthanoids Chemical class 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 abstract description 17
- 239000011888 foil Substances 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 7
- 239000000203 mixture Substances 0.000 abstract description 4
- 150000001247 metal acetylides Chemical class 0.000 abstract description 3
- 150000004767 nitrides Chemical class 0.000 abstract description 3
- 239000000654 additive Substances 0.000 abstract 1
- 230000000996 additive effect Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 12
- 230000003197 catalytic effect Effects 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 238000009864 tensile test Methods 0.000 description 7
- 238000005098 hot rolling Methods 0.000 description 6
- 229910052761 rare earth metal Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 5
- 238000000746 purification Methods 0.000 description 5
- 230000007704 transition Effects 0.000 description 5
- 241000264877 Hippospongia communis Species 0.000 description 4
- 229910052746 lanthanum Inorganic materials 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 229910052684 Cerium Inorganic materials 0.000 description 3
- 229910052779 Neodymium Inorganic materials 0.000 description 3
- 238000000137 annealing Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 229910052878 cordierite Inorganic materials 0.000 description 2
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910017060 Fe Cr Inorganic materials 0.000 description 1
- 229910002544 Fe-Cr Inorganic materials 0.000 description 1
- 229910017112 Fe—C Inorganic materials 0.000 description 1
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、耐酸化性、耐高温脆化性に優れたＦｅ−Ｃｒ
−Ａｌ２系合金に関し、高温酸化性雰囲気下で激しい繰
返し酸化を受ける自動車排ガス浄化用触媒コンバータに
好適である。Detailed Description of the Invention [Industrial Field of Application]
- Regarding Al2-based alloys, it is suitable for catalytic converters for purifying automobile exhaust gas, which are subjected to intense repeated oxidation in high-temperature oxidizing atmospheres.
［従来の技術１
従来、自動車排ガス浄化用触媒コンバータには、コーデ
ィエライト（２Ｍｇ０・２Ａｊ２２０３・５Ｓｉ０２）
の押出焼成ハニカムにγ−アルミナ微粒子を触媒担体と
してコーティングした後、ｐｔなどの触媒をつけたもの
が用いられている。[Conventional technology 1 Conventionally, cordierite (2Mg0, 2Aj2203, 5Si02) has been used in catalytic converters for automobile exhaust gas purification.
An extruded fired honeycomb coated with γ-alumina fine particles as a catalyst carrier and then coated with a catalyst such as PT is used.
特開昭５６−９６７２６号公報に示されているように、
このコーディエライト製ハニカムを耐酸化ステンレス箔
を組立てて製作した金属製ハニカムにすると、コンバー
タの小型化、エンジン性能の向上など、種々の利点があ
る。前記引用公報では耐酸化ステンレス箔としてイツト
リウム（Ｙ）を添加したＦｅ−Ｃｒ−Ａｌ２系合金（Ｃ
ｒ：１５〜２５重量％、Ａｌ２．：３〜６重量％、Ｙ：
０．３〜１．０重量％）を提案しているが、Ｙが希少金
属であるため非常に高価となり、かつ供給量にも不安が
あり、一般に自動車に用いるのは経済性の点で困難であ
った。As shown in Japanese Patent Application Laid-open No. 56-96726,
If this cordierite honeycomb is made into a metal honeycomb manufactured by assembling oxidation-resistant stainless steel foil, there are various advantages such as miniaturization of the converter and improvement of engine performance. In the cited publication, Fe-Cr-Al2 alloy (C
r: 15-25% by weight, Al2. :3-6% by weight, Y:
0.3 to 1.0% by weight), but since Y is a rare metal, it is very expensive and there is also uncertainty about the supply amount, so it is generally difficult to use it in automobiles from an economic point of view. Met.
これに対し、特開昭５８−１７７４３７号公報ではＣｒ
：８〜２５重量％、Ａｌ２：３〜８重屑％、全希土類元
素が０．０６重量％までで。On the other hand, in Japanese Patent Application Laid-open No. 58-177437, Cr
: 8-25% by weight, Al2: 3-8% by weight, total rare earth elements up to 0.06% by weight.
０．００２〜０．０５ｆｆｉｉ％のＣｅ、Ｌａ、Ｎｄ等
を添加した合金（以下これをＦ ｅ −Ｃ’ｒ −Ａ
ｌ２−ＲＥＶ合金と呼ぶ）の使用を提案している。これ
は希土類元素の添加によってスケールの剥離を防いだＦ
ｅ−Ｃｒ−Ａｌ２系合金で、電熱線などには古くから用
いられていたものである。Alloy containing 0.002 to 0.05ffii% of Ce, La, Nd, etc. (hereinafter referred to as Fe-C'r-A
12-REV alloy). This is F, which prevents scale peeling by adding rare earth elements.
It is an e-Cr-Al2 alloy that has been used for heating wires and the like for a long time.
このようなＦｅ−Ｃｒ−Ａｌ２−ＲＥＭ系合金では一般
用途では十分な耐酸化性を持っているが。Such Fe-Cr-Al2-REM alloys have sufficient oxidation resistance for general purposes.
自動車の排気ガス浄化用触媒コンバータのように発進、
加速、停止のたびに過酷な高温繰返し酸化と激しい振動
を受ける場合、酸化スケールが剥離してしまう。Starts like a catalytic converter for purifying automobile exhaust gas,
If the vehicle is subjected to repeated oxidation at high temperatures and violent vibrations each time it accelerates or stops, the oxide scale will peel off.
〔発明が解決しようとする課題］
この耐酸化性不足を解決するため、本発明者らは特開昭
６３−４５３５１に述べるＣｅを除くＬａ、Ｎｄ等を添
加したＦｅ−Ｃｒ−ＡＱ系合金を提供した。この合金系
は耐酸化性に優れ自動車排ガス浄化用触媒コンバータに
好適である。しかし、この合金系も前述のＦｅ−Ｃｒ−
Ａβ−ＲＥＭ系合金と同様に特に板厚が薄い場合に高温
長時間使用すると張力が加わったときに箔が破断するま
での伸びる量が著しく低下する（本発明ではこれを高温
脆化と称する）欠点があった。[Problems to be Solved by the Invention] In order to solve this lack of oxidation resistance, the present inventors developed a Fe-Cr-AQ alloy to which La, Nd, etc. were added, excluding Ce, as described in JP-A No. 63-45351. provided. This alloy system has excellent oxidation resistance and is suitable for catalytic converters for automobile exhaust gas purification. However, this alloy system also has the aforementioned Fe-Cr-
Similar to Aβ-REM alloys, when used for long periods of time at high temperatures especially when the plate thickness is thin, the amount by which the foil stretches until it breaks when tension is applied significantly decreases (this is referred to as high-temperature embrittlement in the present invention). There were drawbacks.
自動車排ガス浄化用触媒コンバータ用の金属製ハニカム
には各種の形式があり、構造によっては使用時の熱膨張
、収縮量が大きく、材料に大きな張力が加わり長時間高
温使用で脆化した合金がその張力に耐えられず破断が生
じるものがある。There are various types of metal honeycombs used in catalytic converters for automobile exhaust gas purification.Depending on the structure, the amount of thermal expansion and contraction during use is large, and the material is subjected to large tension and the alloy becomes brittle due to long-term high-temperature use. Some cannot withstand the tension and break.
触媒コンバータは５０μｍ程度の厚さの箔の上に触媒を
コーティングした構造であるから、破断が生ずるとその
近傍の触媒が剥離し、排ガス浄化能力が低下する。Since the catalytic converter has a structure in which a catalyst is coated on a foil with a thickness of about 50 μm, if a break occurs, the catalyst in the vicinity of the break will peel off, reducing the exhaust gas purification ability.
本発明は特に５０μｍ程度の板厚での高温長時間使用後
の脆化を防ぎ、耐酸化性を同時に満たす成分バランスを
有する材料を提供するものである。The present invention provides a material having a component balance that prevents embrittlement after long-term use at high temperatures, especially when the plate thickness is approximately 50 μm, and satisfies oxidation resistance at the same time.
［課題を解決するための手段］
本発明は上記問題解決のために開発された耐酸化性、耐
高温脆化性に優れたＦｅ−Ｃｒ−Ａβ系合金であって、
Ｃ：０．０７重量％以下
Ｓｉ：１．０重量％以下
Ｃｒ：１３虫量％以上２７重量％以下
八２・３．５重１％以上８重量％以下
Ｃｅを除くランタノイド： ０．０５重機％以上０．２
０重量％以下
Ｔｉ：０．０１重啜％以上
０．１０重量％以下
Ｎ ｂ ： Ｏ，Ｏ１重里％以上
０、１０重量％以下
を含み、残分がＦｅと不可避不純物よりなることを特徴
とするものである。[Means for Solving the Problems] The present invention is a Fe-Cr-Aβ alloy developed to solve the above problems and having excellent oxidation resistance and high temperature embrittlement resistance, C: 0.07 weight % or less Si: 1.0% by weight or less Cr: 13% or more and 27% by weight or less 82.3.5 weight 1% or more and 8% or less Lanthanoids excluding Ce: 0.05 or more heavy machinery 0.2
0% by weight or less Ti: 0.01% by weight or more and 0.10% by weight or less Nb: Contains O, O 1% by weight or more and 0.10% by weight or less, and the remainder consists of Fe and inevitable impurities. It is something to do.
［作用１
本発明合金は各成分の含有量によって、耐酸化性および
耐高温脆化性が極めて高くなる作用を有し、特に耐酸化
性向上はＣｅを積極的に除外したランタノイドを利用し
、耐高温脱化性向上はＴｉとＮｂの複合添加を利用した
ものである。以下各成分の限定理由を述べる。[Effect 1] The alloy of the present invention has the effect of extremely high oxidation resistance and high temperature embrittlement resistance depending on the content of each component, and in particular, the oxidation resistance can be improved by using lanthanoids that actively exclude Ce. The high-temperature deoxidation resistance is improved by using a composite addition of Ti and Nb. The reasons for limiting each component will be described below.
■ ＴｉとＮｂ
この成分は炭化物、窒化物を形成し１合金中に微細に分
散すること、高温使用によって生じた酸化皮膜中に混入
することにより、高温長時間使用による脆化が生じるの
を防ぐ。■ Ti and Nb These components form carbides and nitrides, are finely dispersed in the alloy, and are mixed into the oxide film formed by high-temperature use, thereby preventing embrittlement caused by long-term use at high temperatures. .
特開昭５８−１７７４３７号では
ここで、
（：＜０−０５０％
Ｎ＜０．０５０％
のＮｂを、特開昭６３−４５３５１では「Ｃ市川％の５
倍以上０．１０重量％以下」のＴｉを添加しているが１
本発明者らの研究によると、Ｎｂ。In JP-A No. 58-177437, Nb of (:<0-050% N<0.050%) is used, and in JP-A No. 63-45351, "C Ichikawa% of 5
Ti is added in an amount of 0.10% by weight or more, but 1
According to the research of the present inventors, Nb.
Ｔｉはそれぞれ単独で合金に添加しても、箔の耐高温脆
化性は改善されず、０．０１重量％以上のＴｉとＮｂの
両者を複合して初めて効果あることが明らかになった。It has been revealed that even if Ti is added alone to the alloy, the high-temperature embrittlement resistance of the foil is not improved, and that it is only effective when both Ti and Nb are combined in an amount of 0.01% by weight or more.
ただし、ＴｉとＮｂはそれぞれｏ、ｔｏｉ量％を越えて
添加すると耐酸化性を低下させるので、ＴｉとＮｂはそ
れぞれ０．０１重量％以上０．１０重量％以下とする。However, if Ti and Nb are added in amounts exceeding o and toi %, respectively, the oxidation resistance will be reduced, so Ti and Nb are each set at 0.01% by weight or more and 0.10% by weight or less.
■ Ｃｅを除いたランタノイド：
ランタノイドはＬａ、Ｃｅ、Ｎｄその地厚子番号５１か
ら７１までの１５ｍの金属元素である。Ｃｅを除＜Ｌａ
、Ｎｄ等のランタノイドは耐酸化性および酸化スケール
の耐剥離性向上に対し顕著な効果がある。ただし、含有
量が０．０５重量％未満では厚さ２５〜８０μｍ程度の
箔での耐酸化性を確保することはできず、０．２０重量
％を越えると熱間圧延が不可能になるので、０．０５重
量％以上０．２０重量％以下とした。Ｃｅは熱間加工性
、耐酸化性を恋化させるので除外される。■ Lanthanoids excluding Ce: Lanthanoids are 15m metal elements including La, Ce, and Nd, with thickness numbers 51 to 71. Excluding Ce<La
, Nd, and other lanthanoids have a remarkable effect on improving oxidation resistance and peeling resistance of oxide scale. However, if the content is less than 0.05% by weight, it will not be possible to ensure oxidation resistance in foils with a thickness of approximately 25 to 80 μm, and if the content exceeds 0.20% by weight, hot rolling will not be possible. , 0.05% by weight or more and 0.20% by weight or less. Ce is excluded because it impairs hot workability and oxidation resistance.
■ Ｃｒ：
１３重量％未満では耐酸化性が確保できず、２７重重篤
を超えると靭性が低下し、冷間加工が困難となるので１
３〜２７重量％とした。■ Cr: If it is less than 13% by weight, oxidation resistance cannot be ensured, and if it exceeds 27% by weight, the toughness decreases and cold working becomes difficult.
The content was 3 to 27% by weight.
■ Ａｌ１：
３．５重量％未満では耐酸化性を確保することができず
、８重量％を超えると熱間圧延が困難となるので３．５
〜８重量％とした。■ Al1: If it is less than 3.5% by weight, oxidation resistance cannot be ensured, and if it exceeds 8% by weight, hot rolling becomes difficult.
~8% by weight.
■ Ｓｉ：
１．０重量％を超えると加工性を低下させるので１．０
重量％以下とした。■Si: If it exceeds 1.0% by weight, workability will be reduced, so set it to 1.0% by weight.
% by weight or less.
■ Ｃ二
過剰になると靭性を低下させ、冷間圧延性、加工性を悪
化させるので０．０７重量％以下にする必要がある。(2) An excess of C2 lowers toughness and impairs cold rollability and workability, so it is necessary to limit the content to 0.07% by weight or less.
次に本発明に係る合金の厚さについて述べる。Next, the thickness of the alloy according to the present invention will be described.
高温長時間使用によって伸び性が低下するのは板厚が特
に薄くなった場合に顕著に起こる現象であり、板厚が８
０μｍより大きければ低下の程度も小さく伸び性の低下
は問題とならない。The decrease in elongation due to long-term use at high temperatures is a phenomenon that occurs particularly when the plate thickness becomes thin.
If it is larger than 0 μm, the degree of decrease is small and the decrease in elongation is not a problem.
また、板厚が２５μｍ未満では本合金によっても十分な
耐酸化性を確保することができない。本発明の合金は板
厚が２５μｍ以上８０μｍ以下の箔に適用したときに好
適な性能を発揮するものである。Further, if the plate thickness is less than 25 μm, sufficient oxidation resistance cannot be ensured even with this alloy. The alloy of the present invention exhibits suitable performance when applied to a foil having a thickness of 25 μm or more and 80 μm or less.
次に、高温脆化について説明する。高温脆化は高温酸化
によって生じる表面の酸化皮膜が原因の一つである。本
合金系は自動車排ガス浄化用触媒コンバータが用いられ
る９００〜１０００℃の高温酸化性環境下では表面に厚
さ数μｍのＡｌ２２０３酸化皮膜が生じる。この酸化皮
膜は場所によって、合金の中に深さ数μｍ程度の楔状に
発達してしまい、張力が加わった場合、この楔状酸化皮
膜部分が欠陥となって材料が破断してしまう。板厚が厚
い場合はこの欠陥部分の影響が比較的に少なくなり、高
温脆化は実質的に生じない。Next, high temperature embrittlement will be explained. One of the causes of high-temperature embrittlement is an oxide film on the surface caused by high-temperature oxidation. This alloy system forms an Al2203 oxide film with a thickness of several micrometers on the surface under a high-temperature oxidizing environment of 900 to 1000°C in which a catalytic converter for automobile exhaust gas purification is used. This oxide film develops in the alloy in a wedge shape with a depth of several μm depending on the location, and when tension is applied, this wedge-shaped oxide film portion becomes a defect and the material breaks. When the plate thickness is large, the influence of this defective portion becomes relatively small, and high-temperature embrittlement does not substantially occur.
Ｆｅ−Ｃｒ−ＡＱ−ＲＥＭ系合金にＴｉ、Ｎｂを複合添
加した本発明ではこの楔状酸化皮膜欠陥が発生せず、脆
化が生じない。In the present invention, in which Ti and Nb are added in combination to the Fe-Cr-AQ-REM alloy, this wedge-shaped oxide film defect does not occur and embrittlement does not occur.
一般にＦｅ−Ｃｒ、Ｆｅ−Ｃｒ−Ｎｉ、Ｆｅ−Ｃｒ−，
６ｊ２合金にＮｂ、Ｔｉを添加すると高温使用時の結晶
粒粗大化が押えられ脆化が防がれることは良く知られて
いるが、前述のように本合金箔に対するＴｉ、Ｎｂ？Ｉ
合添加効果はこれと異なる機構によって生ずる。単に結
晶粒粗大化防止の効果だけを見れば、同一添加量ではＮ
ｂ単独添加の方がＮｂ、Ｔｉ複合添加、Ｔｉ単独添加よ
り優れている。本発明は結晶粒粗大化抑制ではなく、楔
状酸化皮膜欠陥発生防止により耐高温脆化性を向上させ
る作用を有するのである。Generally Fe-Cr, Fe-Cr-Ni, Fe-Cr-,
It is well known that adding Nb and Ti to 6j2 alloy suppresses grain coarsening during high temperature use and prevents embrittlement, but as mentioned above, Ti and Nb for this alloy foil? I
The combined effect occurs through a different mechanism. If we simply look at the effect of preventing crystal grain coarsening, the same amount of N
The addition of b alone is superior to the combined addition of Nb and Ti, and the addition of Ti alone. The present invention has the effect of improving high-temperature embrittlement resistance by preventing the generation of wedge-shaped oxide film defects, rather than suppressing grain coarsening.
〔実施例１
第１表に本発明の実施例の合金の化学成分を示し、第２
表に比較例の合金の化学成分を示す。[Example 1 Table 1 shows the chemical composition of the alloy of the example of the present invention,
The table shows the chemical composition of the comparative example alloy.
実施例および比較例はそれぞれ１０ｋｇインゴットに溶
装造塊した後、１２００℃で板厚３ｍｍまで熱間圧延し
た。この段階でＣｅａ度が０．０７重量％のＢ−１，Ａ
Ｉ２濃度が８．１重量％のＢ−２、Ｌａ４度が０．２２
重量％のＢ−３は熱間圧延時に鋼塊が割れたので、その
後の試験は行っていない。In the examples and comparative examples, each ingot was melted into a 10 kg ingot and then hot rolled at 1200° C. to a thickness of 3 mm. At this stage, B-1 and A with a Cea degree of 0.07% by weight
B-2 with I2 concentration of 8.1% by weight, La4 degree of 0.22
As for B-3 (wt%), the steel ingot cracked during hot rolling, so no further tests were conducted.
比較例のうち上記Ｂ−１，２，３を除く比較例および実
施例は、次に９００℃で焼鈍した後シャルビー試験を行
い靭性を調べた。Ｃが０．０８２重量％と高いＢ−６で
は脆性・靭性の遷移温度が２００℃と高く冷間圧延が困
難であった。同様にＳｉが１．８重量％のＢ−４とＣｒ
が２８．４重量％のＢ−５も遷移温度が１５０℃を超え
冷間圧延が困難であり、これらはその後の試験は行って
いな（、Ｓ。Among the comparative examples, the comparative examples and examples excluding B-1, 2, and 3 were annealed at 900° C. and then subjected to a Charby test to examine their toughness. In B-6, which has a high C content of 0.082% by weight, the transition temperature between brittleness and toughness was as high as 200°C, making cold rolling difficult. Similarly, B-4 with Si of 1.8% by weight and Cr
B-5 with 28.4% by weight also had a transition temperature exceeding 150°C and was difficult to cold-roll, and no further tests were conducted on these (S.
実施例Ａ１〜４と比較例Ｂ−７〜１２は脆性、延性遷移
温度は１００℃以下の良好な靭性があり、その後、脱ス
ケール、冷間圧延、焼鈍を繰返し板厚５０ｕｍの箔にし
た。Examples A1 to A4 and Comparative Examples B-7 to B-12 had good toughness with brittle and ductile transition temperatures of 100° C. or lower, and were then repeatedly subjected to descaling, cold rolling, and annealing to form foils with a thickness of 50 μm.
５０μｍ１幅２０ｍｍ、長さ３０ｍｍの試験片を採取し
て、１１５０℃大気中雰囲気で酸化試験を行った。A test piece measuring 50 μm, 20 mm in width, and 30 mm in length was taken and subjected to an oxidation test at 1150° C. in air.
実施例Ａ−１，３，４，比較例Ｂ−７，８，９は２４０
時間後も酸化増量が１．０ｍｇ／ｃｒｎ″程度で良好な
耐酸化性を示した。Examples A-1, 3, 4, Comparative Examples B-7, 8, 9 are 240
Even after hours, the oxidation weight increase was about 1.0 mg/crn'', showing good oxidation resistance.
実施例Ａ−３も１２０時間までは酸化増量１．０ｍ ｇ
／ ｃ ｒｎ”で１４４時間で１．５ｍｇ／ｃｍ”を
超えた。これに対してＡｌ２が３．４重量％と少ないＢ
−７、Ｃｒが１２．５重量％と少ないＢ−８、Ｔｉが０
．１６重量％と多いＢ−１２、Ｎｂが０．１２％と多い
Ｂ−１３と希土類がＣｅであるＢ−１４は９６時間まで
に酸化増量が１．５ｍｇ／ｃｒｎ’を超え、１２０時間
までには箔全体が酸化物となり原形を留めていない。Example A-3 also had an oxidation weight gain of 1.0 mg up to 120 hours.
/ crn” exceeded 1.5 mg/cm” in 144 hours. On the other hand, B contains less Al2 at 3.4% by weight.
-7, B-8 with low Cr content of 12.5% by weight, 0 Ti content
．． For B-12 with a high content of 16% by weight, B-13 with a large content of Nb of 0.12%, and B-14 with a rare earth of Ce, the oxidation weight increase exceeded 1.5 mg/crn' by 96 hours, and by 120 hours. The entire foil becomes oxide and does not retain its original shape.
この内、実施例Ａ−１〜４、比較例Ｂ−９〜１４の板厚
０．５ ｍ ｍと５０ｕｍの試料を９００°Ｃで１分間
焼鈍した後、板厚０．５ ｍ ｍの試料はＪＩＳ１３号
Ｂ （ＪＩＳ Ｚ ２２０１）の引張試験片を１０
本採取し、板厚５０μｍの試料は幅１５ｍｍ、長さ１５
０ｍｍの引張試験片を１０本採取した。これらの引張試
験Ｑ内容５本はそのまま引張試験を行い伸びを測定した
。残りの５本は大気雰囲気中で９２５℃Ｘ９６ｈｒの熱
処理した後、引張試験を行った。Among these, after annealing the samples of Examples A-1 to 4 and Comparative Examples B-9 to 14 with a plate thickness of 0.5 mm and 50 um at 900°C for 1 minute, the samples with a plate thickness of 0.5 mm 10 tensile test pieces of JIS No. 13 B (JIS Z 2201)
The actual sample with a plate thickness of 50 μm has a width of 15 mm and a length of 15 mm.
Ten tensile test pieces of 0 mm were collected. These five tensile test Q contents were subjected to a tensile test as they were, and the elongation was measured. The remaining five pieces were heat treated at 925°C for 96 hours in the air, and then subjected to a tensile test.
その結果を第３表に示す。実施例、比較例とも板厚０．
５ ｍ ｍの試験片では熱処理後も熱処理前とほぼ同様
の伸びを示し脆化していない。The results are shown in Table 3. Both the example and the comparative example have a plate thickness of 0.
The 5 mm test piece showed almost the same elongation after heat treatment as before heat treatment and was not embrittled.
板厚５０μｍの試験片ではＴｉ、Ｎｂを添加していない
Ｂ−９、Ｎｂを添加していないＢ−１０、Ｔｉの添加量
がＯ，ＯＯ５％と少ないＢ−１１は熱処理後の伸びが３
〜５％と完全に脆化している。これに対して、Ｔｉ、Ｎ
ｂを適量複合添加した実施例Ａ−１〜４．Ｂ−１２〜１
４は熱処理後も１２％以上の伸びがあり、脆化していな
い。In the test specimens with a thickness of 50 μm, B-9 with no added Ti and Nb, B-10 with no added Nb, and B-11 with a small amount of Ti added of 5% O and OO had an elongation of 3 after heat treatment.
~5%, completely embrittled. On the other hand, Ti, N
Examples A-1 to A-4 in which an appropriate amount of b was added in combination. B-12~1
No. 4 had an elongation of 12% or more even after heat treatment, and was not brittle.
以上の結果を総合して第１表、第２表中に合わせて評価
したが１本発明の範囲にある第１表のＦｅ−Ｃｒ−Ａｌ
１合金は製造性および特性の両方において優れているこ
とは明白である。The above results were combined and evaluated in Tables 1 and 2.
It is clear that the No. 1 alloy is superior in both manufacturability and properties.
なお、第１表、第２表中における評価の区分は以下の基
準による。The classification of evaluation in Tables 1 and 2 is based on the following criteria.
熱間圧延性： ○：１２００°Ｃ加熱後、熱間圧延可能であったもの。Hot rollability: ○: Hot rolling was possible after heating at 1200°C.
Ｘ：１２００°Ｃ加熱後、熱間圧延不可能であったもの
。X: Hot rolling was impossible after heating at 1200°C.
靭 性：
○：熱延焼鈍扱での脆性−延性遷移温度が１５０℃未満
のもの。Toughness: ○: The brittle-ductile transition temperature during hot rolling annealing is less than 150°C.
×：熱延焼鈍板での脆性−延性遷移温度が１５０℃以上
のもの。×: The brittle-ductile transition temperature of the hot-rolled annealed plate is 150°C or higher.
耐酸化性：
○：！５０ｕｍ厚の箔で１１５０°ＣＸ１２０時間大気
中加熱後の重量増加が１．５ｍｇ／ｃｒｎ″未満。Oxidation resistance: ○:! Weight increase of 50 um thick foil after heating in air at 1150°C for 120 hours is less than 1.5 mg/crn''.
ｘ ： ５０ｇｍ厚の箔で１１５０℃×１２０時間大気
中加熱後の重量増加が１．５ｍｇ／ｃｒｎ”以上。x: Weight increase of 50 gm thick foil after heating in air at 1150° C. for 120 hours is 1.5 mg/crn” or more.
耐高温脆化性：
○：５０μｍ厚の箔で９２５℃×９６時間大気中加熱後
の引張試験結果の伸びが１０％以上。High temperature embrittlement resistance: ○: 50 μm thick foil has an elongation of 10% or more in the tensile test result after heating at 925° C. in the air for 96 hours.
×：５０μｍ厚の箔で９２５℃×９６時間大気中加熱後
の引張試験結果の伸びが１０％未満。×: The elongation of a 50 μm thick foil in a tensile test after heating in the air at 925° C. for 96 hours was less than 10%.
［発明の効果１
本発明によれば、板厚２５μｍ〜８０μｍのＴｉ、Ｎｂ
を複合添加した耐酸化性、耐高温脆化性に優れたＦｅ−
Ｃｒ−Ａｌ１系合金箔が提供され、高温酸化性雰囲気下
で激しい繰返し酸化を受ける自動車排ガス浄化用触媒コ
ンバータに好適である。[Effect of the invention 1 According to the present invention, Ti, Nb with a plate thickness of 25 μm to 80 μm
Fe-, which has excellent oxidation resistance and high temperature embrittlement resistance with composite addition of
A Cr-Al1 alloy foil is provided and is suitable for a catalytic converter for purifying automobile exhaust gas, which is subjected to intense and repeated oxidation in a high-temperature oxidizing atmosphere.
また、＠述の特開昭５６−９６７２６号公報では特殊な
熱処理で表面に長さ数μｍのＡｌ２２０３ウイスカーを
生成した上に、触媒のコーティングを行っている６本発
明鋼もこれと同一の熱処理を行った場合、良好なＡｆ１
２０３ウィスカーが生成するので、この製造方法による
触媒コンバータにも好適である。In addition, in JP-A No. 56-96726 mentioned in @, Al2203 whiskers several μm in length are generated on the surface by special heat treatment, and the 6 invention steel is also coated with a catalyst. Good Af1
Since 203 whiskers are generated, this manufacturing method is also suitable for catalytic converters.
Claims (1)
とする耐酸化性、耐高温脆化性に優れたＦｅ−Ｃｒ−Ａ
ｌ系合金。[Claims] 1 C: 0.07 wt% or less Si: 1.0 wt% or less Cr: 13 wt% or more and 27 wt% or less Al: 3.5 wt% or more and 8 wt% or less Lanthanoids excluding Ce: Contains 0.05 wt% or more and 0.20 wt% or less Ti: 0.01 wt% or more and 0.10 wt% or less Nb: 0.01 wt% or more and 0.10 wt% or less, the remainder being Fe and inevitable impurities Fe-Cr-A with excellent oxidation resistance and high temperature embrittlement resistance, characterized by
l-based alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8221688A JPH01255648A (en) | 1988-04-05 | 1988-04-05 | Fe-cr-al alloy excellent in oxidation resistance and resistance to high temperature embrittlement |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8221688A JPH01255648A (en) | 1988-04-05 | 1988-04-05 | Fe-cr-al alloy excellent in oxidation resistance and resistance to high temperature embrittlement |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH01255648A true JPH01255648A (en) | 1989-10-12 |
Family
ID=13768223
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8221688A Pending JPH01255648A (en) | 1988-04-05 | 1988-04-05 | Fe-cr-al alloy excellent in oxidation resistance and resistance to high temperature embrittlement |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH01255648A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02254136A (en) * | 1989-03-27 | 1990-10-12 | Nippon Steel Corp | Heat-resistant and oxidation-resistant fe-cr-al series alloy having excellent manufacturability |
| CN104831174A (en) * | 2015-05-08 | 2015-08-12 | 上海蓝铸特种合金材料有限公司 | High-temperature oxidation resistant metal material and preparation method thereof |
| CN110669998A (en) * | 2019-10-28 | 2020-01-10 | 常熟市夸克电阻合金有限公司 | Preparation process of high-stability iron-chromium-aluminum resistance wire |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49115927A (en) * | 1973-03-10 | 1974-11-06 | ||
| JPS5436125A (en) * | 1977-08-26 | 1979-03-16 | Hitachi Denshi Ltd | Generator circuit for jitter-less pulse signal |
| JPS6345351A (en) * | 1986-04-21 | 1988-02-26 | Kawasaki Steel Corp | Fe-cr-al alloy having superior resistance to stripping of oxide scale |
-
1988
- 1988-04-05 JP JP8221688A patent/JPH01255648A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS49115927A (en) * | 1973-03-10 | 1974-11-06 | ||
| JPS5436125A (en) * | 1977-08-26 | 1979-03-16 | Hitachi Denshi Ltd | Generator circuit for jitter-less pulse signal |
| JPS6345351A (en) * | 1986-04-21 | 1988-02-26 | Kawasaki Steel Corp | Fe-cr-al alloy having superior resistance to stripping of oxide scale |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH02254136A (en) * | 1989-03-27 | 1990-10-12 | Nippon Steel Corp | Heat-resistant and oxidation-resistant fe-cr-al series alloy having excellent manufacturability |
| CN104831174A (en) * | 2015-05-08 | 2015-08-12 | 上海蓝铸特种合金材料有限公司 | High-temperature oxidation resistant metal material and preparation method thereof |
| CN110669998A (en) * | 2019-10-28 | 2020-01-10 | 常熟市夸克电阻合金有限公司 | Preparation process of high-stability iron-chromium-aluminum resistance wire |
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