JP2009035756A - Al-PLATED STEEL SHEET FOR EXHAUST GAS PASSAGEWAY MEMBER OF MOTORCYCLE EXCELLENT IN HIGH-TEMPERATURE STRENGTH AND THE GAS PASSAGE WAY MEMBER USING THE STEEL SHEET - Google Patents

Al-PLATED STEEL SHEET FOR EXHAUST GAS PASSAGEWAY MEMBER OF MOTORCYCLE EXCELLENT IN HIGH-TEMPERATURE STRENGTH AND THE GAS PASSAGE WAY MEMBER USING THE STEEL SHEET Download PDF

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JP2009035756A
JP2009035756A JP2007198903A JP2007198903A JP2009035756A JP 2009035756 A JP2009035756 A JP 2009035756A JP 2007198903 A JP2007198903 A JP 2007198903A JP 2007198903 A JP2007198903 A JP 2007198903A JP 2009035756 A JP2009035756 A JP 2009035756A
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steel sheet
exhaust gas
plating
plated steel
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Yoshiaki Hori
芳明 堀
Sadayuki Nakamura
定幸 中村
Manabu Oku
学 奥
Susumu Ueno
晋 上野
Yasunori Hattori
保徳 服部
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Nippon Steel Nisshin Co Ltd
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Nisshin Steel Co Ltd
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Priority to JP2007198903A priority Critical patent/JP2009035756A/en
Priority to US12/671,300 priority patent/US20100203357A1/en
Priority to PCT/JP2008/063939 priority patent/WO2009017246A1/en
Priority to CA2697138A priority patent/CA2697138A1/en
Priority to CN200880100740.5A priority patent/CN101765675A/en
Priority to EP08778367A priority patent/EP2184376A4/en
Priority to KR1020107000059A priority patent/KR20100035700A/en
Publication of JP2009035756A publication Critical patent/JP2009035756A/en
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/12—Aluminium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C21/00—Alloys based on aluminium
    • C22C21/02—Alloys based on aluminium with silicon as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/002—Ferrous alloys, e.g. steel alloys containing In, Mg, or other elements not provided for in one single group C22C38/001 - C22C38/60
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/26—Ferrous alloys, e.g. steel alloys containing chromium with niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/28—Ferrous alloys, e.g. steel alloys containing chromium with titanium or zirconium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/34—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of silicon
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C38/00—Ferrous alloys, e.g. steel alloys
    • C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
    • C22C38/38—Ferrous alloys, e.g. steel alloys containing chromium with more than 1.5% by weight of manganese
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/14—Removing excess of molten coatings; Controlling or regulating the coating thickness
    • C23C2/16—Removing excess of molten coatings; Controlling or regulating the coating thickness using fluids under pressure, e.g. air knives
    • C23C2/18—Removing excess of molten coatings from elongated material
    • C23C2/20—Strips; Plates
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N13/00—Exhaust or silencing apparatus characterised by constructional features ; Exhaust or silencing apparatus, or parts thereof, having pertinent characteristics not provided for in, or of interest apart from, groups F01N1/00 - F01N5/00, F01N9/00, F01N11/00
    • F01N13/16—Selection of particular materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2590/00—Exhaust or silencing apparatus adapted to particular use, e.g. for military applications, airplanes, submarines
    • F01N2590/04—Exhaust or silencing apparatus adapted to particular use, e.g. for military applications, airplanes, submarines for motorcycles
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
    • Y10T428/12736—Al-base component
    • Y10T428/1275—Next to Group VIII or IB metal-base component
    • Y10T428/12757—Fe

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • General Engineering & Computer Science (AREA)
  • Coating With Molten Metal (AREA)
  • Exhaust Silencers (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide an inexpensive Al-plated steel sheet having excellent red scale resistance, peeling resistance of a plating-coated layer, formability and low temperature toughness and high strength at high temperature. <P>SOLUTION: An Al-plated steel sheet for exhaust gas passageway members of motorcycles which is produced by dipping a substrate steel sheet which contains by mass C: 0.02% or below, Si: 2% or below, Mn: 2% or below, Cr: 5 to 25%, Nb: more than 0.1% to 1%, Ti: 0.3% or below, N: 0.02% or below, and, if necessary, one or more of Ni: 0.6% or below, Al: 0.2% or below, Mo: 3% or below, Cu: 3% or below, W: 3% or below, V: 0.5% or below, Co: 0.5% or below and B: 0.01% or below with the balance consisting of Fe and unavoidable impurities in a molten Al-based plating bath to form a hot-dip plating layer having a mean thickness of 3 to 20 μm on the surface of the sheet and which is excellent in high-temperature strength and red scale resistance. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

本発明は、二輪車のエンジン排ガス経路部材（例えばマフラー、触媒担持体、エキゾーストパイプなど）に使用する高温強度および耐赤スケール性に優れたアルミニウム系めっき鋼板、並びにそれを用いた二輪車排ガス経路部材に関する。   TECHNICAL FIELD The present invention relates to an aluminum-based plated steel sheet excellent in high-temperature strength and red scale resistance used for an engine exhaust gas path member (for example, a muffler, a catalyst carrier, an exhaust pipe) of a motorcycle, and a motorcycle exhaust gas path member using the same. .

二輪車のエンジン排ガス経路は、四輪車と比べ短く、マフラー等の下流部材でも４００℃以上の温度に曝されることが珍しくない。最近では排気ガス規制の強化から二輪車にも三元触媒を用いた排ガス浄化装置が搭載されつつあるが、その浄化装置は二輪車の場合、マフラーの中に装着されることが多い。二輪車の排ガス経路部材には、耐熱性の観点からＳＵＨ４０９ＬやＳＵＳ４３６等の耐熱性フェライト系ステンレス鋼が使用されている。   The engine exhaust gas path of a two-wheeled vehicle is shorter than that of a four-wheeled vehicle, and it is not uncommon for downstream members such as a muffler to be exposed to a temperature of 400 ° C. or higher. Recently, exhaust gas regulations have been strengthened and exhaust gas purification devices using a three-way catalyst are being mounted on motorcycles. In the case of motorcycles, the purification devices are often mounted in a muffler. A heat-resistant ferritic stainless steel such as SUH409L or SUS436 is used for an exhaust gas passage member of a motorcycle from the viewpoint of heat resistance.

ステンレス鋼を使用した排ガス経路部材では、赤褐色のスケール（以下「赤スケール」という）が発生することがある。これは排ガス温度が４００〜７００℃であり、かつ低酸素高水蒸気雰囲気で生じやすい現象である。赤スケールが発生し、それが凝結水と混ざると、赤褐色の液体となる。排ガス経路中の凝結水は排ガスとともに排気口から放出されることがあるが、上記のような赤褐色の液体の放出は外観上非常に好ましくない。   In an exhaust gas path member using stainless steel, a reddish brown scale (hereinafter referred to as “red scale”) may occur. This is a phenomenon in which the exhaust gas temperature is 400 to 700 ° C. and is likely to occur in a low oxygen and high water vapor atmosphere. When a red scale develops and mixes with condensed water, it becomes a reddish brown liquid. Condensed water in the exhaust gas path may be released from the exhaust port together with the exhaust gas, but the release of the reddish brown liquid as described above is very undesirable in appearance.

排ガス経路部材の中でマフラーは凝結水が溜まりやすい部位である。一般的な四輪車の場合、マフラーが４００℃以上の排ガスに曝されることは稀であり、マフラー内部に生成する赤スケールよりも、内部に結露する凝結水に起因した腐食が問題となりやすい。ところが二輪車の場合、前述のようにマフラーでも４００℃以上に曝されることが多いため、マフラー内に赤スケールが生成し、それに起因した赤褐色の液体の放出が問題となりやすい。   The muffler in the exhaust gas passage member is a portion where condensed water tends to accumulate. In the case of a general four-wheeled vehicle, the muffler is rarely exposed to exhaust gas of 400 ° C. or higher, and corrosion caused by condensed water condensing inside is more likely to be a problem than the red scale generated inside the muffler. . However, in the case of a two-wheeled vehicle, since the muffler is often exposed to 400 ° C. or more as described above, a red scale is generated in the muffler, and the discharge of reddish brown liquid due to the red scale tends to be a problem.

特許文献１には、予めＣｒ系酸化物を主体とする酸化皮膜を表面に生成させることによってストーブ燃焼筒等における赤スケールの発生を抑制する技術が開示されている。しかし、その酸化皮膜は耐食性に劣るため鋼素地の耐食性を向上させる対策が必要となり、素材コストの上昇を招く。このため、排ガス経路部材への適用は困難である。特許文献２、３には、ＡｌやＳｉを多量に添加した鋼により赤スケールを改善する手法が開示されている。しかし、このような高Ａｌ、Ｓｉ添加鋼の成形性は、ＳＵＨ２１（１８Ｃｒ−３Ａｌ系の耐スケール性が良好な鋼種）と比較すると良好であるが、ＳＵＨ４０９Ｌ、ＳＵＳ４１０Ｌ、ＳＵＳ４３０ＬＸ等のフェライト系ステンレス鋼種よりはかなり劣る。このため、二輪車の排ガス経路部材には適さない。   Patent Document 1 discloses a technique for suppressing the generation of red scale in a stove combustion cylinder or the like by generating an oxide film mainly composed of Cr-based oxide on the surface in advance. However, since the oxide film is inferior in corrosion resistance, it is necessary to take measures to improve the corrosion resistance of the steel substrate, leading to an increase in material cost. For this reason, application to an exhaust gas path member is difficult. Patent Documents 2 and 3 disclose methods for improving the red scale by using a steel to which a large amount of Al or Si is added. However, the formability of such high Al, Si-added steel is better than SUH21 (18Cr-3Al type steel type with good scale resistance), but ferritic stainless steel types such as SUH409L, SUS410L, and SUS430LX. Considerably worse than. For this reason, it is not suitable for an exhaust gas passage member of a motorcycle.

一方、ステンレス鋼等のＣｒ含有鋼にＡｌ系めっきを施した鋼板は、良好な耐酸化性を示すことから、自動車排気系部材に使用可能な種々のものが開発されている（特許文献４〜１３）。   On the other hand, steel plates obtained by applying Al-based plating to Cr-containing steels such as stainless steel exhibit good oxidation resistance, and therefore various types that can be used for automobile exhaust system members have been developed (Patent Documents 4 to 4). 13).

特開２００１−２４０９１１号公報JP 2001-240911 A 特開２００１−３１６７７３号公報JP 2001-316773 A 特開２００３−１６０８４４号公報JP 2003-160844 A 特開平８−３１９５４３号公報JP-A-8-319543 特開平５−１１２８５９号公報Japanese Patent Laid-Open No. 5-112859 特開平５−２９５５１３号公報Japanese Patent Laid-Open No. 5-295513 特開昭６１−１４７８６６号公報JP-A 61-147866 特開昭６１−１４７８６５号公報JP-A 61-147865 特開平７−２３３４５１号公報JP-A-7-233451 特開昭６３−４７３５６号公報JP 63-47356 A 特開平３−２７７７６１号公報Japanese Patent Laid-Open No. 3-277761 特開平７−１８８８８７号公報Japanese Patent Laid-Open No. 7-188887 特開平８−３２５６９１号公報JP-A-8-325691

発明者らの検討によれば、ステンレス鋼等のＣｒ含有鋼板の赤スケール発生に対する抵抗力（以下「耐赤スケール性」という）を向上させるためにはＡｌ系めっきを施すことが有効である。しかしながら、発明者らが上記公知のＡｌ系めっき鋼板について詳細に調査したところ、これらは二輪車排ガス経路部材として広く実用化を図るうえで、改善すべき問題を有していることがわかった。   According to the study by the inventors, it is effective to apply Al-based plating in order to improve the resistance against red scale generation of a Cr-containing steel plate such as stainless steel (hereinafter referred to as “red scale resistance”). However, when the inventors investigated the above-mentioned known Al-based plated steel sheet in detail, it was found that these had problems to be improved when they were widely put into practical use as motorcycle exhaust gas passage members.

すなわち、特許文献４のＡｌ系めっき鋼板は、合金層にＭｎ等を濃化させたものであり、まためっき層厚さも十分に薄いとは言えないため、めっき被覆層（本明細書では合金層を含んだ溶融めっき被覆層を「めっき被覆層」と呼ぶ）の耐剥離性が不十分であると判断された。特許文献５、６のめっき鋼板は、めっき層厚さが厚いので、これもめっき被覆層の耐剥離性が不足する。特許文献７、８、１０のめっき鋼板は、Ｎｉ等のプレめっきを行った後にＡｌ系めっきを施すことによって得られるものであるが、そのような工程を採用すると製造コストが増大し、コストダウンが強く求められるマフラーや触媒担持体等の排ガス経路部材には容易に採用するわけにいかない。また、４００〜７００℃域に加熱される場合のめっき被覆層の耐剥離性については、必ずしも満足できるレベルにない。特許文献９のめっき鋼板は、基材に希土類元素またはＹを必須添加した鋼を使用することによって１１５０〜１２５０℃という高温での異常酸化を防止したものであるが、めっき層と基材との密着性が不十分であるため４００〜７００℃域への加熱・冷却を繰り返すとめっき被覆層が剥離しやすい。特許文献１１、１２のめっき鋼板は、めっき層厚さが十分に薄くないので、４００〜７００℃域への加熱・冷却に対するめっき被覆層の耐剥離性が不十分である。なお、特許文献１１に記載される「赤錆」は常温下で腐食が進行した普通鋼に典型的に見られる赤錆であり、本願でいう「赤スケール」とは異質のものである。   That is, since the Al-based plated steel sheet of Patent Document 4 is obtained by concentrating an alloy layer with Mn and the like, and the plating layer thickness cannot be said to be sufficiently thin, the plating coating layer (in this specification, the alloy layer) It was judged that the peel resistance of the hot-plated coating layer containing the metal was called “plating coating layer”. Since the plated steel sheets of Patent Documents 5 and 6 have a large plating layer thickness, they also lack the peel resistance of the plating coating layer. Although the plated steel sheets of Patent Documents 7, 8, and 10 are obtained by performing Al-based plating after pre-plating of Ni or the like, the use of such a process increases the manufacturing cost and reduces the cost. However, it cannot be easily adopted for exhaust gas passage members such as mufflers and catalyst carriers. Moreover, about the peeling resistance of the plating coating layer when heated to 400-700 degreeC area, it is not necessarily in the level which can be satisfied. The plated steel sheet of Patent Document 9 prevents abnormal oxidation at a high temperature of 1150 to 1250 ° C. by using a steel in which a rare earth element or Y is essentially added to the base material. Since the adhesiveness is insufficient, the plating coating layer tends to peel off when heating and cooling to 400 to 700 ° C. are repeated. Since the plated steel sheets of Patent Documents 11 and 12 do not have a sufficiently thin plating layer thickness, the plating coating layer has insufficient peel resistance against heating and cooling to a range of 400 to 700 ° C. Note that “red rust” described in Patent Document 11 is red rust typically seen in ordinary steel that has been corroded at room temperature, and is different from “red scale” in the present application.

このように、公知のＡｌ系めっきステンレス鋼板は、基本的に４００〜７００℃の温度域に加熱した場合のめっき被覆層の耐剥離性が十分とは言えない。したがって、従来のＡｌ系めっきステンレス鋼板は、４００〜７００℃の温度域で使用される二輪車のマフラー、触媒担持体などに適用すると、初期には良好な耐食性および耐赤スケール性を呈しても、長期間使用している間にめっき被覆層の剥離が生じ、耐食性の低下や耐赤スケール性の低下を招くようになる。つまり耐久性の点で不安要因を抱えている。一方、排ガス規制の強化から二輪車にも排ガス浄化触媒を搭載する車種が増加している。触媒を搭載すれば反応により排ガス温度が上昇し、マフラー等の排ガス経路部材は一層高温に曝されることになる。したがって、二輪車の排ガス経路部材には従来にも増して高温強度の高い材料の適用が望まれるようになってきた。また、排ガス部材用の鋼板としては成形性や低温靭性が良好であることも要求される。さらに、低コストであることも実用化にとって重要である。   Thus, the known Al-plated stainless steel sheet cannot be said to have sufficient peeling resistance of the plating coating layer when heated to a temperature range of 400 to 700 ° C. basically. Therefore, when the conventional Al-plated stainless steel sheet is applied to a muffler of a two-wheeled vehicle used in a temperature range of 400 to 700 ° C., a catalyst carrier, etc., even when initially exhibiting good corrosion resistance and red scale resistance, The plating coating layer peels off during long-term use, leading to a reduction in corrosion resistance and red scale resistance. In other words, it has an anxiety factor in terms of durability. On the other hand, due to stricter exhaust gas regulations, motorcycles equipped with exhaust gas purification catalysts are increasing. If the catalyst is mounted, the exhaust gas temperature rises due to the reaction, and the exhaust gas path member such as the muffler is exposed to a higher temperature. Therefore, it has been desired to apply a material having higher high-temperature strength to the exhaust gas path member of a motorcycle than ever before. Further, the steel plate for exhaust gas member is also required to have good formability and low temperature toughness. Furthermore, low cost is also important for practical use.

本発明は、二輪車排ガス経路部材に用いるためのＡｌ系めっき鋼板であって、優れた耐赤スケール性、成形性、低温靭性を具備し、かつ４００〜７００℃の温度域に繰り返し加熱した際には、めっき被覆層の耐剥離性が顕著に改善される、安価で高温強度の高いＡｌ系めっき鋼板を提供することを目的とする。   The present invention is an Al-based plated steel sheet for use in a motorcycle exhaust gas path member, which has excellent red scale resistance, formability, and low temperature toughness, and is repeatedly heated to a temperature range of 400 to 700 ° C. An object of the present invention is to provide an inexpensive, high-temperature strength Al-based plated steel sheet in which the peel resistance of the plating coating layer is remarkably improved.

発明者らは詳細な検討の結果、Ａｌ系めっき層の厚さを２０μｍ以下に薄くコントロールすることによってＡｌ系めっき被覆層の耐剥離性が顕著に改善されることを見出し、本発明を完成するに至った。   As a result of detailed studies, the inventors have found that the peel resistance of the Al-based plating coating layer is remarkably improved by controlling the thickness of the Al-based plating layer to 20 μm or less, and complete the present invention. It came to.

すなわち本発明は、鋼素地の組成が質量％で、Ｃ：０.０２％以下、Ｓｉ：２％以下、Ｍｎ：２％以下、Ｃｒ：５〜２５％、Ｎｂ：０.１超え〜１％、Ｔｉ：０.３％以下、Ｎ：０.０２％以下であり、さらに必要に応じてＮｉ：０.６％以下、Ａｌ：０.２％以下、Ｍｏ：３％以下、Ｃｕ：３％以下、Ｗ：３％以下、Ｖ：０.５％以下、Ｃｏ：０.５％以下、Ｂ：０.０１％以下の１種以上を含有し、残部がＦｅおよび不可避的不純物である鋼板を基材とし、
前記基材を、質量％で、Ｓｉ：３〜１２％を含有し、場合によってはさらにＴｉ、Ｂ、Ｓｒ、Ｃｒ、Ｍｎ、Ｍｇ、Ｚｒの１種以上を合計１％以下の範囲で含有し、残部Ａｌおよび不可避的不純物からなる溶融めっき浴に浸漬したのち引き上げ、めっき付着量を調整することにより、平均厚さ３〜２０μｍの溶融めっき層を表面に形成した耐赤スケール性に優れた二輪車排ガス経路部材用Ａｌ系めっき鋼板が提供される。 That is, according to the present invention, the composition of the steel base is mass%, C: 0.02% or less, Si: 2% or less, Mn: 2% or less, Cr: 5 to 25%, Nb: more than 0.1 to 1% Ti: 0.3% or less, N: 0.02% or less, Ni: 0.6% or less, Al: 0.2% or less, Mo: 3% or less, Cu: 3% as required Hereinafter, a steel sheet containing at least one of W: 3% or less, V: 0.5% or less, Co: 0.5% or less, and B: 0.01% or less, with the balance being Fe and inevitable impurities. As a base material,
The base material contains Si: 3 to 12% by mass, and optionally further contains at least one of Ti, B, Sr, Cr, Mn, Mg, and Zr in a range of 1% or less in total. A motorcycle excellent in red scale resistance in which a molten plating layer having an average thickness of 3 to 20 μm is formed on the surface by dipping in a molten plating bath composed of the remaining Al and inevitable impurities, and then adjusting the amount of plating attached. An Al-based plated steel sheet for an exhaust gas path member is provided.

また本発明では、上記のめっき鋼板を素材に用いて構成され、前記めっき層が排ガスと接触する構造を有する、最高使用温度が４００℃以上の二輪車排ガス経路部材が提供される。   Further, the present invention provides a two-wheeled vehicle exhaust gas path member having a maximum use temperature of 400 ° C. or more, which is configured by using the plated steel sheet as a raw material and has a structure in which the plating layer is in contact with exhaust gas.

本発明のＡｌ系めっき鋼板は、耐赤スケール性に優れるとともに、４００〜７００℃の温度域に繰り返し加熱された場合におけるめっき被覆層の耐剥離性に優れるので、当該温度域に加熱されて赤スケールの生じやすい環境で使用される二輪車の排ガス経路部材（例えばマフラー部材）に好適である。高温強度の高い基材鋼板を使用しているので排ガス経路部材の設計自由度が拡大し、この点は排ガス浄化触媒を搭載して排ガス温度が上昇する車種において特に有利となる。また製造コストも一般的なＡｌめっきステンレス鋼板と同等以下に抑えられる。したがって本発明は、二輪車の排ガス経路部材の品質向上、耐久性向上および設計自由度の向上に寄与しうる。   The Al-based plated steel sheet of the present invention is excellent in red scale resistance and excellent in peeling resistance of the plating coating layer when repeatedly heated in a temperature range of 400 to 700 ° C. It is suitable for an exhaust gas passage member (for example, a muffler member) of a two-wheeled vehicle used in an environment where scale is likely to occur. Since a base steel plate having a high temperature strength is used, the degree of freedom in designing the exhaust gas path member is expanded. This is particularly advantageous in a vehicle type in which an exhaust gas purification catalyst is mounted and the exhaust gas temperature rises. Further, the manufacturing cost can be suppressed to the same level or lower as that of a general Al-plated stainless steel plate. Therefore, the present invention can contribute to improving the quality, durability and design flexibility of the exhaust gas path member of a motorcycle.

フェライト系ステンレス鋼等の高Ｃｒ鋼を高温に加熱すると、一般にＣｒ濃度の高い酸化物（Ｃｒ系酸化物）が鋼素地表面に形成される。このＣｒ系酸化物は保護性が高いので、高Ｃｒ鋼は低Ｃｒ鋼に比べ一般的に良好な耐高温酸化性を有する。ところが、このような高Ｃｒ鋼であっても、４００〜７００℃の温度域で、かつ低酸素高水蒸気雰囲気に加熱した場合には、その初期酸化過程においてＣｒ系酸化物よりもＦｅ系酸化物が生成されやすいことがわかっている。これは、当該温度域では鋼素地表面をＣｒ系酸化物で覆うに足るだけのＣｒが表面に迅速に拡散することができず、むしろ表面に多量に存在するＦｅの方が低酸素高水蒸気雰囲気下では優先的に酸化されるためであると考えられる。赤スケールは、上記のようにして表面に生成するＦｅ濃度の高い酸化物によって構成される。   When high Cr steel such as ferritic stainless steel is heated to a high temperature, an oxide having a high Cr concentration (Cr oxide) is generally formed on the surface of the steel base. Since this Cr-based oxide is highly protective, high Cr steel generally has better high-temperature oxidation resistance than low Cr steel. However, even in such high Cr steel, when heated in a temperature range of 400 to 700 ° C. and in a low-oxygen high-water vapor atmosphere, Fe-based oxide is more preferable than Cr-based oxide in the initial oxidation process. Is known to be easily generated. This is because, in this temperature range, Cr sufficient to cover the steel substrate surface with Cr-based oxides cannot be diffused rapidly on the surface, but rather Fe that is present in a large amount on the surface is in a low oxygen high water vapor atmosphere. This is probably because it is preferentially oxidized below. A red scale is comprised by the oxide with high Fe density | concentration produced | generated on the surface as mentioned above.

赤スケールの生成を防止するには、上記温度および雰囲気において、鋼素地表面にＦｅ系酸化物が形成されないようにすればよい。その一手段として、Ａｌ系めっきを施すことが有効である。この場合、めっき層表面のＡｌが迅速に酸化され、鋼板表面はＡｌ系酸化皮膜で覆われる。   In order to prevent the formation of red scale, it is only necessary to prevent the formation of Fe-based oxides on the surface of the steel base at the above temperature and atmosphere. As one means, it is effective to apply Al-based plating. In this case, Al on the plating layer surface is rapidly oxidized, and the steel plate surface is covered with an Al-based oxide film.

しかしながら、発明者らの調査によると、Ａｌ系めっき被覆層は、４００〜７００℃の温度への加熱および冷却を繰り返すと、鋼素地表面から剥離しやすいことがわかった。このことが従来のＡｌ系めっき鋼板を二輪車のマフラー部材等に使用した場合に必ずしも良好な耐久性を示さない大きな要因になっている。溶融Ａｌ系めっき鋼板を４００〜７００℃に加熱すると、めっき層中のＡｌと鋼素地のＦｅが相互拡散することによりＦｅ−Ａｌ系の金属間化合物層が生成し、この金属間化合物層と鋼素地の間で剥離が生じる。このようにしてめっき被覆層が剥離すると、そこから新たに赤スケールが発生するようになる。   However, according to investigations by the inventors, it has been found that the Al-based plating coating layer easily peels from the surface of the steel substrate when heating and cooling to a temperature of 400 to 700 ° C. are repeated. This is a major factor that does not necessarily show good durability when a conventional Al-based plated steel sheet is used for a muffler member of a motorcycle. When the molten Al-based plated steel sheet is heated to 400 to 700 ° C., the Al in the plating layer and the Fe in the steel base are interdiffused to form an Fe—Al based intermetallic compound layer. Delamination occurs between the substrates. When the plating coating layer peels in this way, a new red scale is generated therefrom.

発明者らはＡｌ系めっき鋼板のめっき被覆層剥離を防止する手法について詳細に検討を行ってきた。その結果、Ａｌ系めっき層の厚さを薄くすることが、４００〜７００℃の温度域で、かつ低酸素高水蒸気雰囲気に加熱した場合のＡｌ系めっき被覆層の剥離現象を抑止する上で極めて有効であることを見出した。この場合、Ａｌ系めっき層の組成・組織状態、あるいは合金層の組成等に特別の規制を設ける必要はない。   Inventors have examined in detail about the method of preventing the plating coating layer peeling-off of the Al system plating steel plate. As a result, reducing the thickness of the Al-based plating layer is extremely effective in suppressing the peeling phenomenon of the Al-based plating coating layer when heated to a low oxygen high-water vapor atmosphere in the temperature range of 400 to 700 ° C. I found it effective. In this case, it is not necessary to provide special restrictions on the composition / structure of the Al-based plating layer or the composition of the alloy layer.

〔Ａｌ系めっき層の厚さ〕
具体的には、溶融Ａｌ系めっき鋼板において、Ａｌ系めっき層の平均厚さを片面当たり２０μｍ以下に抑えることにより、安定して優れた耐剥離性を呈するようになる。ここで、Ａｌ系めっき層の平均厚さは、合金層を含まない厚さである。溶融めっき付着量は周知のようにガスワイピング法等により調整できるが、片面当たりのめっき付着量そのものが２０μｍ以下になるようにコントロールすれば、その一部は鋼素地と反応して合金層となるので、形成されるＡｌ系めっき層の平均厚さが２０μｍを超えることはない。合金層が比較的厚めに形成される操業条件であれば、めっき付着量を２０μｍより多少厚めに設定しても、めっき層の平均厚さを２０μｍ以下とすることができる場合がある。Ａｌ系めっき層の平均厚さを１５μｍ未満とすることにより、耐剥離性は一段と向上する。したがって、片面当たりのＡｌ系めっき層の平均厚さが１５μｍ未満であるものは、本発明において特に好ましい対象となる。 [Al-based plating layer thickness]
Specifically, in the hot-dip Al-based plated steel sheet, the average thickness of the Al-based plating layer is suppressed to 20 μm or less per side, and thus excellent peel resistance is stably exhibited. Here, the average thickness of the Al-based plating layer is a thickness not including the alloy layer. As is well known, the amount of hot-dip plating can be adjusted by a gas wiping method or the like. However, if the amount of hot metal plating per side is controlled to be 20 μm or less, a part of it reacts with the steel substrate to become an alloy layer. Therefore, the average thickness of the Al-based plating layer to be formed does not exceed 20 μm. If the operating conditions are such that the alloy layer is formed relatively thick, the average thickness of the plating layer may be 20 μm or less even if the plating adhesion amount is set to be slightly thicker than 20 μm. By making the average thickness of the Al-based plating layer less than 15 μm, the peel resistance is further improved. Therefore, those having an average thickness of the Al-based plating layer per side of less than 15 μm are particularly preferred objects in the present invention.

一方、赤スケールを防止する観点からは、Ａｌ系めっき層の厚さは厚いほど好ましい。種々検討の結果、後述のように組成調整された基材鋼板を使用した上で、片面当たりのＡｌ系めっき層の平均厚さを３μｍ以上を確保する必要がある。それよりめっき層が薄くなると赤スケールの発生を安定して防止することが難しくなる。４μｍ以上の平均厚さを確保することがより好ましく、５μｍ以上とすることが一層好ましい。   On the other hand, from the viewpoint of preventing red scale, the thickness of the Al-based plating layer is preferably as thick as possible. As a result of various studies, it is necessary to secure an average thickness of the Al-based plating layer per side of 3 μm or more after using a base steel plate whose composition is adjusted as described later. If the plating layer becomes thinner than that, it is difficult to stably prevent the occurrence of red scale. It is more preferable to ensure an average thickness of 4 μm or more, and it is even more preferable to set it to 5 μm or more.

〔合金層の厚さ〕
合金層は、鋼素地やめっき層に比べて脆い。このため、合金層の厚さは加工性を考慮すると薄い方が好ましい。加工度の低い部材用途では特にこだわる必要はないが、厳しい加工を施す場合には片面当たりの合金層平均厚さは５μｍ以下であることが好ましく、４μｍ以下であることがより好ましい。ガスワイピング法を用いた溶融Ａｌ系めっきラインにおいて、このような薄い合金層厚さのものを製造することが十分可能である。めっき層厚さと合金層厚さの合計厚さで見ると、片面当たりの「Ａｌ系めっき層の平均厚さ＋合金層の平均厚さ」が２４μｍ以下になるように合金層厚さをコントロールすることが望ましい [Alloy layer thickness]
The alloy layer is brittle compared to the steel substrate or the plated layer. For this reason, the thickness of the alloy layer is preferably thinner in consideration of workability. There is no need to pay particular attention to the use of a member with a low degree of processing. However, when severe processing is performed, the average thickness of the alloy layer per one side is preferably 5 μm or less, and more preferably 4 μm or less. In a hot Al plating line using the gas wiping method, it is sufficiently possible to manufacture a thin alloy layer having such a thickness. When viewed from the total thickness of the plating layer thickness and the alloy layer thickness, the alloy layer thickness is controlled so that the “average thickness of the Al-based plating layer + the average thickness of the alloy layer” per side is 24 μm or less. Is desirable

〔Ａｌ系めっき浴の組成〕
Ａｌ−Ｓｉ合金系では、ＡｌにＳｉを添加していくと液相線温度が低下し、約１２質量％Ｓｉ付近で共晶組成となる。本発明では３質量％以上のＳｉを含有する溶融Ａｌ系めっき浴を使用する。それよりＡｌリッチの組成になると浴温が高くなるので、合金層の平均厚さを薄く（例えば５μｍ以下に）抑制することが難しくなる。また、浴温の上昇は製造コストの増大を招く要因にもなる。ただし、Ｓｉ含有量が１２質量％を超えるとＡｌ系めっき層自体の加工性が低下し、問題となりやすい。したがって、本発明では３〜１２質量％のＳｉを含有する溶融Ａｌ系めっき浴を使用して製造されるめっき鋼板を対象とする。 [Composition of Al plating bath]
In the Al—Si alloy system, the liquidus temperature decreases as Si is added to Al, and a eutectic composition is obtained in the vicinity of about 12 mass% Si. In the present invention, a molten Al-based plating bath containing 3% by mass or more of Si is used. When the composition is richer than that, the bath temperature becomes high, and it becomes difficult to suppress the average thickness of the alloy layer to be thin (for example, 5 μm or less). In addition, an increase in bath temperature also causes an increase in manufacturing cost. However, if the Si content exceeds 12% by mass, the workability of the Al-based plating layer itself is lowered, which tends to cause a problem. Therefore, in this invention, the plated steel plate manufactured using the molten Al type plating bath containing 3-12 mass% Si is made into object.

Ａｌ系めっき浴中には、Ｔｉ、Ｂ、Ｓｒ、Ｃｒ、Ｍｎ、Ｍｇ、Ｚｒの１種以上が合計１％以下の範囲で含有されていて構わない。その他、浴中には不可避的不純物としてＦｅが含まれるが、Ｆｅの混入は２.５質量％以下の範囲で許容される。   In the Al-based plating bath, one or more of Ti, B, Sr, Cr, Mn, Mg, and Zr may be contained within a total range of 1% or less. In addition, Fe is contained as an inevitable impurity in the bath, but mixing of Fe is allowed in a range of 2.5 mass% or less.

〔基材鋼板〕
めっき原板となる基材鋼板は、Ｃｒを５〜２５質量％含有する高Ｃｒ鋼が対象となる。Ａｌ系めっきを施すことによって耐食性および耐酸化性が向上することから、必ずしもステンレス鋼レベルのＣｒ含有量は必要としないが、結露水や水蒸気と接触する環境に曝される二輪車排ガス経路部材として要求される耐食性を確保し、かつ耐赤スケール性を確保するためには、少なくとも５質量％以上のＣｒ含有量が必要である。１０質量％以上のＣｒ含有量を確保することがより好ましい。Ｃｒ含有量の増加に伴って耐食性および耐熱性は向上するが、過剰のＣｒ含有は不経済であり、また成形性や低温靭性を阻害する要因になるので、基材鋼板のＣｒ含有量は２５質量％以下の範囲に規定される。 [Base steel plate]
The base steel plate used as the plating base plate is a high Cr steel containing 5 to 25% by mass of Cr. Since corrosion resistance and oxidation resistance are improved by applying Al-based plating, Cr content at the stainless steel level is not necessarily required, but it is required as a motorcycle exhaust gas path member exposed to the environment in contact with condensed water or water vapor In order to ensure the corrosion resistance and the red scale resistance, a Cr content of at least 5% by mass is required. It is more preferable to ensure a Cr content of 10% by mass or more. Corrosion resistance and heat resistance are improved with an increase in Cr content, but excessive Cr content is uneconomical and becomes a factor that hinders formability and low temperature toughness, so the Cr content of the base steel sheet is 25. It is specified in the range of mass% or less.

Ｎｂは、高温強度を向上させる作用を有する。また、Ｃ、Ｎ含有量が比較的多い場合には低温靭性を改善する作用もある。これらの作用を十分に得るために本発明では０.１質量％を超えるＮｂを含有するフェライト系鋼を採用する。ただし、発明者らの研究によれば、基材鋼板に含まれるＮｂは溶融Ａｌ系めっき層の耐剥離性を阻害する要因を有していることが明らかになった。詳細な検討の結果、上述のようにＡｌ系めっき層の平均厚さを２０μｍ以下とすることを前提に、基材鋼板中のＮｂ含有量は１％まで許容できることがわかった。したがって、本発明ではＮｂを０.１超え〜１％の範囲で含有する基材鋼板を使用する。   Nb has the effect | action which improves high temperature strength. In addition, when the C and N contents are relatively large, there is an effect of improving the low temperature toughness. In order to obtain these effects sufficiently, the present invention employs a ferritic steel containing Nb exceeding 0.1% by mass. However, the inventors' research has revealed that Nb contained in the base steel sheet has a factor that impairs the peel resistance of the molten Al-based plating layer. As a result of detailed studies, it was found that the Nb content in the base steel sheet can be tolerated up to 1% on the assumption that the average thickness of the Al-based plating layer is 20 μm or less as described above. Therefore, in the present invention, a base steel sheet containing Nb in a range exceeding 0.1 to 1% is used.

Ｔｉは、鋼中のＣ、Ｎを固定し、フェライト相の安定化を図るとともに、低温靭性や成形性を高めるために有効な元素である。これらの作用を十分に引き出すためには０.０５質量％以上のＴｉ含有量を確保することが好ましく、０.１質量％以上とすることがより好ましい。しかし、過剰のＴｉ含有は鋼を硬質化し、逆に加工性および低温靭性の低下を招くことになる。したがってＴｉ含有量は０.３質量％以下の範囲に制限され、０.２質量％以下の範囲で添加することがより好ましい。   Ti is an element effective for fixing C and N in steel, stabilizing the ferrite phase, and improving low temperature toughness and formability. In order to sufficiently bring out these effects, it is preferable to secure a Ti content of 0.05% by mass or more, and more preferably 0.1% by mass or more. However, excessive Ti content hardens the steel and conversely causes a decrease in workability and low temperature toughness. Therefore, the Ti content is limited to a range of 0.3% by mass or less, and it is more preferable to add in a range of 0.2% by mass or less.

Ｃ、Ｓｉ、Ｍｎ、Ｎは鋼中に含まれる基本元素であり、Ｃは０.０２質量％以下、Ｎは０.０２質量％以下の範囲とすることができる。Ｓｉ、Ｍｎの含有量が多くなると低温靭性が低下するが、本発明ではＳｉ、Ｍｎとも２質量％までの含有が許容される。その他の元素として、Ｎｉ：０.６％以下、Ａｌ：０.２％以下、Ｍｏ：３％以下、Ｃｕ：３％以下、Ｗ：３％以下、Ｖ：０.５％以下、Ｃｏ：０.５％以下、Ｂ：０.０１％以下の１種以上を含有して構わないが、これらの元素の含有量が上記規定を超えると成形性や低温靭性に悪影響を及ぼすことがある。不可避的不純物であるＰは０.１０質量％程度まで、またＳは０.０３質量％程度まで許容される。   C, Si, Mn, and N are basic elements contained in the steel. C can be 0.02 mass% or less, and N can be 0.02 mass% or less. When the Si and Mn contents increase, the low temperature toughness decreases, but in the present invention, the Si and Mn contents up to 2% by mass are allowed. As other elements, Ni: 0.6% or less, Al: 0.2% or less, Mo: 3% or less, Cu: 3% or less, W: 3% or less, V: 0.5% or less, Co: 0 One or more of 0.5% or less and B: 0.01% or less may be contained. However, if the content of these elements exceeds the above-mentioned rules, the moldability and the low temperature toughness may be adversely affected. Inevitable impurities such as P are allowed up to about 0.10% by mass, and S is allowed up to about 0.03% by mass.

〔製造方法〕
基材鋼板は、一般的な鋼板製造プロセスによって製造することができ、その製造法は特に規定されるものではない。例えば酸洗仕上の冷延鋼板を基材とすることができ、基材鋼板の表面が活性化された状態で溶融Ａｌ系めっき浴に浸漬したのち引き上げ、めっき付着量を調整することにより、本発明の溶融Ａｌ系めっき鋼板を製造することができる。また、めっき性を向上させるためにＦｅプレめっきを施したものを基材鋼板として採用することができる。基材鋼板を鋼帯の状態で連続溶融めっきラインに通板することにより、安定した品質の溶融Ａｌ系めっき鋼板を大量生産することができる。めっき条件は、めっき層の平均厚さが片面当たり２０μｍ以下になるようにライン速度やワイピング条件をコントロールすることが重要であるが、それ以外は従来一般的な条件を採用すればよい。得られためっき鋼板は、所定の成形加工を経て二輪車用の排ガス経路部材に加工される。部材によっては溶接造管に供された後、成形加工される。 〔Production method〕
The base steel plate can be manufactured by a general steel plate manufacturing process, and the manufacturing method is not particularly defined. For example, a cold-rolled steel plate with pickling finish can be used as a base material, and the surface of the base steel plate is dipped in a molten Al-based plating bath in an activated state, and then adjusted by adjusting the plating adhesion amount. The hot-dip Al-based plated steel sheet of the invention can be manufactured. Moreover, what gave Fe pre-plating in order to improve plating property is employable as a base-material steel plate. By passing the base steel sheet through a continuous hot dipping line in the state of a steel strip, it is possible to mass-produce hot quality hot-dip aluminum-based plated steel sheets. As for the plating conditions, it is important to control the line speed and the wiping conditions so that the average thickness of the plating layer is 20 μm or less per side, but otherwise conventional conditions may be adopted. The obtained plated steel sheet is processed into an exhaust gas path member for a motorcycle through a predetermined forming process. Depending on the member, it is subjected to a forming process after being used for welding pipe making.

表１に示す組成のフェライト系鋼種を溶製し、常法により板厚１.２ｍｍの冷延焼鈍鋼板（酸洗仕上げ材）を得た。いずれの鋼種も不可避的不純物であるＰは０.１０質量％以下、Ｓは０.０１質量％以下に収まっている。これらの鋼板を基材（めっき原板）に用いて、種々の溶融Ａｌ系めっきを施した。なお、Ｎｏ.１１、２７については冷延焼鈍鋼板の表面にＦｅプレめっき（２ｇ／ｍ2）を施したものを基材とした。また、全ての実施例のめっき浴中には不可避的不純物としてＦｅが１.７質量％程度含まれている。得られた溶融Ａｌ系めっき鋼板（供試材）の断面をＳＥＭ（走査型電子顕微鏡）で観察することにより、Ａｌ系めっき層の平均厚さを求めた。なお、その際、合金層の平均厚さも調べた結果、一部の比較例を除き、全て４μｍ以下であった。 Ferritic steel types having the compositions shown in Table 1 were melted, and a cold-rolled annealed steel sheet (pickling finish) having a thickness of 1.2 mm was obtained by a conventional method. In all steel types, P, which is an inevitable impurity, is 0.10% by mass or less, and S is 0.01% by mass or less. Using these steel plates as a base material (plating original plate), various hot-dip Al-based platings were performed. Note that No.11,27 were those subjected to Fe pre-plating (2g / m 2) on the surface of the cold-rolled annealed steel sheet with a substrate. Further, the plating baths of all the examples contain about 1.7% by mass of Fe as an inevitable impurity. The average thickness of the Al-based plating layer was determined by observing the cross section of the obtained molten Al-based plated steel sheet (test material) with an SEM (scanning electron microscope). In addition, as a result of examining the average thickness of the alloy layer at that time, all of them were 4 μm or less except for some comparative examples.

Figure 2009035756
Figure 2009035756

各供試材について、耐赤スケール性、めっき被覆層の耐剥離性、成形性、低温靭性を以下のようにして評価した。   About each test material, red scale resistance, peeling resistance of a plating coating layer, moldability, and low temperature toughness were evaluated as follows.

〔耐赤スケール性〕
供試材から２５ｍｍ×３５ｍｍの試験片を切り出し、これを用いて以下の２通りの加熱モードで酸化試験を実施した。試験数は各モードｎ＝３とした。
・連続加熱； 露点８０℃の窒素雰囲気中、６００℃で１００時間連続加熱する。
・サイクル加熱； 「露点８０℃の窒素雰囲気中、６００℃で３０分加熱（うち均熱時間２５分）→空冷５分」を１サイクルとし、これを５００サイクル繰り返す。
各加熱モードを実施した試験片について、目視観察により赤褐色の変色の有無を調べた。また、酸化増量および酸化減量（スケール剥離量）を測定した。ｎ＝３全ての試験片について、（i）赤褐色の変色が認められないこと、（ii）酸化増量が０.２ｍｇ／ｃｍ2未満であること、（iii）酸化減量が０.２ｍｇ／ｃｍ2未満であること、の３つをクリアした供試材を○（良好）、それ以外を×（不良）と評価した。 [Red scale resistance]
A test piece of 25 mm × 35 mm was cut out from the test material, and an oxidation test was performed using the test piece in the following two heating modes. The number of tests was set to each mode n = 3.
Continuous heating: Continuous heating at 600 ° C. for 100 hours in a nitrogen atmosphere with a dew point of 80 ° C.
-Cycle heating: “Heating for 30 minutes at 600 ° C. in a nitrogen atmosphere with a dew point of 80 ° C. (of which soaking time is 25 minutes) → air cooling for 5 minutes” is one cycle and this is repeated 500 cycles.
About the test piece which implemented each heating mode, the presence or absence of reddish brown discoloration was investigated by visual observation. Moreover, the oxidation increase and oxidation loss (scale peeling amount) were measured. n = 3 For all the test pieces, (i) no reddish brown discoloration was observed, (ii) oxidation increase was less than 0.2 mg / cm 2 , (iii) oxidation loss was 0.2 mg / cm 2 The test materials that cleared three of the following were evaluated as ○ (good) and the other samples as × (defect).

〔めっき被覆層の耐剥離性〕
供試材から２５ｍｍ×３５ｍｍの試験片を切り出し、これを用いて以下に示す６００℃サイクル加熱、および７００℃サイクル加熱を実施した。試験数は各温度ｎ＝５とした。
・６００℃サイクル加熱； 「露点８０℃の窒素雰囲気中、６００℃で３０分加熱（うち均熱時間２５分）→空冷５分」を１サイクルとし、これを１０００サイクル繰り返す。
・７００℃サイクル加熱； 「露点８０℃の窒素雰囲気中、７００℃で３０分加熱（うち均熱時間２５分）→空冷５分」を１サイクルとし、これを１０００サイクル繰り返す。
各温度で実施した試験片について、目視観察によりめっき被覆層の剥離の有無を調べた。各温度５個（ｎ＝５）×温度２水準の計１０個の試験片全てについて、めっき層の剥離が認められなかった供試材を○（良好）、それ以外を（不良）と評価した。 [Peeling resistance of plating coating layer]
A test piece of 25 mm × 35 mm was cut out from the test material, and the 600 ° C. cycle heating and 700 ° C. cycle heating shown below were performed using the test piece. The number of tests was each temperature n = 5.
• 600 ° C. cycle heating: “Heating for 30 minutes at 600 ° C. in a nitrogen atmosphere with a dew point of 80 ° C. (of which soaking time is 25 minutes) → air cooling for 5 minutes” is one cycle, and this is repeated 1000 cycles.
700 ° C. cycle heating; “In a nitrogen atmosphere with a dew point of 80 ° C., heating at 700 ° C. for 30 minutes (including soaking time 25 minutes) → air cooling 5 minutes” is one cycle, and this is repeated 1000 cycles.
About the test piece implemented at each temperature, the presence or absence of peeling of a plating coating layer was investigated by visual observation. For all 10 test pieces each having 5 temperatures (n = 5) × 2 temperature levels, the test material in which no peeling of the plating layer was observed was evaluated as good (good), and the others were evaluated as poor. .

また、上記１０００サイクルの試験で○評価が得られた供試材については、同様の６００℃サイクル加熱、および７００℃サイクル加熱を２０００サイクルまで実施した。２０００サイクル後に、各温度５個（ｎ＝５）×温度２水準の計１０個の試験片全てについて、めっき被覆層の剥離が認められなかった供試材を◎（特に良好）と評価した。   Moreover, about the sample material by which (circle) evaluation was obtained by the test of the said 1000 cycle, the same 600 degreeC cycle heating and 700 degreeC cycle heating were implemented to 2000 cycles. After 2000 cycles, for all 10 test pieces each having a temperature of 5 (n = 5) × temperature 2 levels, the specimens in which no peeling of the plating coating layer was observed were evaluated as ◎ (particularly good).

〔成形性〕
各供試材（板厚１.２ｍｍの溶融Ａｌ系めっき鋼板）から圧延方向を長手方向とする引張試験片（ＪＩＳ １３Ｂ号）を作成し、ｎ＝３でＪＩＳ Ｚ２２４１に準拠した引張試験を実施して伸びを測定した。ｎ＝３の伸びの平均値をその供試材の伸びとした。板厚１.２ｍｍの材料において伸びが３０％以上であれば二輪車用の排ガス経路部材に加工可能な良好な成形性を具備すると判断できることが、種々の実験から判っている。したがって、伸びが３０％以上の供試材を○（良好）、それ以外を×（不良）と評価した。 [Formability]
A tensile test piece (JIS 13B) with the rolling direction as the longitudinal direction is created from each test material (melted Al-based plated steel sheet with a thickness of 1.2 mm), and a tensile test based on JIS Z2241 is performed with n = 3 Then, the elongation was measured. The average value of the elongation of n = 3 was defined as the elongation of the test material. It has been found from various experiments that a material having a thickness of 1.2 mm can be judged to have good formability that can be processed into an exhaust gas passage member for a motorcycle if the elongation is 30% or more. Therefore, the specimens having an elongation of 30% or more were evaluated as ◯ (good), and the others were evaluated as x (defective).

〔低温靭性〕
各供試材（板厚１.２ｍｍの溶融Ａｌ系めっき鋼板）から長手方向が圧延方向に対して直角方向となるように５５ｍｍ×１０ｍｍの試験片を切り出し、その中央部に２ｍｍＶノッチを形成することにより、ノッチ付き衝撃試験片を作製した。ＪＩＳ Ｚ２２０２の定義によると、高さ１０ｍｍ、幅１.２ｍｍ、長さ５５ｍｍ、ノッチ下の高さ８ｍｍとなる。この試験片を用いてＪＩＳ Ｚ２２４２に準拠したシャルピー衝撃試験を実施し、脆性破断発生温度が−５０℃以下と判断された供試材を○（良好）、それ以外を×（不良）と評価した。
これらの結果を表２、表３に示す。 (Low temperature toughness)
A 55 mm × 10 mm test piece is cut out from each sample material (hot Al-plated steel sheet having a thickness of 1.2 mm) so that the longitudinal direction is perpendicular to the rolling direction, and a 2 mm V notch is formed at the center. Thus, an impact test piece with a notch was produced. According to the definition of JIS Z2202, the height is 10 mm, the width is 1.2 mm, the length is 55 mm, and the height below the notch is 8 mm. Using this test piece, a Charpy impact test according to JIS Z2242 was carried out, and the test material judged to have a brittle fracture occurrence temperature of −50 ° C. or lower was evaluated as “good” and the others were evaluated as “poor”. .
These results are shown in Tables 2 and 3.

Figure 2009035756
Figure 2009035756

Figure 2009035756
Figure 2009035756

表２からわかるように、Ａｌ系めっき層の平均厚さが３〜２０μｍの範囲にある本発明例のものは、いずれも優れた耐赤スケール性およびめっき被覆層の耐剥離性を示した。特にめっき層の平均厚さを１５μｍ未満としたものは、一層優れた耐剥離性を呈した。   As can be seen from Table 2, all of the examples of the present invention in which the average thickness of the Al-based plating layer was in the range of 3 to 20 μm exhibited excellent red scale resistance and peeling resistance of the plating coating layer. In particular, those having an average thickness of the plating layer of less than 15 μm exhibited more excellent peeling resistance.

これに対し、比較例であるＮｏ.５２、５４はＡｌ系めっき層の平均厚さが薄すぎたことにより耐赤スケール性に劣った。Ｎｏ.５１、５３、５５、５６はＡｌ系めっき層の平均厚さが２０μｍを超えて厚かったことにより、めっき被覆層の耐剥離性に劣った。Ｎｏ.５７は基材鋼板のＮｂ含有量が高すぎたのでめっき被覆層の耐剥離性に劣った。Ｎｏ.５８、５９、６０および６２はそれぞれ基材鋼板のＣｒ、Ｔｉ、ＭｏおよびＣｕの含有量が高すぎたことにより、これらはいずれも成形性および低温靭性に劣った。Ｎｏ.６１は基材鋼板のＣｒ含有量が少なすぎたことにより耐赤スケール性に劣った。   On the other hand, Nos. 52 and 54 as comparative examples were inferior in red scale resistance because the average thickness of the Al-based plating layer was too thin. Nos. 51, 53, 55, and 56 were inferior in peeling resistance of the plating coating layer because the average thickness of the Al-based plating layer exceeded 20 μm. No. 57 was inferior in the peel resistance of the plating coating layer because the Nb content of the base steel sheet was too high. Nos. 58, 59, 60, and 62 were inferior in formability and low-temperature toughness, respectively, because the content of Cr, Ti, Mo, and Cu in the base steel sheet was too high. No. 61 was inferior in red scale resistance due to the Cr content of the base steel sheet being too small.

Claims (4)

質量％で、Ｃ：０.０２％以下、Ｓｉ：２％以下、Ｍｎ：２％以下、Ｃｒ：５〜２５％、Ｎｂ：０.１超え〜１％、Ｔｉ：０.３％以下、Ｎ：０.０２％以下、残部Ｆｅおよび不可避的不純物からなる鋼板を基材とし、
前記基材を、質量％で、Ｓｉ：３〜１２％、残部Ａｌおよび不可避的不純物からなる溶融めっき浴に浸漬したのち引き上げ、めっき付着量を調整することにより、平均厚さ３〜２０μｍのめっき層を表面に形成した耐赤スケール性に優れた二輪車排ガス経路部材用Ａｌ系めっき鋼板。 In mass%, C: 0.02% or less, Si: 2% or less, Mn: 2% or less, Cr: 5-25%, Nb: more than 0.1-1%, Ti: 0.3% or less, N : 0.02% or less, the steel sheet comprising the balance Fe and inevitable impurities as a base material,
The substrate is dipped in a hot dipping bath composed of Si: 3 to 12%, the balance Al and unavoidable impurities in mass%, and then pulled up, and the plating thickness is adjusted to adjust the plating adhesion amount, thereby plating with an average thickness of 3 to 20 μm. An Al-plated steel sheet for motorcycle exhaust gas passage members with a layer formed on the surface and excellent red scale resistance. 基材の鋼板は、さらにＮｉ：０.６％以下、Ａｌ：０.２％以下、Ｍｏ：３％以下、Ｃｕ：３％以下、Ｗ：３％以下、Ｖ：０.５％以下、Ｃｏ：０.５％以下、Ｂ：０.０１％以下の１種以上を含有するものである請求項１に記載の耐赤スケール性に優れた二輪車排ガス経路部材用Ａｌ系めっき鋼板。   The steel plate of the base material is further Ni: 0.6% or less, Al: 0.2% or less, Mo: 3% or less, Cu: 3% or less, W: 3% or less, V: 0.5% or less, Co The Al-based plated steel sheet for a motorcycle exhaust gas passage member having excellent red scale resistance according to claim 1, which contains at least one of: 0.5% or less and B: 0.01% or less. 前記溶融めっき浴は、さらにＴｉ、Ｂ、Ｓｒ、Ｃｒ、Ｍｎ、Ｍｇ、Ｚｒの１種以上を合計１％以下の範囲で含有するものである請求項１または２に記載の耐赤スケール性に優れた二輪車排ガス経路部材用Ａｌ系めっき鋼板。   3. The red scale resistance according to claim 1, wherein the hot dipping bath further contains one or more of Ti, B, Sr, Cr, Mn, Mg, and Zr within a total range of 1% or less. Excellent Al-based plated steel sheet for motorcycle exhaust gas path members. 請求項１〜３のいずれかに記載のめっき鋼板を素材に用いて構成され、前記めっき層が排ガスと接触する構造を有する、最高使用温度が４００℃以上の二輪車排ガス経路部材。   A motorcycle exhaust gas path member having a maximum use temperature of 400 ° C or higher, wherein the plated steel sheet according to any one of claims 1 to 3 is used as a material, and the plating layer is in contact with exhaust gas.
JP2007198903A 2007-07-31 2007-07-31 Al-PLATED STEEL SHEET FOR EXHAUST GAS PASSAGEWAY MEMBER OF MOTORCYCLE EXCELLENT IN HIGH-TEMPERATURE STRENGTH AND THE GAS PASSAGE WAY MEMBER USING THE STEEL SHEET Withdrawn JP2009035756A (en)

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PCT/JP2008/063939 WO2009017246A1 (en) 2007-07-31 2008-07-29 Al-plated steel sheet for exhaust gas passageway members of motorcycles excellent in high-temperature strength and members
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