JP5387057B2 - Ferritic stainless steel with excellent heat resistance and toughness - Google Patents

Ferritic stainless steel with excellent heat resistance and toughness Download PDF

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JP5387057B2
JP5387057B2 JP2009050160A JP2009050160A JP5387057B2 JP 5387057 B2 JP5387057 B2 JP 5387057B2 JP 2009050160 A JP2009050160 A JP 2009050160A JP 2009050160 A JP2009050160 A JP 2009050160A JP 5387057 B2 JP5387057 B2 JP 5387057B2
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康 加藤
知正 平田
徹之 中村
工 宇城
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    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/001Ferrous alloys, e.g. steel alloys containing N
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/20Ferrous alloys, e.g. steel alloys containing chromium with copper
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/004Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/005Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/02Ferrous alloys, e.g. steel alloys containing silicon
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/04Ferrous alloys, e.g. steel alloys containing manganese
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/06Ferrous alloys, e.g. steel alloys containing aluminium
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/22Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22CALLOYS
    • C22C38/00Ferrous alloys, e.g. steel alloys
    • C22C38/18Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium

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  • Engineering & Computer Science (AREA)
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Description

本発明は、Cr含有鋼に係り、とくに自動車やオートバイの排気管、コンバーターケースや火力発電プラントの排気ダクト等の高温環境下で使用される排気系部材に用いて好適な、高い耐熱性(耐熱疲労特性、耐酸化性)と母材の靭性に優れるフェライト系ステンレス鋼に関するものである。   TECHNICAL FIELD The present invention relates to Cr-containing steel, and particularly has high heat resistance (heat resistant) suitable for use in exhaust system members used in high-temperature environments such as exhaust pipes of automobiles and motorcycles, converter cases and exhaust ducts of thermal power plants. It relates to a ferritic stainless steel having excellent fatigue properties and oxidation resistance and toughness of the base material.

自動車の排気系環境下で使用されるエキゾーストマニホールド、排気パイプ、コンバーターケース、マフラー等の排気系部材には、熱疲労特性や耐酸化性(以下、両特性をまとめて「耐熱性」と呼ぶ。)に優れることが要求されている。このような耐熱性が求められる用途には、現在、NbとSiを添加した、例えば、Type429(14Cr−0.9Si−0.4Nb系)のようなCr含有鋼が多く使用されている。しかし、エンジン性能の向上に伴って、排ガス温度が900℃を超えるような温度まで上昇してくると、Type429では、熱疲労特性が不十分となってきた。   Exhaust manifolds, exhaust pipes, converter cases, mufflers and other exhaust system members used in the exhaust system environment of automobiles are called thermal fatigue characteristics and oxidation resistance (hereinafter, both characteristics are collectively referred to as “heat resistance”). ). In applications where such heat resistance is required, Cr-containing steels such as Type 429 (14Cr-0.9Si-0.4Nb system) to which Nb and Si are added are currently widely used. However, when the exhaust gas temperature rises to a temperature exceeding 900 ° C. as the engine performance is improved, Type 429 has insufficient thermal fatigue characteristics.

この問題に対しては、NbとMoを添加して高温耐力を向上させたCr含有鋼や、JIS G4305に規定されるSUS444(19Cr−0.5Nb−2Mo鋼)、Nb,Mo,Wを添加したフェライト系ステンレス鋼等が開発されている(例えば、特許文献1参照)。しかしながら、昨今におけるMoやW等の希少金属原料の異常な高騰から、安価な原料を用いて同等の耐熱性を有する材料の開発が要求されるようになってきた。   For this problem, Cr-containing steel with improved high-temperature proof stress by adding Nb and Mo, SUS444 (19Cr-0.5Nb-2Mo steel), Nb, Mo, and W specified in JIS G4305 are added. Ferritic stainless steel and the like have been developed (see, for example, Patent Document 1). However, due to the recent abnormal rise of rare metal raw materials such as Mo and W, development of materials having equivalent heat resistance using inexpensive raw materials has been required.

高価な元素であるMoやWを用いない耐熱性に優れた材料としては、例えば、特許文献2には、10〜20mass%Cr鋼に、Nb:0.50mass%以下、Cu:0.8〜2.0mass%、V:0.03〜0.20mass%を添加した自動車排ガス流路部材用フェライト系ステンレス鋼が、また特許文献3には、10〜20mass%Cr鋼に、Ti:0.05〜0.30mass%、Nb:0.10〜0.60mass%、Cu:0.8〜2.0mass%、B:0.0005〜0.02mass%を添加した熱疲労特性に優れたフェライト系ステンレス鋼が、また特許文献4には、15〜25mass%Cr鋼に、Cu:1〜3mass%を添加した自動車排気系部品用フェライト系ステンレス鋼が開示されている。これらの鋼はいずれも、Cuを添加することによって、熱疲労特性を向上させているのが特徴である。   As a material excellent in heat resistance that does not use expensive elements such as Mo and W, for example, in Patent Document 2, 10 to 20 mass% Cr steel, Nb: 0.50 mass% or less, Cu: 0.8 to Ferritic stainless steel for automobile exhaust gas flow channel member to which 2.0 mass%, V: 0.03 to 0.20 mass% is added, and Patent Document 3 discloses that 10-20 mass% Cr steel, Ti: 0.05 -0.30 mass%, Nb: 0.10-0.60 mass%, Cu: 0.8-2.0 mass%, B: ferritic stainless steel with excellent thermal fatigue properties with addition of 0.0005-0.02 mass% Steel and Patent Document 4 disclose ferritic stainless steel for automotive exhaust system parts in which Cu: 1 to 3 mass% is added to 15 to 25 mass% Cr steel. All of these steels are characterized by improving thermal fatigue properties by adding Cu.

特開2004−018921号公報JP 2004-018921 A WO2003/004714号パンフレットWO2003 / 004714 pamphlet 特開2006−117985号公報JP 2006-117985 A 特開2000−297355号公報JP 2000-297355 A

しかしながら、発明者らの研究によれば、上記特許文献2〜4の技術のようにCuを添加した場合には、耐熱疲労特性は向上するものの、鋼自身の耐酸化性が却って低下し、総体的に見ると、耐熱性が劣化することが明らかとなってきた。また、SUS444は、Type429に比べてCrの含有量が高く、かつ多量のMoが添加されているため、母材の靭性に劣るという問題点も残存していた。   However, according to the researches of the inventors, when Cu is added as in the techniques of Patent Documents 2 to 4, although the thermal fatigue resistance is improved, the oxidation resistance of the steel itself is decreased, and the whole From a standpoint, it has become clear that heat resistance deteriorates. Further, SUS444 has a higher Cr content than Type 429, and a large amount of Mo is added, so that the toughness of the base material is inferior.

そこで、本発明の目的は、Cu添加による耐酸化性の低下を防止する技術を開発することによって、MoやW等の高価な元素を添加することなく、熱疲労特性と耐酸化性に優れると共に、Type429と同等以上の靭性を有するフェライト系ステンレス鋼を提供することにある。ここで、本発明でいう「優れた耐酸化性と耐熱疲労特性」とは、SUS444と同等以上の特性を有すること、具体的には、耐酸化性は、950℃における耐酸化性が、また、熱疲労特性は、100℃−850℃間での繰り返しの熱疲労特性が、SUS444と同等以上であることをいう。また、Type429と同等の靭性とは、板厚2mmの冷延板を−40℃でシャルピー衝撃試験したときの脆性破面率がType429と同等であることをいう。   Therefore, the object of the present invention is to develop a technique for preventing a decrease in oxidation resistance due to the addition of Cu, and is excellent in thermal fatigue characteristics and oxidation resistance without adding expensive elements such as Mo and W. An object of the present invention is to provide a ferritic stainless steel having toughness equivalent to or better than Type 429. Here, the “excellent oxidation resistance and thermal fatigue characteristics” as used in the present invention has characteristics equal to or higher than those of SUS444. Specifically, the oxidation resistance is oxidation resistance at 950 ° C. The thermal fatigue property means that the repeated thermal fatigue property between 100 ° C. and 850 ° C. is equal to or higher than that of SUS444. Further, toughness equivalent to Type 429 means that the brittle fracture surface ratio when a cold-rolled sheet having a thickness of 2 mm is subjected to a Charpy impact test at −40 ° C. is equivalent to Type 429.

発明者らは、従来技術が抱えるCu添加による耐酸化性の低下を防止すると共に、MoやW等の高価な元素を添加することなく、熱疲労特性と耐酸化性が優れると共に、靭性にも優れるフェライト系ステンレス鋼を開発すべく鋭意検討を重ねた。その結果、Nbを0.3〜0.55mass%、Cuを1.0〜2.5mass%の範囲で複合添加することによって幅広い温度域で高い高温強度が得られ、熱疲労特性が改善されること、また、Cu添加による耐酸化性の低下は、Alを0.2mass%以上添加することにより防止し得ること、したがって、Nb,CuおよびAlを上記適正範囲に制御することによって、MoやWを添加しなくても、SUS444と同等以上の耐熱性(熱疲労特性、耐酸化性)が得られることを見出した。さらに、Cu,Al添加鋼の繰返し酸化試験による耐スケール剥離性は、Siの添加量を最適化(0.5mass%以下)することにより向上すること、および、靭性は、Mn,AlおよびTiの添加量を最適化(Mn:0.5mass%以下、Al:1.2mass%以下、Ti:0.01mass%以下)することにより、Type429と同等以上とすることができることを見出し、本発明を完成させた。   The inventors have prevented the deterioration of oxidation resistance due to the addition of Cu, which the prior art has, and are excellent in thermal fatigue characteristics and oxidation resistance without adding expensive elements such as Mo and W, and also in toughness. We intensively studied to develop an excellent ferritic stainless steel. As a result, by adding Nb in a range of 0.3 to 0.55 mass% and Cu in a range of 1.0 to 2.5 mass%, high high-temperature strength is obtained in a wide temperature range, and thermal fatigue characteristics are improved. In addition, a decrease in oxidation resistance due to the addition of Cu can be prevented by adding Al in an amount of 0.2 mass% or more. Therefore, by controlling Nb, Cu and Al to the above appropriate ranges, Mo and W It has been found that heat resistance (thermal fatigue characteristics, oxidation resistance) equal to or higher than that of SUS444 can be obtained without addition of. Furthermore, the peel resistance of the Cu and Al-added steel by the repeated oxidation test is improved by optimizing the addition amount of Si (0.5 mass% or less), and the toughness is Mn, Al and Ti. The present invention has been found by optimizing the amount added (Mn: 0.5 mass% or less, Al: 1.2 mass% or less, Ti: 0.01 mass% or less), which can be equal to or higher than Type 429. I let you.

すなわち、本発明は、C:0.015mass%以下、Si:0.5mass%以下、Mn:0.5mass%以下、P:0.04mass%以下、S:0.006mass%以下、Cr:16〜20mass%以下、N:0.015mass%以下、Nb:0.3〜0.55mass%、Ti:0.01mass%以下、Mo:0.1mass%以下、W:0.1mass%以下、Cu:1.0〜2.5mass%、Al:0.2〜1.2mass%を含有し、残部がFeおよび不可避的不純物からなるフェライト系ステンレス鋼である。   That is, the present invention is C: 0.015 mass% or less, Si: 0.5 mass% or less, Mn: 0.5 mass% or less, P: 0.04 mass% or less, S: 0.006 mass% or less, Cr: 16 to 20 mass% or less, N: 0.015 mass% or less, Nb: 0.3 to 0.55 mass%, Ti: 0.01 mass% or less, Mo: 0.1 mass% or less, W: 0.1 mass% or less, Cu: 1 Ferritic stainless steel containing 0.0 to 2.5 mass%, Al: 0.2 to 1.2 mass%, the balance being Fe and inevitable impurities.

また、本発明のフェライト系ステンレス鋼は、上記の成分組成に加えてさらに、B:0.003mass%以下、REM:0.08mass%以下、Zr:0.5mass%以下、V:0.5mass%以下、Co:0.5mass%以下およびNi:0.5mass%以下のうちから選ばれる1種または2種以上を含有することを特徴とする。   In addition to the above component composition, the ferritic stainless steel of the present invention further includes B: 0.003 mass% or less, REM: 0.08 mass% or less, Zr: 0.5 mass% or less, V: 0.5 mass%. Hereinafter, it is characterized by containing one or more selected from Co: 0.5 mass% or less and Ni: 0.5 mass% or less.

本発明によれば、高価なMoやWを添加することなく、SUS444と同等以上の耐熱性(熱疲労特性、耐酸化性)を有すると共に、Type429と同等以上の靭性を有するフェライト系ステンレス鋼を安価に得ることができる。したがって、本発明の鋼は、自動車排気系部材に用いて好適である。   According to the present invention, a ferritic stainless steel having heat resistance (thermal fatigue characteristics, oxidation resistance) equivalent to or better than SUS444 and toughness equivalent to or better than Type 429, without adding expensive Mo or W. It can be obtained inexpensively. Therefore, the steel of the present invention is suitable for use in automobile exhaust system members.

熱疲労試験片を説明する図である。It is a figure explaining a thermal fatigue test piece. 熱疲労試験における温度、拘束条件を説明する図である。It is a figure explaining the temperature in a thermal fatigue test, and constraint conditions. 熱疲労特性に及ぼすCu含有量の影響を示すグラフである。It is a graph which shows the influence of Cu content which acts on a thermal fatigue characteristic. 耐酸化性(酸化増量)に及ぼすAl含有量の影響を示すグラフである。It is a graph which shows the influence of Al content which affects oxidation resistance (oxidation increase). 耐酸化性(スケール剥離量)に及ぼすAl含有量の影響を示すグラフである。It is a graph which shows the influence of Al content which affects oxidation resistance (scale peeling amount). 耐酸化性(スケール剥離量)に及ぼすSi含有量の影響を示すグラフである。It is a graph which shows the influence of Si content which acts on oxidation resistance (scale peeling amount). 靭性(脆性破面率)に及ぼすMn含有量の影響を示すグラフである。It is a graph which shows the influence of Mn content which affects toughness (brittle fracture surface ratio). 靭性(脆性破面率)に及ぼすAl含有量の影響を示すグラフである。It is a graph which shows the influence of Al content which affects toughness (brittle fracture surface ratio). 靭性(脆性破面率)に及ぼすTi含有量の影響を示すグラフである。It is a graph which shows the influence of Ti content which affects toughness (brittle fracture surface ratio).

まず、本発明を開発するに至った基礎実験について、説明する。
C:0.005〜0.007mass%、N:0.004〜0.006mass%、Si:0.3mass%、Mn:0.2mass%、Cr:17mass%、Nb:0.45mass%およびAl:0.35mass%からなる成分組成をベースとし、これにCuの添加量を種々に変化させた鋼を実験室的に溶製して50kg鋼塊とし、この鋼塊を1170℃に加熱後、熱間圧延して厚さ:30mm×幅:150mmのシートバーとした。その後、このシートバーを鍛造し、35mm×35mmのバーとし、1030℃の温度で焼鈍後、機械加工し、図1に示した寸法の熱疲労試験片に加工した。そして、図2に示したような、拘束率:0.35で100℃−850℃間を加熱・冷却する熱処理を繰り返し付与し、熱疲労寿命を測定した。なお、上記熱疲労寿命は、100℃において検出された荷重を、図1に示した試験片均熱平行部の断面積で割って応力を算出し、前のサイクルの応力に対して連続的に応力が低下し始めたときの最小のサイクル数とした。これは、試験片に亀裂が発生したサイクル数に相当する。なお、比較として、SUS444(Cr:19mass%−Nb:0.5mass%−Mo:2mass%鋼)についても、同様の試験を行った。
First, the basic experiment that led to the development of the present invention will be described.
C: 0.005-0.007 mass%, N: 0.004-0.006 mass%, Si: 0.3 mass%, Mn: 0.2 mass%, Cr: 17 mass%, Nb: 0.45 mass% and Al: A steel with a component composition of 0.35 mass% as a base and various amounts of Cu added thereto was melted in the laboratory to form a 50 kg steel ingot. After heating this steel ingot to 1170 ° C, A sheet bar having a thickness of 30 mm and a width of 150 mm was obtained by hot rolling. Thereafter, the sheet bar was forged into a bar of 35 mm × 35 mm, annealed at a temperature of 1030 ° C., machined, and processed into a thermal fatigue test piece having the dimensions shown in FIG. Then, as shown in FIG. 2, heat treatment for heating / cooling between 100 ° C. and 850 ° C. was performed at a constraint ratio of 0.35, and the thermal fatigue life was measured. The thermal fatigue life is calculated by dividing the load detected at 100 ° C. by the cross-sectional area of the test piece soaking parallel section shown in FIG. The minimum number of cycles when the stress began to decrease was taken. This corresponds to the number of cycles in which a crack occurred in the test piece. For comparison, the same test was performed on SUS444 (Cr: 19 mass% -Nb: 0.5 mass% -Mo: 2 mass% steel).

図3は、上記熱疲労試験の結果を示したものである。この図から、Cuを1.0mass%以上添加することにより、SUS444の熱疲労寿命(約1100サイクル)と同等以上の熱疲労寿命が得られること、したがって、熱疲労特性を改善するには、Cuを1mass%以上添加することが有効であることがわかる。   FIG. 3 shows the results of the thermal fatigue test. From this figure, it is possible to obtain a thermal fatigue life equal to or greater than that of SUS444 (about 1100 cycles) by adding Cu by 1.0 mass% or more. It can be seen that it is effective to add 1 mass% or more.

次に、C:0.006mass%、N:0.007mass%、Mn:0.2mass%、Si:0.3mass%、Cr:17mass%、Nb:0.49mass%およびCu:1.5mass%からなる成分組成をベースとし、これにAlの添加量を種々に変化させた鋼を実験室的に溶製し、50kg鋼塊とし、この鋼塊を、熱間圧延し、熱延板焼鈍し、冷間圧延し、仕上焼鈍して、板厚2mmの冷延焼鈍板とした。上記のようにして得た冷延鋼板から30mm×20mmの試験片を切り出し、この試験片上部に4mmφの穴をあけ、表面および端面を#320のエメリー紙で研磨し、脱脂後、下記の試験に供した。
<連続酸化試験>
上記試験片を、950℃に加熱された大気雰囲気の炉中に300時間保持し、加熱試験前後における試験片の質量の差を測定し、単位面積当たりの酸化増量(g/m)を求めた。
<繰り返し酸化試験>
上記試験片を用いて、大気中において、100℃×1minと950℃×25minの温度に加熱・冷却を繰り返す熱処理を600サイクル行い、試験前後における質量差から、試験片表面から剥離したスケール量(g/m)を測定した。なお、上記試験における加熱、冷却速度は、それぞれ5℃/sec、1.5℃/secで行った。
Next, from C: 0.006 mass%, N: 0.007 mass%, Mn: 0.2 mass%, Si: 0.3 mass%, Cr: 17 mass%, Nb: 0.49 mass% and Cu: 1.5 mass% Based on this component composition, steel with various addition amounts of Al was varied in the laboratory and made into a 50 kg steel ingot. This steel ingot was hot-rolled and hot-rolled sheet annealed, Cold-rolled and finish-annealed to obtain a cold-rolled annealed plate having a thickness of 2 mm. A test piece of 30 mm × 20 mm was cut out from the cold-rolled steel sheet obtained as described above, a hole of 4 mmφ was made in the upper part of the test piece, the surface and the end surface were polished with # 320 emery paper, degreased, and then subjected to the following test. It was used for.
<Continuous oxidation test>
The test piece is held in a furnace in an air atmosphere heated to 950 ° C. for 300 hours, the difference in the mass of the test piece before and after the heating test is measured, and the increase in oxidation per unit area (g / m 2 ) is obtained. It was.
<Repetitive oxidation test>
Using the above test piece, 600 cycles of heat treatment that repeats heating and cooling to temperatures of 100 ° C. × 1 min and 950 ° C. × 25 min in the atmosphere were performed, and the amount of scale peeled from the test piece surface from the mass difference before and after the test ( g / m 2 ) was measured. The heating and cooling rates in the above test were performed at 5 ° C./sec and 1.5 ° C./sec, respectively.

図4は、酸化増量の測定結果を、また、図5は、スケール剥離量の測定結果を示したものである。これらの図から、Alを0.2mass%以上添加することで、SUS444と同等以上の耐酸化性(酸化増量:27g/m以下、スケール剥離量:4g/m未満)が得られることがわかる。 FIG. 4 shows the measurement result of the oxidation increase amount, and FIG. 5 shows the measurement result of the scale peeling amount. From these figures, it can be seen that by adding 0.2 mass% or more of Al, oxidation resistance equal to or higher than that of SUS444 (oxidation increase amount: 27 g / m 2 or less, scale peeling amount: less than 4 g / m 2 ) can be obtained. Recognize.

次に、C:0.006mass%、N:0.007mass%、Mn:0.2mass%、Al:0.45mass%、Cr:17mass%、Nb:0.49mass%、Cu:1.5mass%からなる成分組成をベースとし、これにSiの添加量を種々に変化させた鋼を実験室的に溶製し、50kg鋼塊とし、上記と同様にして板厚2mmの冷延焼鈍板とし、上記と同様にして、繰り返し酸化試験を行い、スケール剥離量を測定し、その結果を、図6に示した。これから、Alを適正量添加しても、Siが0.5%を超えるとスケール密着性が低下して剥離量が増え、SUS444と同等の耐熱性が得られなくなることがわかった。   Next, from C: 0.006 mass%, N: 0.007 mass%, Mn: 0.2 mass%, Al: 0.45 mass%, Cr: 17 mass%, Nb: 0.49 mass%, Cu: 1.5 mass% Based on this component composition, steel with various amounts of Si added to this was melted in the laboratory to form a 50 kg steel ingot, a cold-rolled annealed plate with a thickness of 2 mm in the same manner as above, In the same manner as described above, the oxidation test was repeatedly performed, the amount of scale peeling was measured, and the result is shown in FIG. From this, it has been found that even when an appropriate amount of Al is added, when Si exceeds 0.5%, the adhesion to the scale is lowered and the amount of peeling is increased, so that heat resistance equivalent to SUS444 cannot be obtained.

最後に、C:0.006〜0.007mass%、N:0.006〜0.007mass%、Si:0.3mass%、Cr:17mass%、Nb:0.45mass%およびCu:1.5mass%からなる成分組成をベースとし、これにMn,AlおよびTiの含有量を種々変化させた鋼を実験室的に溶製し、50kg鋼塊とし、この鋼塊を、熱間圧延し、熱延板焼鈍し、冷間圧延し、仕上焼鈍して、板厚2mmの冷延焼鈍板とした。この冷延焼鈍板から、サブサイズのシャルピー衝撃試験片を採取し、−40℃の温度においてシャルピー衝撃試験を行い、脆性破面率を測定し、靭性を評価した。   Finally, C: 0.006 to 0.007 mass%, N: 0.006 to 0.007 mass%, Si: 0.3 mass%, Cr: 17 mass%, Nb: 0.45 mass%, and Cu: 1.5 mass% Based on the component composition consisting of the above, steel with various contents of Mn, Al and Ti being melted in the laboratory was made into a 50 kg steel ingot, which was hot-rolled and hot rolled. Sheet annealing, cold rolling, and finish annealing were performed to obtain a cold-rolled annealing sheet having a thickness of 2 mm. From this cold-rolled annealed plate, a sub-size Charpy impact test piece was collected, subjected to a Charpy impact test at a temperature of −40 ° C., the brittle fracture surface ratio was measured, and the toughness was evaluated.

図7は、Al:0.25mass%、Ti:0.006mass%のときにおけるMn含有量が靭性に及ぼす影響を、図8は、Mn:0.1mass%、Ti:0.005mass%のときにおけるAl含有量が靭性に及ぼす影響を、また、図9は、Al:0.25mass%、Mn:0.1mass%のときにおけるTi含有量が靭性に及ぼす影響を示したものである。これらの図から、Type429と同等以上の靭性を得るには、Mn:0.3mass%以下、Al:1.2mass%以下、Ti:0.01mass%以下でなければならないことがわかった。
本発明は、上記知見に、さらに検討を加えて完成したものである。
FIG. 7 shows the effect of Mn content on toughness when Al: 0.25 mass% and Ti: 0.006 mass%. FIG. 8 shows the effect when Mn: 0.1 mass% and Ti: 0.005 mass%. FIG. 9 shows the influence of the Ti content on toughness when Al content is 0.25 mass% and Mn: 0.1 mass%. From these figures, it was found that Mn: 0.3 mass% or less, Al: 1.2 mass% or less, and Ti: 0.01 mass% or less were required to obtain toughness equivalent to or better than Type 429.
The present invention has been completed by further studying the above findings.

次に、本発明のフェライト系ステンレス鋼の成分組成について説明する。
C:0.015mass%以下
Cは、鋼の強度を高めるのに有効な元素であるが、0.015mass%を超えて含有すると、靭性および成形性の低下が顕著となる。よって、本発明では、Cは0.015mass%以下とする。なお、成形性を確保する観点からは、Cは低いほど好ましく、0.008mass%以下とするのが望ましい。一方、排気系部材としての強度を確保するには、Cは0.001mass%以上であることが好ましい。より好ましくは0.002〜0.008mass%の範囲である。
Next, the component composition of the ferritic stainless steel of the present invention will be described.
C: 0.015 mass% or less C is an element effective for increasing the strength of steel, but if it exceeds 0.015 mass%, the toughness and formability are significantly reduced. Therefore, in this invention, C shall be 0.015 mass% or less. From the viewpoint of securing moldability, C is preferably as low as possible, and is preferably 0.008 mass% or less. On the other hand, in order to ensure the strength as an exhaust system member, C is preferably 0.001 mass% or more. More preferably, it is the range of 0.002-0.008 mass%.

Si:0.5mass%以下
Siは、脱酸材として添加される元素であり、0.05mass%以上添加するのが好ましい。また、Siは、本発明が主眼とする耐酸化性を向上する効果を有するが、Alほどの効果は得られない。一方、図6からわかるように、0.5mass%を超えるSiの過剰な添加は、耐スケール剥離性が低下し、SUS444と同等以上の耐酸化性が得られない。よって、Siの上限は0.5mass%とする。
Si: 0.5 mass% or less Si is an element added as a deoxidizing material, and it is preferable to add 0.05 mass% or more. In addition, Si has an effect of improving the oxidation resistance which is the main subject of the present invention, but cannot be as effective as Al. On the other hand, as can be seen from FIG. 6, excessive addition of Si exceeding 0.5 mass% decreases the scale peel resistance, and the oxidation resistance equal to or higher than that of SUS444 cannot be obtained. Therefore, the upper limit of Si is 0.5 mass%.

Mn:0.5mass%以下
Mnは、鋼の強度を高める元素であり、また、脱酸剤としての作用も有するため、0.05mass%以上添加するのが好ましい。しかし、過剰な添加は、高温でγ相が生成しやすくなり、耐熱性を低下させる。また、図7からわかるように、0.5mass%を超えて添加するとType429と同等以上の靭性が得られず、本発明の目的を達成できない。よって、本発明ではMnを0.5mass%以下とする。
Mn: 0.5 mass% or less Mn is an element that increases the strength of steel, and also has an action as a deoxidizer, so it is preferable to add 0.05 mass% or more. However, excessive addition tends to generate a γ phase at a high temperature and reduces heat resistance. Further, as can be seen from FIG. 7, when the addition exceeds 0.5 mass%, the toughness equal to or higher than Type 429 cannot be obtained, and the object of the present invention cannot be achieved. Therefore, in the present invention, Mn is 0.5 mass% or less.

P:0.04mass%以下
Pは、靭性を低下させる有害元素であり、可能な限り低減するのが望ましい。そこで、本発明では、Pは0.04mass%以下とする。好ましくは、0.03mass%以下である。
P: 0.04 mass% or less P is a harmful element that lowers toughness, and is desirably reduced as much as possible. Therefore, in the present invention, P is set to 0.04 mass% or less. Preferably, it is 0.03 mass% or less.

S:0.006mass%以下
Sは、伸びやr値を低下し、成形性に悪影響を及ぼすとともに、ステンレス鋼の基本特性である耐食性を低下させる有害元素でもあるため、できるだけ低減するのが望ましい。よって、本発明では、Sは0.006mass%以下とする。好ましくは、0.003mass%以下である。
S: 0.006 mass% or less S is a harmful element that lowers the elongation and r value, adversely affects the formability, and lowers the corrosion resistance, which is a basic characteristic of stainless steel, so it is desirable to reduce it as much as possible. Therefore, in the present invention, S is set to 0.006 mass% or less. Preferably, it is 0.003 mass% or less.

Cr:16〜20mass%
Crは、ステンレス鋼の特徴である耐食性、耐酸化性を向上させるのに有効な重要元素であるが、16mass%未満では、十分な耐酸化性が得られない。一方、Crは、室温において鋼を固溶強化し、硬質化・低延性化する元素であり、特に20mass%を超えて含有すると、上記弊害が顕著となり、Type429と同等以上の加工性や靭性が得られなくなる。よって、本発明では、Crは16〜20mass%の範囲とする。好ましくは、16〜19mass%の範囲である。
Cr: 16-20 mass%
Cr is an important element effective for improving the corrosion resistance and oxidation resistance, which are the characteristics of stainless steel, but if it is less than 16 mass%, sufficient oxidation resistance cannot be obtained. On the other hand, Cr is an element that solidifies and strengthens steel at room temperature, and makes it harder and lower ductile. Especially when it exceeds 20 mass%, the above-described adverse effects become remarkable, and workability and toughness equivalent to or better than Type 429 are obtained. It can no longer be obtained. Therefore, in this invention, Cr is taken as the range of 16-20 mass%. Preferably, it is the range of 16-19 mass%.

N:0.015mass%以下
Nは、鋼の靭性および成形性を低下させる元素であり、0.015mass%を超えて含有すると、上記低下が顕著となる。よって、Nは0.015mass%以下とする。なお、Nは、より高い靭性が求められる場合は、さらに低減し、0.010mass%未満とするのが好ましい。
N: 0.015 mass% or less N is an element that decreases the toughness and formability of steel. When the content exceeds 0.015 mass%, the above-described decrease becomes significant. Therefore, N is set to 0.015 mass% or less. In addition, when higher toughness is calculated | required, N reduces further, and it is preferable to set it as less than 0.010 mass%.

Nb:0.3〜0.55mass%
Nbは、C,Nと炭窒化物を形成して固定し、耐食性や成形性、溶接部の耐粒界腐食性を高める作用を有するとともに、高温強度を上昇させて熱疲労特性を向上する効果を有する元素である。このような効果は、0.3mass%以上の添加で認められる。一方、0.55mass%を超える添加は、Laves相が析出しやすくなり、脆性が低下する。よって、Nbは0.3〜0.55mass%の範囲とする。好ましくは、0.4〜0.5mass%の範囲である。
Nb: 0.3-0.55 mass%
Nb forms and fixes C, N and carbonitrides, and has the effect of improving corrosion resistance and formability, intergranular corrosion resistance of welded parts, and increasing the high temperature strength and improving the thermal fatigue characteristics. It is an element having Such an effect is recognized by addition of 0.3 mass% or more. On the other hand, when it exceeds 0.55 mass%, the Laves phase is likely to precipitate, and the brittleness decreases. Therefore, Nb is set to a range of 0.3 to 0.55 mass%. Preferably, it is in the range of 0.4 to 0.5 mass%.

Ti:0.01mass%以下
Tiは、Nbに比べてNと結合しやすく粗大なTiNを形成しやすい元素であり、この粗大なTiNは、切り欠けとして作用し、靭性を著しく低下させる。特に、図9示したように、Tiの含有量が0.01mass%を超えると、この悪影響が顕著となる。よって、本発明では、Tiは0.01%以下に制限する。
Ti: 0.01 mass% or less Ti is an element that is easier to bond with N than Nb and easily forms coarse TiN, and this coarse TiN acts as a notch and significantly reduces toughness. In particular, as shown in FIG. 9, when the Ti content exceeds 0.01 mass%, this adverse effect becomes significant. Therefore, in the present invention, Ti is limited to 0.01% or less.

Mo:0.1mass%以下
Moは、高価な元素であり、本発明の趣旨からも積極的な添加は行わない。しかし、原料であるスクラップ等から0.1mass%以下混入することがある。よって、Moは0.1mass%以下とする。
Mo: 0.1 mass% or less Mo is an expensive element, and is not actively added for the purpose of the present invention. However, it may be mixed in by 0.1 mass% or less from raw materials such as scrap. Therefore, Mo is set to 0.1 mass% or less.

W:0.1mass%以下
Wは、Moと同様に高価な元素であり、本発明の趣旨からも積極的な添加は行わない。しかし、原料であるスクラップ等から0.1mass%以下混入することがある。よって、Wは0.1mass%以下とする。
W: 0.1 mass% or less W is an expensive element like Mo and is not actively added from the gist of the present invention. However, it may be mixed in by 0.1 mass% or less from raw materials such as scrap. Therefore, W is set to 0.1 mass% or less.

Cu:1.0〜2.5mass%
Cuは、熱疲労特性の向上には非常に有効な元素である。図3に示したように、SUS444と同等以上の耐熱疲労特性を得るには、Cuを1.0mass%以上添加することが必要である。しかし、2.5mass%を超える添加は、熱処理後の冷却時にε−Cuが析出し、鋼を硬質化するとともに、熱間加工時に脆化を起こしやすくなる。さらに重要なことは、Cuの添加は、耐熱疲労特性は向上するものの、鋼自身の耐酸化性が却って低下し、総体的に見ると、耐熱性が低下してしまうことである。この原因は、十分に明らかとはなっていないが、生成したスケール直下の脱Cr層にCuが濃化し、ステンレス鋼本来の耐酸化性を向上する元素であるCrの再拡散を抑制するためと考えられる。よって、Cuは、1.0〜2.5mass%の範囲とする。好ましくは、1.1〜1.8mass%の範囲である。
Cu: 1.0-2.5 mass%
Cu is an extremely effective element for improving thermal fatigue characteristics. As shown in FIG. 3, it is necessary to add 1.0 mass% or more of Cu in order to obtain the heat fatigue characteristics equivalent to or higher than that of SUS444. However, addition exceeding 2.5 mass% causes ε-Cu to precipitate during cooling after heat treatment, hardens the steel, and easily causes embrittlement during hot working. More importantly, the addition of Cu improves the thermal fatigue resistance, but decreases the oxidation resistance of the steel itself, and the overall heat resistance decreases. The cause of this is not sufficiently clear, but it is because Cu concentrates in the deCr layer formed directly under the scale, and suppresses the re-diffusion of Cr, which is an element that improves the original oxidation resistance of stainless steel. Conceivable. Therefore, Cu is set to a range of 1.0 to 2.5 mass%. Preferably, it is the range of 1.1-1.8 mass%.

Al:0.2〜1.2mass%
Alは、図4および図5に示したように、Cu添加鋼の耐酸化性を向上するために必要不可欠な元素である。特に、本発明の目的であるSUS444と同等以上の耐酸化性を得るには0.2mass%以上の添加が必要である。一方、図8に示したように、1.2mass%を超えて添加すると、鋼が硬質化してType429と同等以上の靭性が得られなくなるので、上限は1.2mass%とする。好ましくは、0.3〜1.0mass%の範囲である。
Al: 0.2-1.2 mass%
As shown in FIGS. 4 and 5, Al is an indispensable element for improving the oxidation resistance of the Cu-added steel. In particular, in order to obtain oxidation resistance equal to or higher than that of SUS444 which is the object of the present invention, addition of 0.2 mass% or more is necessary. On the other hand, as shown in FIG. 8, if added exceeding 1.2 mass%, the steel becomes hard and toughness equal to or higher than Type 429 cannot be obtained, so the upper limit is set to 1.2 mass%. Preferably, it is in the range of 0.3 to 1.0 mass%.

本発明のフェライト系ステンレス鋼は、上記必須とする成分に加えてさらに、B,REM,Zr,V,CoおよびNiのうちから選ばれる1種または2種以上を、下記の範囲で添加することができる。
B:0.003mass%以下
Bは、加工性、とくに2次加工性を向上させるのに有効な元素である。この顕著な効果は、0.0005mass%以上の添加で得ることができるが、0.003mass%を超える多量の添加は、BNを生成して加工性を低下させる。よって、Bを添加する場合は、0.003mass%以下とする。より好ましくは、0.0005〜0.002mass%の範囲である。
In the ferritic stainless steel of the present invention, in addition to the essential components, one or more selected from B, REM, Zr, V, Co and Ni should be added within the following range. Can do.
B: 0.003 mass% or less B is an element effective for improving workability, particularly secondary workability. This remarkable effect can be obtained by addition of 0.0005 mass% or more. However, addition of a large amount exceeding 0.003 mass% generates BN and deteriorates workability. Therefore, when adding B, it is made into 0.003 mass% or less. More preferably, it is the range of 0.0005-0.002 mass%.

REM:0.08mass%以下、Zr:0.5mass%以下
REM(希土類元素)およびZrはいずれも、耐酸化性を改善する元素であり、上記効果を得るためには、それぞれ0.01mass%以上、0.05mass%以上添加するのが好ましい。しかし、REMの0.08mass%を超える添加は、鋼を脆化させ、また、Zrの0.5mass%を超える添加は、Zr金属間化合物が析出して、鋼を脆化させ「る。よって、REMを添加する場合は0.08mass%以下、Zrを添加する場合は0.5mass%以下とする。
REM: 0.08 mass% or less, Zr: 0.5 mass% or less REM (rare earth element) and Zr are both elements that improve oxidation resistance. , 0.05 mass% or more is preferably added. However, the addition exceeding 0.08 mass% of REM causes the steel to become brittle, and the addition exceeding 0.5 mass% of Zr causes the Zr intermetallic compound to precipitate and embrittles the steel. When adding REM, 0.08 mass% or less, and when adding Zr, 0.5 mass% or less.

V:0.5mass%以下
Vは、加工性および耐酸化性の向上に有効な元素であり、特に耐酸化性の向上効果を得るためには0.15mass%以上の添加が好ましい。しかし、0.5mass%を超える過剰な添加は、粗大なV(C,N)を析出し、表面性状を劣化させる。よって、Vを添加する場合は、0.5mass%以下添加するのが好ましく、0.15〜0.4mass%の範囲で添加するのがより好ましい。
V: 0.5 mass% or less V is an element effective for improving workability and oxidation resistance. In particular, in order to obtain an effect of improving oxidation resistance, addition of 0.15 mass% or more is preferable. However, excessive addition exceeding 0.5 mass% precipitates coarse V (C, N) and degrades the surface properties. Therefore, when adding V, it is preferable to add 0.5 mass% or less, and it is more preferable to add in the range of 0.15-0.4 mass%.

Co:0.5mass%以下
Coは、靭性の向上に有効な元素であり、0.02mass%以上添加するのが好ましい。しかし、Coは、高価な元素であり、また、0.5mass%を超えて添加しても、上記効果は飽和する。よって、Coを添加する場合は0.5mass%以下とするのが好ましい。より好ましくは、0.02〜0.2mass%の範囲である。
Co: 0.5 mass% or less Co is an element effective for improving toughness, and is preferably added in an amount of 0.02 mass% or more. However, Co is an expensive element, and the above effect is saturated even if it is added in an amount exceeding 0.5 mass%. Therefore, when adding Co, it is preferable to set it as 0.5 mass% or less. More preferably, it is the range of 0.02-0.2 mass%.

Ni:0.5mass%以下
Niは、靭性を向上させる元素である。しかし、Niは、高価であり、また、強力なγ相形成元素であるため、高温でγ相を生成し、耐酸化性を低下させる。よって、Niを添加する場合は、0.5mass%以下とするのが好ましい。より好ましくは、0.05〜0.4mass%の範囲である。
Ni: 0.5 mass% or less Ni is an element that improves toughness. However, since Ni is expensive and is a strong γ-phase forming element, it generates a γ-phase at a high temperature and reduces oxidation resistance. Therefore, when adding Ni, it is preferable to set it as 0.5 mass% or less. More preferably, it is the range of 0.05-0.4 mass%.

次に、本発明のフェライト系ステンレス鋼の製造方法について説明する。
本発明のステンレス鋼の製造方法は、フェライト系ステンレス鋼の通常の製造方法であれば好適に用いることができ、特に限定されるものではない。例えば、転炉、電気炉等の溶製炉で鋼を溶製し、あるいはさらに取鍋精錬、真空精錬等の2次精錬を経て上述した本発明の成分組成を有する溶鋼とし、次いで、その溶鋼を連続鋳造法あるいは造塊−分塊圧延法で鋼片(スラブ)とし、熱間圧延して熱延板とし、必要に応じて熱延板焼鈍を施し、さらに、その熱延板を酸洗し、冷間圧延し、仕上焼鈍し、酸洗する等の工程を経て冷延焼鈍板とするのが好ましい。上記冷間圧延は、1回または中間焼鈍を挟む2回以上の冷間圧延を行ってもよく、また、冷間圧延、仕上焼鈍、酸洗の各工程は、繰り返して行ってもよい。さらに、場合によっては、熱延板焼鈍は省略してもよく、鋼板表面の光沢性が要求される場合には、冷延後あるいは仕上焼鈍後、スキンパスを施してもよい。なお、上記熱間圧延前のスラブ加熱温度は1000〜1250℃、熱延板焼鈍温度は900〜1100℃、仕上焼鈍温度は900〜1120℃の範囲であるのが好ましい。
Next, the manufacturing method of the ferritic stainless steel of this invention is demonstrated.
The method for producing stainless steel of the present invention can be suitably used as long as it is a normal method for producing ferritic stainless steel, and is not particularly limited. For example, steel is melted in a melting furnace such as a converter or an electric furnace, or is further subjected to secondary refining such as ladle refining or vacuum refining to obtain a molten steel having the above-described component composition of the present invention. Is formed into a steel slab by continuous casting or ingot-bundling, and hot-rolled into a hot-rolled sheet, subjected to hot-rolled sheet annealing as necessary, and the hot-rolled sheet is pickled. Then, it is preferable to form a cold-rolled annealed plate through processes such as cold rolling, finish annealing, and pickling. The cold rolling may be performed once or twice or more with intermediate annealing, and the steps of cold rolling, finish annealing, and pickling may be performed repeatedly. Further, depending on the case, the hot-rolled sheet annealing may be omitted, and when the gloss of the steel sheet surface is required, a skin pass may be applied after cold rolling or after finish annealing. In addition, it is preferable that the slab heating temperature before the said hot rolling is 1000-1250 degreeC, the hot-rolled sheet annealing temperature is 900-1100 degreeC, and a finish annealing temperature is the range of 900-1120 degreeC.

上記のようにして得た本発明のフェライト系ステンレス鋼は、その後、それぞれの用途に応じて切断加工、曲げ加工、プレス加工等の加工を施されて、自動車やオートバイの排気管、コンバーターケースや火力発電プラントの排気ダクト等の高温環境下で使用される各種排気系部材とされる。なお、上記部材に用いる本発明のステンレス鋼は、冷延焼鈍板に限定されるものではなく、熱延板あるいは熱延板焼鈍として用いてもよく、さらに必要に応じて脱スケール処理して用いてもよい。また、上記部材に組み立てる際の溶接方法は、特に限定されるものではなく、MIG、TIG、MAG等の通常のアーク溶接や、スポット溶接、シーム溶接等の電気抵抗溶接および電縫溶接に用いられる高周波抵抗溶接、高周波誘導溶接、レーザー溶接などの方法を用いることができる。   The ferritic stainless steel of the present invention obtained as described above is then subjected to processing such as cutting, bending, pressing, etc. according to each application, and the exhaust pipe, converter case, etc. of automobiles and motorcycles. Various exhaust system members used in a high temperature environment such as an exhaust duct of a thermal power plant. The stainless steel of the present invention used for the above-mentioned member is not limited to the cold-rolled annealed plate, and may be used as a hot-rolled plate or a hot-rolled plate annealed, and further, descaled as necessary. May be. Moreover, the welding method at the time of assembling to the said member is not specifically limited, It uses for normal arc welding, such as MIG, TIG, and MAG, electric resistance welding, such as spot welding and seam welding, and electric resistance welding. Methods such as high-frequency resistance welding, high-frequency induction welding, and laser welding can be used.

表1に示す成分組成を有するNo.1〜27の鋼を真空溶解炉で溶製し、鋳造して50kg鋼塊とし、鍛造して2分割した。その後、2分割した片方の鋼塊を、1170℃に加熱後、熱間圧延して板厚5mmの熱延板とし、1020℃の温度で熱延板焼鈍し、酸洗し、圧下率60%の冷間圧延し、1030℃の温度で仕上焼鈍し、平均冷却速度20℃/secで冷却し、酸洗して板厚が2mmの冷延焼鈍板とし、以下の耐酸化性試験および衝撃試験に供した。なお、参考として、表1のNo.28〜32に示したSUS444、Type429および特許文献2〜4の発明鋼についても、上記と同様にして冷延焼鈍板を作製し、同様の評価試験に供した。   No. having the component composition shown in Table 1. Steels 1 to 27 were melted in a vacuum melting furnace, cast into a 50 kg steel ingot, and forged into two parts. Thereafter, one of the two steel ingots was heated to 1170 ° C., and then hot-rolled to form a hot-rolled sheet having a thickness of 5 mm. Cold-rolled, finish-annealed at a temperature of 1030 ° C., cooled at an average cooling rate of 20 ° C./sec, pickled to form a cold-rolled annealed plate having a thickness of 2 mm, and the following oxidation resistance test and impact test It was used for. For reference, No. 1 in Table 1 was used. For the SUS444, Type 429, and invention steels of Patent Documents 2 to 4 shown in 28 to 32, cold-rolled annealed plates were produced in the same manner as described above and subjected to the same evaluation test.

Figure 0005387057
Figure 0005387057

<大気中連続酸化試験>
上記のようにして得た各種冷延焼鈍板から30mm×20mmのサンプルを切り出し、サンプル上部に4mmφの穴をあけ、表面および端面を#320のエメリー紙で研磨し、脱脂後、950℃に加熱保持された大気雰囲気の炉内に吊り下げて、300時間保持した。試験後、サンプルの質量を測定し、予め測定しておいた試験前の質量との差を求め、酸化増量(g/m)を算出した。なお、試験は各2回実施し、その平均値で耐連続酸化性を評価した。
<大気中繰り返し酸化試験>
上記各種の冷延焼鈍板から30mm×20mmのサンプルを切り出し、サンプル上部に4mmφの穴をあけ、表面および端面を#320のエメリー紙で研磨し、脱脂後、大気雰囲気中で、100℃と950℃との間を昇温・降温を繰り返す酸化試験を行った。なお、昇温、降温速度はそれぞれ5℃/sec、1.5℃/secとし、保持時間は100℃が1min、950℃が25minとし、これを600サイクル行った。耐繰り返し酸化性の評価は、試験後のサンプルの質量を測定し、予め測定しておいた試験前の質量との差を求め、スケール剥離量(g/m)を求めた。なお、試験は各2回実施し、その平均値で耐繰り返し酸化性を評価した。
<シャルピー衝撃試験>
上記各種の冷延焼鈍板から、Vノッチを圧延方向に直角に入れたシャルピー衝撃試験片を各3本ずつ採取し、−40℃の温度でのシャルピー衝撃試験を行い、脆性破面率を測定し、3本の平均値を求めて、靭性を評価した。
<Atmospheric continuous oxidation test>
Cut out a 30mm x 20mm sample from the various cold-rolled annealed plates obtained as described above, drill a 4mmφ hole at the top of the sample, polish the surface and end face with # 320 emery paper, degrease, and heat to 950 ° C It was suspended in a furnace in a maintained atmospheric atmosphere and held for 300 hours. After the test, the mass of the sample was measured, the difference from the pre-measured mass before the test was determined, and the increase in oxidation (g / m 2 ) was calculated. In addition, the test was implemented twice and the continuous oxidation resistance was evaluated by the average value.
<Atmospheric repeated oxidation test>
Samples of 30 mm × 20 mm were cut out from the various cold-rolled annealed plates, 4 mmφ holes were made in the upper part of the sample, the surface and end surfaces were polished with # 320 emery paper, degreased, and then at 100 ° C. and 950 in the atmosphere. An oxidation test was repeated in which the temperature was raised and lowered between the temperatures. The temperature increase and decrease rates were 5 ° C./sec and 1.5 ° C./sec, respectively, and the holding times were 100 ° C. for 1 min and 950 ° C. for 25 min, and this was performed for 600 cycles. For the evaluation of the repeated oxidation resistance, the mass of the sample after the test was measured, and the difference from the pre-test mass that had been measured in advance was determined to determine the scale peeling amount (g / m 2 ). The test was performed twice, and the oxidation resistance was evaluated with the average value.
<Charpy impact test>
Three Charpy impact test pieces with V notches perpendicular to the rolling direction were sampled from each of the various cold-rolled annealed plates, and Charpy impact tests were performed at a temperature of −40 ° C. to measure the brittle fracture surface ratio. And the average value of three was calculated | required and toughness was evaluated.

Figure 0005387057
Figure 0005387057

実施例1において2分割した50kg鋼塊の残りの鋼塊を、1170℃に加熱後、熱間圧延して厚さ:30mm×幅:150mmのシートバーとした。その後、このシートバーを鍛造し、35mm×35mmのバーとし、1030℃の温度で焼鈍後、機械加工し、図1に示した寸法の熱疲労試験片に加工し、下記の熱疲労試験に供した。なお、参考例として、実施例1と同様、SUS444、Type429および特許文献2〜4の発明鋼についても同様に試料を作製し、熱疲労試験に供した。   The remaining steel ingot of the 50 kg steel ingot divided into two in Example 1 was heated to 1170 ° C. and hot-rolled to obtain a sheet bar having a thickness of 30 mm × width: 150 mm. Thereafter, this sheet bar is forged into a 35 mm × 35 mm bar, annealed at a temperature of 1030 ° C., machined, processed into a thermal fatigue test piece having the dimensions shown in FIG. 1, and subjected to the following thermal fatigue test. did. As a reference example, similarly to Example 1, samples were similarly prepared for SUS444, Type 429, and invention steels of Patent Documents 2 to 4, and subjected to a thermal fatigue test.

<熱疲労試験>
熱疲労試験は、拘束率0.35で、100℃と850℃の温度間を繰り返して昇温・降温し、熱疲労寿命を測定した。この際、昇温・降温速度は、それぞれ10℃/secとし、100℃での保持時間は2min、850℃での保持時間は5minとした。また、熱疲労寿命は、100℃において検出された荷重を試験片均熱平行部の断面積で割って応力を算出し、前のサイクルの応力に対して連続的に応力が低下し始めたときの最小のサイクル数とした。
<Thermal fatigue test>
In the thermal fatigue test, the thermal fatigue life was measured by repeatedly raising and lowering the temperature between 100 ° C. and 850 ° C. with a restraint ratio of 0.35. At this time, the temperature increase / decrease rate was 10 ° C./sec, the retention time at 100 ° C. was 2 min, and the retention time at 850 ° C. was 5 min. The thermal fatigue life is calculated by dividing the load detected at 100 ° C by the cross-sectional area of the test piece soaking parallel part, and when the stress begins to decrease continuously with respect to the stress of the previous cycle. The minimum number of cycles.

上記実施例1の大気中連続酸化試験、大気中繰返し酸化試験、シャルピー衝撃試験の結果および実施例2の耐熱疲労性試験の結果を表2にまとめて示した。表2から明らかなように、本発明に適合している発明例の鋼は、いずれもSUS444と同等以上の耐酸化特性と耐熱疲労特性を有していると共に、Type429と同等以上の靭性を有しており、本発明の目標を満たしている。これに対して、本発明の範囲を外れる比較例の鋼あるいは先行技術の参考例の鋼は、耐酸化特性、耐熱疲労特性および母材の靭性のすべてが同時に優れるものはなく、本発明の目標とする特性が得られていない。   Table 2 summarizes the results of the atmospheric continuous oxidation test, the atmospheric repeated oxidation test, and the Charpy impact test of Example 1 and the heat fatigue resistance test of Example 2. As is clear from Table 2, all of the steels of the inventive examples conforming to the present invention have oxidation resistance and thermal fatigue characteristics equivalent to or better than SUS444, and have toughness equivalent to or better than Type 429. And meets the goals of the present invention. On the other hand, the steel of the comparative example which is out of the scope of the present invention or the steel of the reference example of the prior art does not have excellent oxidation resistance, heat fatigue resistance and toughness of the base material at the same time. The characteristics are not obtained.

本発明の鋼は、自動車等の排気系部材用として好適であるだけでなく、同様の特性が要求される火力発電システムの排気系部材や固体酸化物タイプの燃料電池用部材としても好適に用いることができる。   The steel of the present invention is not only suitable for exhaust system members such as automobiles, but also suitably used as exhaust system members for thermal power generation systems and solid oxide fuel cell members that require similar characteristics. be able to.

Claims (2)

C:0.015mass%以下、
Si:0.5mass%以下、
Mn:0.5mass%以下、
P:0.04mass%以下、
S:0.006mass%以下、
Cr:16〜20mass%以下、
N:0.015mass%以下、
Nb:0.3〜0.55mass%、
Ti:0.01mass%以下、
Mo:0.1mass%以下、
W:0.1mass%以下、
Cu:1.0〜2.5mass%、
Al:0.2〜1.2mass%を含有し、残部がFeおよび不可避的不純物からなるフェライト系ステンレス鋼。
C: 0.015 mass% or less,
Si: 0.5 mass% or less,
Mn: 0.5 mass% or less,
P: 0.04 mass% or less,
S: 0.006 mass% or less,
Cr: 16-20 mass% or less,
N: 0.015 mass% or less,
Nb: 0.3 to 0.55 mass%,
Ti: 0.01 mass% or less,
Mo: 0.1 mass% or less,
W: 0.1 mass% or less,
Cu: 1.0 to 2.5 mass%,
Al: Ferritic stainless steel containing 0.2 to 1.2 mass%, with the balance being Fe and inevitable impurities.
上記の成分組成に加えてさらに、B:0.003mass%以下、REM:0.08mass%以下、Zr:0.5mass%以下、V:0.5mass%以下、Co:0.5mass%以下およびNi:0.5mass%以下のうちから選ばれる1種または2種以上を含有することを特徴とする請求項1に記載のフェライト系ステンレス鋼。 In addition to the above component composition, B: 0.003 mass% or less, REM: 0.08 mass% or less, Zr: 0.5 mass% or less, V: 0.5 mass% or less, Co: 0.5 mass% or less, and Ni The ferritic stainless steel according to claim 1, comprising one or more selected from: 0.5 mass% or less.
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