JP5837258B2 - Ferritic stainless steel having excellent surface corrosion resistance after polishing and method for producing the same - Google Patents
Ferritic stainless steel having excellent surface corrosion resistance after polishing and method for producing the same Download PDFInfo
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- JP5837258B2 JP5837258B2 JP2015508733A JP2015508733A JP5837258B2 JP 5837258 B2 JP5837258 B2 JP 5837258B2 JP 2015508733 A JP2015508733 A JP 2015508733A JP 2015508733 A JP2015508733 A JP 2015508733A JP 5837258 B2 JP5837258 B2 JP 5837258B2
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- 238000005498 polishing Methods 0.000 title claims description 85
- 238000005260 corrosion Methods 0.000 title claims description 82
- 230000007797 corrosion Effects 0.000 title claims description 82
- 229910001220 stainless steel Inorganic materials 0.000 title claims description 56
- 238000004519 manufacturing process Methods 0.000 title claims description 18
- 238000005096 rolling process Methods 0.000 claims description 39
- 229910052757 nitrogen Inorganic materials 0.000 claims description 20
- 229910052799 carbon Inorganic materials 0.000 claims description 17
- 238000001336 glow discharge atomic emission spectroscopy Methods 0.000 claims description 17
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 229910052758 niobium Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 10
- 229910052782 aluminium Inorganic materials 0.000 claims description 9
- 239000012535 impurity Substances 0.000 claims description 9
- 229910052748 manganese Inorganic materials 0.000 claims description 9
- 229910052717 sulfur Inorganic materials 0.000 claims description 9
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 229910052718 tin Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052787 antimony Inorganic materials 0.000 claims description 4
- 229910052733 gallium Inorganic materials 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 30
- 239000010935 stainless steel Substances 0.000 description 23
- 229910000831 Steel Inorganic materials 0.000 description 17
- 239000010959 steel Substances 0.000 description 17
- 238000011156 evaluation Methods 0.000 description 15
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 239000006061 abrasive grain Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 230000007423 decrease Effects 0.000 description 8
- 238000000227 grinding Methods 0.000 description 8
- 238000000137 annealing Methods 0.000 description 7
- 239000000460 chlorine Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- 229910052804 chromium Inorganic materials 0.000 description 6
- 230000020169 heat generation Effects 0.000 description 6
- 238000005259 measurement Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 229920006395 saturated elastomer Polymers 0.000 description 6
- 229910000859 α-Fe Inorganic materials 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000010960 cold rolled steel Substances 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000007670 refining Methods 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- 230000003746 surface roughness Effects 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- 238000009628 steelmaking Methods 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005097 cold rolling Methods 0.000 description 2
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- 239000002932 luster Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000005482 strain hardening Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000001629 suppression Effects 0.000 description 2
- 201000004569 Blindness Diseases 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- NJFMNPFATSYWHB-UHFFFAOYSA-N ac1l9hgr Chemical compound [Fe].[Fe] NJFMNPFATSYWHB-UHFFFAOYSA-N 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 230000003666 anti-fingerprint Effects 0.000 description 1
- 239000003963 antioxidant agent Substances 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009749 continuous casting Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003635 deoxygenating effect Effects 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
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- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/18—Ferrous alloys, e.g. steel alloys containing chromium
- C22C38/40—Ferrous alloys, e.g. steel alloys containing chromium with nickel
- C22C38/54—Ferrous alloys, e.g. steel alloys containing chromium with nickel with boron
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- C21D6/00—Heat treatment of ferrous alloys
- C21D6/002—Heat treatment of ferrous alloys containing Cr
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- C21D8/00—Modifying the physical properties by deformation combined with, or followed by, heat treatment
- C21D8/02—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
- C21D8/0278—Modifying the physical properties by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment
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- C21D9/00—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor
- C21D9/46—Heat treatment, e.g. annealing, hardening, quenching or tempering, adapted for particular articles; Furnaces therefor for sheet metals
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Description
本発明は、研磨後の表面耐食性に優れるフェライト系ステンレス鋼及びその製造方法に関するものである。 The present invention relates to a ferritic stainless steel having excellent surface corrosion resistance after polishing and a method for producing the same.
ステンレス鋼は普通鋼などに比較して耐食性に優れるため、金属光沢を意匠として有効に利用する目的で、防錆のためのコーティング処理を行わずに素地表面を露出させた状態で使用する場合が多い。しかし、厨房機器、家電製品、電子機器、器物などの製品のうちエレベーターや冷蔵庫、キッチンシンク、食器などの人目に触れ易い外装や日用品への適用においては、研磨によって一定の粗さ範囲での凹凸をもった筋模様、例えば研磨目を付与することで防眩性や耐指紋汚れ性を向上させ、かつ表面の金属光沢を担保する場合がある。研磨目を付与として、ステンレス鋼板の製造ライン上において砥粒を接着剤で固着させた研磨ベルトを鋼板に押し当てる方法や、製品出荷後において砥粒を樹脂に混合して固めたスポンジで加工したステンレス製品を擦る方法を例示することができる。或いは、砥粒を接着剤で固着させた研磨紙を束ねたものをリング状につないだホイール(フラップホイール)を回転させてステンレス鋼に押し付ける方法などが挙げられる。研磨目の表面粗度に関しては、日本工業規格で制定されているJIS G 4305に、冷間圧延ステンレス鋼板の表面仕上げとして、No.3、No.4、#240、#320、#400およびHLなどの記号によって、それぞれ所定の表面粗度を指定可能なことが規定されている。 Stainless steel is superior in corrosion resistance compared to ordinary steel, etc., so it may be used with the surface of the base exposed without the use of rust-proof coating for the purpose of effectively using metallic luster as a design. Many. However, in applications such as kitchen appliances, home appliances, electronic devices, and appliances that are easily accessible to the public, such as elevators, refrigerators, kitchen sinks, and tableware, irregularities within a certain roughness range can be obtained by polishing. In some cases, the anti-glare property and the anti-fingerprint stain resistance are improved by providing a streak pattern having, for example, polished eyes, and the metallic luster of the surface is secured. As a polishing tool, a polishing belt with abrasive grains fixed with an adhesive on the stainless steel plate production line is pressed against the steel plate, or processed with a sponge that is mixed with resin and hardened after product shipment. A method of rubbing a stainless steel product can be exemplified. Or the method of rotating the wheel (flap wheel) which bundled the thing which bundled the abrasive paper which fixed the abrasive grain with the adhesive agent in a ring shape, and pressed on stainless steel etc. is mentioned. Regarding the surface roughness of the polished eyes, JIS G 4305 established by the Japanese Industrial Standards, No. 3, no. The symbols such as 4, # 240, # 320, # 400, and HL define that a predetermined surface roughness can be designated.
従来から研磨ベルトによる研磨の際には、冷却および研削性を向上させる目的で、研磨油が使用される。特許文献1には、摩擦熱による昇温時の研磨油自体の酸化防止剤、油膜切れの防止剤、および研削性の向上剤を研磨油に含有させることで酸化物の形成を抑制し、耐食性の低下を防いでいる。 Conventionally, when polishing with a polishing belt, a polishing oil is used for the purpose of improving cooling and grindability. In Patent Document 1, the formation of oxides is suppressed by adding an antioxidant to the polishing oil itself at the time of temperature rise due to frictional heat, an agent for preventing oil film breakage, and an agent for improving grindability, thereby preventing corrosion. Is preventing the decline.
また、特許文献2には、表面の粗さである算術平均粗さRaが0.23以上で0.31μm以下の範囲となるようなJIS R 6001で規定する#400の砥粒に相当する研磨目を有し、表面の色調がLab系で赤色度を示すa値で1.0以下となるステンレス鋼製品を規定することによって、研磨による表面の酸化の程度が小さく、良好な耐食性を有することを記載している。 Patent Document 2 discloses polishing corresponding to # 400 abrasive grains defined by JIS R 6001 such that the arithmetic average roughness Ra, which is the roughness of the surface, is in the range of 0.23 to 0.31 μm. By specifying a stainless steel product that has eyes and has a surface color tone of Lab and a red value of 1.0 or less, the degree of surface oxidation by polishing is small, and it has good corrosion resistance. Is described.
また、特許文献3には、Moを添加したステンレス鋼において、焼鈍工程で表面に形成された緻密なMoに起因する酸化皮膜を除去し、研磨性を向上させる目的で、ハロゲンを含んだ酸処理をおこなっている。しかし、この時、溶解が不均一で、なおかつ粒界浸食もまた生じるために、Cr添加量を増やし、Cu、Niを添加し、さらにSiO2酸化皮膜を残存させることで、研磨性に優れ、かつ耐食性に優れるステンレス鋼板の製造方法を記載している。Patent Document 3 discloses that in stainless steel to which Mo is added, a halogen-containing acid treatment is performed for the purpose of removing the oxide film caused by the dense Mo formed on the surface in the annealing process and improving the polishability. Is doing. However, at this time, since the dissolution is non-uniform and grain boundary erosion also occurs, the Cr addition amount is increased, Cu, Ni is added, and the SiO 2 oxide film is left, so that the polishing property is excellent. In addition, a method for producing a stainless steel plate having excellent corrosion resistance is described.
また、特許文献4には、フェライトステンレス鋼板の研磨後に露点が−40℃以下の水素ガス雰囲気、いわゆるBA雰囲気中で、温度が1000℃以上、かつ当該温度に保持される時間が10秒以上となるように連続的に熱処理することによって、研磨で生成される酸化皮膜中の酸化物を還元することを特徴とする製造方法が記載されている。
フェライト系ステンレス鋼は、研磨時の発熱による研磨焼けによって表面耐食性の低下を引き起こし易い。すなわち、意匠性を創出するために、研磨目を付与する際には、これらの砥粒とステンレス素地の摩擦によって生じる熱により、研磨後の表面にFeを多く含む酸化物が形成される。このFeなどの酸化物へCl−を含む水溶液が付着した場合、Feなどの酸化物は水溶液へ溶解した後、大気中の酸素と化学反応してFe(OH)2などのような水酸化物を形成して、析出沈殿する。結果として、ステンレス表面に赤さびが発生し、素地の耐食性が低下したような外観となってしまう。Ferritic stainless steel is liable to cause a decrease in surface corrosion resistance due to polishing burn due to heat generated during polishing. That is, in order to create design properties, when a polishing eye is provided, an oxide containing a large amount of Fe is formed on the polished surface by heat generated by friction between these abrasive grains and the stainless steel substrate. When an aqueous solution containing Cl − adheres to the oxide such as Fe, the oxide such as Fe dissolves in the aqueous solution, and then chemically reacts with oxygen in the atmosphere to generate a hydroxide such as Fe (OH) 2. To form a precipitate. As a result, red rust is generated on the stainless steel surface, resulting in an appearance in which the corrosion resistance of the substrate is lowered.
特許文献1に記載の方法では、表面粗度が小さいステンレス鋼帯を研磨する時に、研磨抵抗が大きくなる場合、研磨油の工夫だけでは昇温を防ぐことができず、Cl−を含む水溶液の付着によって生じる表面上の赤さびを抑制することはできない。In the method described in Patent Document 1, when polishing a small stainless steel strip surface roughness, if the polishing resistance increases, only the devising of polishing oil can not be prevented heated, Cl - of aqueous solution containing Red rust on the surface caused by adhesion cannot be suppressed.
特許文献2に記載の範囲には、表面のRaと色調を規定しているが、多くの製品にはRaが0.45〜5.0μmとなるような比較的粗い研磨目が付与される。この場合も、Cl−を含む水溶液の付着によって生じる表面上の赤さびを抑制することはできない。The range described in Patent Document 2 defines Ra and color tone of the surface, but many products are provided with relatively rough polishing marks such that Ra is 0.45 to 5.0 μm. Also in this case, red rust on the surface caused by adhesion of an aqueous solution containing Cl − cannot be suppressed.
特許文献3に記載の方法では、焼鈍時に形成させた酸化皮膜を敢えて鋼板表面に残存させることによって、地鉄の溶解、特に、粒界における浸食を最小限に抑制し、研磨後の耐食性を確保している。しかし、比較的粗い研磨目を付与する場合、例え焼鈍後の酸洗工程を工夫して焼鈍時の酸化皮膜を残したとしても、研磨時に全ての酸化皮膜は除去されてしまう。そのため、地鉄表面に付着したFe化合物が腐食するために、表面上の赤さびの発生を抑制することはできない。 In the method described in Patent Document 3, the oxide film formed at the time of annealing is intentionally left on the surface of the steel sheet, thereby minimizing the dissolution of the base iron, especially the erosion at the grain boundary, and ensuring the corrosion resistance after polishing. doing. However, when a relatively rough polishing grain is provided, even if the pickling process after annealing is devised to leave an oxide film during annealing, all the oxide film is removed during polishing. Therefore, since the Fe compound adhering to the surface of the ground iron corrodes, generation of red rust on the surface cannot be suppressed.
特許文献4に記載の方法では、BA雰囲気とするため、製造コストが高くなる。
In the method described in
本発明の目的は、より粗い研磨を施した場合においても、Cl−を含む水溶液の付着に起因する表面上の赤さびを抑制するフェライト系ステンレス鋼、およびより少ない工程で研磨後にCl−を含む水溶液の付着に起因する表面上の赤さびを抑制することができる、表面耐食性に優れるフェライト系ステンレス鋼の製造方法を提供することである。An object of the present invention is to provide a ferritic stainless steel that suppresses red rust on the surface caused by adhesion of an aqueous solution containing Cl − even when coarser polishing is performed, and an aqueous solution containing Cl − after polishing in fewer steps. It is an object to provide a method for producing a ferritic stainless steel having excellent surface corrosion resistance that can suppress red rust on the surface due to adhesion of steel.
発明者らは、従来技術が抱える上記問題点を解決し、研磨後の表面耐食性に優れるフェライト系ステンレス鋼板を開発するべく、研磨後の表面に形成された酸化物構造と塩水中での前記酸化物構造の耐食性について鋭意検討を重ねた。その結果、Siの微量添加および調質圧延の圧下率を高くする製造方法の適用によるステンレス鋼の表面硬化によって、研磨時の研削量を抑制し、発熱を抑えることができることを知見した。加えて、Siの微量添加と研磨時の発熱が抑えられることとが相まって、表面にSiO2を多く含む酸化物を形成させることができ、塩水中での赤さびの原因となる表面酸化物中のFeを酸化物表面に濃化することを抑制し、さらにSiO2が表面の熱伝導性を低下させることで地鉄界面にあるFeの酸化物の発生を抑制し、Cl−を含む水との接触によるFe酸化物の赤さびへの変質を抑制することを知見した。また、Snを微量添加すると、Siと同様にステンレス鋼の表面を硬化させ、研磨時の研削量および発熱の抑制に寄与することも知見した。In order to solve the above-mentioned problems of the prior art and develop a ferritic stainless steel sheet having excellent surface corrosion resistance after polishing, the inventors have developed the oxide structure formed on the surface after polishing and the oxidation in salt water. We intensively investigated the corrosion resistance of the structure. As a result, it was found that the amount of grinding at the time of polishing can be suppressed and heat generation can be suppressed by adding a small amount of Si and surface hardening of stainless steel by applying a manufacturing method that increases the rolling reduction of temper rolling. In addition, combined with the addition of a small amount of Si and the suppression of heat generation during polishing, it is possible to form an oxide containing a large amount of SiO 2 on the surface, which causes red rust in salt water. Concentration of Fe on the oxide surface is suppressed, and further, SiO 2 reduces the thermal conductivity of the surface, thereby suppressing the generation of Fe oxide at the iron-iron interface, and with water containing Cl − It has been found that the iron oxide is prevented from changing into red rust due to contact. It was also found that the addition of a small amount of Sn hardens the surface of stainless steel in the same way as Si, and contributes to the amount of grinding and the suppression of heat generation during polishing.
すなわち本発明は、以下の通りである。
(1)質量%で、C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、残部はFeおよび不可避的不純物であり、表面硬さHvが175以上195以下であって、表面に算術平均粗さRaが0.45〜5.0μmの研磨目を付与した時に、表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み、さらに表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。
(2)質量%で、C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、残部はFeおよび不可避的不純物であり、表面硬さHvが175以上195以下であって、表面の算術平均粗さRaが0.45〜5.0μmとなるような研磨目を有し、さらに表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み、表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。
(3)質量%で、C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、さらに質量%で、Sn:0.005〜1.0%、Ni:0.50%以下、Cu:1.50%以下、Mo:3.0%以下、V:1.0%以下、B:0.003%以下、Sb:0.001〜0.3%、Ga:0.0002〜0.1%、及びTa:0.50%以下のうち1種以上を含有し、残部はFeおよび不可避的不純物であり、表面硬さHvが175以上195以下であって、表面に算術平均粗さRaが0.45〜5.0μmの研磨目を付与した時に、表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み、さらに表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。
(4)質量%で、C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、さらに質量%で、Sn:0.005〜1.0%、Ni:0.50%以下、Cu:1.50%以下、Mo:3.0%以下、V:1.0%以下、B:0.003%以下、Sb:0.001〜0.3%、Ga:0.0002〜0.1%、及びTa:0.50%以下のうち1種以上を含有し、残部はFeおよび不可避的不純物であり、表面硬さHvが175以上195以下であって、表面に算術平均粗さRaが0.45〜5.0μmの研磨目を有し、さらに表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。
(5)Siを、0.3〜3.0%含有することを特徴とする、(3)又は(4)に記載の研磨後の表面耐食性に優れるフェライト系ステンレス鋼。
(6)さらに質量%で、W:0.50%以下、Co:0.50%以下、Mg:0.01%以下、Ca:0.0030%以下、Zr:0.30%以下、REM(希土類元素):0.20%以下のうち1種以上を含有することを特徴とする、(1)〜(5)のうちいずれかに記載の研磨後の表面耐食性に優れるフェライト系ステンレス鋼。
(7)(1)〜(6)のうちいずれかに記載の研磨後の表面耐食性に優れるフェライト系ステンレス鋼を用いたことを特徴とする、フェライト系ステンレス鋼部品。
(8)圧下率が0.5%以上4.8%以下の調質圧延を行うことを特徴とする、(1)〜(6)のうちいずれかに記載の研磨後の表面耐食性に優れるフェライト系ステンレス鋼の製造方法。
(9)圧下率が0.5%以上4.0%以下の調質圧延を行うことを特徴とする(1)〜(6)のうちいずれかに記載の研磨後の表面耐食性に優れるフェライト系ステンレス鋼の製造方法を提案する。That is, the present invention is as follows.
(1) By mass%, C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less, Cr: 12-22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less, the balance being Fe and inevitable When the surface hardness Hv is 175 or more and 195 or less, and the surface has an arithmetic mean roughness Ra of 0.45 to 5.0 μm, the element concentration of the surface is determined by glow discharge emission spectrometry. When measured by (GD-OES), at a depth of 10 nm from the surface, the average mass concentration of the ratio of elements excluding C, O and N includes 5% or more of Si and 75% or less of Fe, further lightness L * value of the surface is characterized by taking 70 or more values, the surface corrosion resistance after polishing Ferritic stainless steels.
(2) In mass%, C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less, Cr: 12-22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less, the balance being Fe and inevitable It is an impurity, has a polishing hardness such that the surface hardness Hv is 175 or more and 195 or less, and the arithmetic average roughness Ra of the surface is 0.45 to 5.0 μm. When measured by emission spectrometry (GD-OES), Si is 5% or more and Fe is 75% at an average mass concentration of the elements excluding C, O and N at a depth of 10 nm from the surface. wherein following lightness L * value of the surface is characterized by taking 70 or more values, the surface corrosion resistance after polishing Ferritic stainless steel, which is excellent.
(3) In mass%, C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less, Cr: 12 to 22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less, and further by mass%, Sn : 0.005 to 1.0%, Ni: 0.50% or less, Cu: 1.50% or less, Mo: 3.0% or less, V: 1.0% or less, B: 0.003% or less, Sb: 0.001 to 0.3%, Ga: 0.0002 to 0.1%, and Ta: 0.5% or less, containing one or more, the balance being Fe and inevitable impurities, When the hardness Hv is 175 or more and 195 or less, and the surface has an arithmetic mean roughness Ra of 0.45 to 5.0 μm, the surface element concentration is -When measured by discharge optical emission spectrometry (GD-OES), at a depth of 10 nm from the surface, at an average mass concentration of the ratio of elements excluding C, O and N, Si is 5% or more, Fe is A ferritic stainless steel containing 75% or less and having a surface lightness L * value of 70 or more and excellent in surface corrosion resistance after polishing.
(4) By mass%, C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less, Cr: 12 to 22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less, and further by mass%, Sn : 0.005 to 1.0%, Ni: 0.50% or less, Cu: 1.50% or less, Mo: 3.0% or less, V: 1.0% or less, B: 0.003% or less, Sb: 0.001 to 0.3%, Ga: 0.0002 to 0.1%, and Ta: 0.5% or less, containing one or more, the balance being Fe and inevitable impurities, The hardness Hv is 175 or more and 195 or less, the surface has an arithmetic mean roughness Ra of 0.45 to 5.0 μm, and the surface element concentration is When measured by discharge optical emission spectrometry (GD-OES), Si is 5% or more and Fe is 75% at an average mass concentration of elements excluding C, O and N at a depth of 10 nm from the surface. % Ferritic stainless steel with excellent surface corrosion resistance after polishing, characterized by having a surface brightness L * value of 70% or more.
(5) Ferritic stainless steel having excellent surface corrosion resistance after polishing according to (3) or (4), wherein Si is contained in an amount of 0.3 to 3.0%.
(6) Further, by mass%, W: 0.50% or less, Co: 0.50% or less, Mg: 0.01% or less, Ca: 0.0030% or less, Zr: 0.30% or less, REM ( Rare earth element): Ferritic stainless steel excellent in surface corrosion resistance after polishing according to any one of (1) to (5), characterized by containing one or more of 0.20% or less.
(7) A ferritic stainless steel part using the ferritic stainless steel having excellent surface corrosion resistance after polishing according to any one of (1) to (6).
(8) Ferrite having excellent surface corrosion resistance after polishing according to any one of (1) to (6), wherein temper rolling is performed at a rolling reduction of 0.5% to 4.8% Of manufacturing stainless steel.
(9) Ferrite based on excellent surface corrosion resistance after polishing according to any one of (1) to (6), wherein temper rolling is performed at a rolling reduction of 0.5% to 4.0% A method for producing stainless steel is proposed.
本発明によれば、比較的粗い粗度の研磨をおこなった場合でも表面耐食性に優れたフェライト系ステンレス鋼を得ることを、耐食性試験結果で確認している。そのため、本発明によるフェライト系ステンレス鋼は、塩素を含む水道水が接する屋内での用途において、良好な表面耐食性を有し、研磨をおこなっても赤さびの発生が抑制されて、表面の審美性が維持される。 According to the present invention, it is confirmed from the corrosion resistance test results that a ferritic stainless steel having excellent surface corrosion resistance is obtained even when polishing with a relatively rough roughness is performed. Therefore, the ferritic stainless steel according to the present invention has good surface corrosion resistance in indoor applications that come into contact with chlorine-containing tap water, and the occurrence of red rust is suppressed even after polishing, and the surface aesthetics are improved. Maintained.
また、本発明のフェライト系ステンレス鋼を目的に応じて所定の形状に成型した後に、本発明に記載のような研磨をすることによって、厨房機器、家電製品、電子機器、器物などの製品のうち人目に触れ易い外装や日用品の部品として好適に使用することができる。 In addition, after forming the ferritic stainless steel of the present invention into a predetermined shape according to the purpose, by polishing as described in the present invention, among products such as kitchen appliances, home appliances, electronic devices, and instruments It can be suitably used as a part for exterior and daily necessities that are easy to touch.
本発明に係るフェライト系ステンレス鋼成分の詳細な規定について以下に説明する。なお、組成についての%の表記は、特に断りのない場合は、質量%を意味する。 The detailed definition of the ferritic stainless steel component according to the present invention will be described below. In addition, the description of% about a composition means the mass% unless there is particular notice.
C:0.030%以下
Cは、硬化や安定化元素との組合せによる結晶粒粗大化抑制による強度向上等の効果があるが、溶接部の耐粒界腐食性、加工性を低下させる。高純度系フェライト系ステンレス鋼ではその含有量を低減させる必要があるため、上限を0.030%とした。過度に低減させることは精錬コストを悪化させるため、より望ましくは、下限を0.002%とし、上限を0.020%とすることである。C: 0.030% or less C has an effect of improving strength by suppressing coarsening of grains by combination with hardening or a stabilizing element, but reduces intergranular corrosion resistance and workability of a welded portion. In high-purity ferritic stainless steel, the content must be reduced, so the upper limit was made 0.030%. To reduce excessively deteriorates the refining cost, more desirably, the lower limit is made 0.002% and the upper limit is made 0.020%.
N:0.030%以下
Nは、Cと同様に耐粒界腐食性、加工性を低下させるため、その含有量を低減させる必要があることから、その上限を0.030%とした。ただし過度に低減させることは精錬コストを悪化させるため、より望ましくは、下限を0.002%とし、上限を0.020%とすることである。N: 0.030% or less N, like C, reduces intergranular corrosion resistance and workability, so its content must be reduced, so its upper limit was made 0.030%. However, reducing excessively deteriorates the refining cost. More desirably, the lower limit is 0.002% and the upper limit is 0.020%.
Mn:1.5%以下
Mnは、本発明において含有しなくてもよい元素であるが、脱酸元素として有用な元素でもある。但し、Mnを過剰に添加すると腐食の起点となるMnSを生成しやすくなるので、上限を1.5%とした。脱酸元素として使用するので0.01%以上が好ましい。またフェライト組織を不安定化させるため、その含有量の下限を0.01%とし、上限を0.60%とするのが好ましい。より望ましくは、下限を0.05%とし、上限を0.3%とすることである。Mn: 1.5% or less Mn is an element that may not be contained in the present invention, but is also an element useful as a deoxidizing element. However, if Mn is added excessively, MnS that becomes a starting point of corrosion tends to be generated, so the upper limit was made 1.5%. Since it is used as a deoxidizing element, 0.01% or more is preferable. In order to destabilize the ferrite structure, the lower limit of the content is preferably 0.01% and the upper limit is preferably 0.60%. More desirably, the lower limit is 0.05% and the upper limit is 0.3%.
P:0.04%以下
Pは、溶接性、加工性を低下させるだけでなく、粒界腐食を生じやすくもするため、低く抑える必要がある。そのため含有量を0.04%以下とした。より望ましくは下限を0.001%とし、上限を0.03%とすることである。P: 0.04% or less P not only lowers weldability and workability, but also tends to cause intergranular corrosion, so P needs to be kept low. Therefore, the content is set to 0.04% or less. More preferably, the lower limit is 0.001% and the upper limit is 0.03%.
S:0.01%以下
Sは、先述のCaSやMnS等の腐食の起点となる水溶性介在物を生成させるため、低減させる必要がある。そのため含有率は0.01%以下とする。ただし過度の低減はコストの悪化を招くため、より望ましくは下限を0.0001%とし、上限を0.006%とすることである。S: 0.01% or less S needs to be reduced because water-soluble inclusions such as the above-mentioned CaS and MnS, which are the starting points of corrosion, are generated. Therefore, the content is made 0.01% or less. However, excessive reduction leads to cost deterioration. More preferably, the lower limit is 0.0001% and the upper limit is 0.006%.
Cr:12〜22.5%
Crは、ステンレス鋼の耐食性を確保する上で最も重要な元素であり、フェライト組織を安定化するので少なくとも12%は必要である。Crは後述するSiと同様に表面の酸化皮膜中に濃化し、Feの濃化を相対的に抑制することで、研磨後の赤さび発生を抑える。Crを増加させると、研磨後の耐食性も向上するが、加工性、製造性を低下させるため、上限を22.5%とした。望ましくは下限を13.5%とし、上限を21.0%とすることであり、より望ましくは下限を16.0%とし、上限を20.0%とすることである。さらに好ましくは、下限を16.5%とし、上限を18.0%とすることである。Cr: 12-22.5%
Cr is the most important element for securing the corrosion resistance of stainless steel, and at least 12% is necessary because it stabilizes the ferrite structure. Cr is concentrated in the oxide film on the surface in the same manner as Si described later, and the generation of red rust after polishing is suppressed by relatively suppressing the concentration of Fe. Increasing Cr improves the corrosion resistance after polishing, but lowers workability and manufacturability, so the upper limit was made 22.5%. Preferably, the lower limit is 13.5% and the upper limit is 21.0%, more preferably the lower limit is 16.0% and the upper limit is 20.0%. More preferably, the lower limit is 16.5% and the upper limit is 18.0%.
Si:0.15〜3.0%
Siは、本発明に非常に重要な元素であり、一般的に耐食性、耐酸化性にも有効であり、脱酸剤として添加する元素である。発明者らの知見によれば、鋼中にSiを0.15%以上添加すると、研磨後の最表層にSiO2の酸化皮膜が形成され、Fe酸化物の濃化を相対的に抑制することで、研磨後の赤さび発生を抑える。また、Siの添加と調質圧延の圧下率を高くすることによって金属組織が硬化するため、研磨時の研削量を低減することができ、結果として研磨熱を抑制し、酸化物形成を抑える。しかし、過度な添加は加工性、製造性を低下させる。そのため上限を3.0%とした。望ましくは上限値は2.5%未満である。より望ましくは1.5%以下である。さらに望ましくは1.0%以下である。下限値は望ましくは0.3%以上であり、さらに望ましくは0.4%以上である。Si: 0.15-3.0%
Si is an extremely important element in the present invention, is generally effective in corrosion resistance and oxidation resistance, and is an element added as a deoxidizer. According to the knowledge of the inventors, when 0.15% or more of Si is added to the steel, an oxide film of SiO 2 is formed on the outermost layer after polishing, and the concentration of Fe oxide is relatively suppressed. Therefore, the occurrence of red rust after polishing is suppressed. In addition, since the metal structure is hardened by adding Si and increasing the rolling reduction of temper rolling, the amount of grinding during polishing can be reduced, and as a result, polishing heat is suppressed and oxide formation is suppressed. However, excessive addition reduces processability and manufacturability. Therefore, the upper limit was made 3.0%. Desirably, the upper limit is less than 2.5%. More desirably, it is 1.5% or less. More desirably, it is 1.0% or less. The lower limit is desirably 0.3% or more, and more desirably 0.4% or more.
Al:0.80%以下
Alは含有しなくても良い元素であるが、Siと同様に脱酸元素として有用であり、また非金属介在物の組成を制御し組織を微細化する効果もある。しかし過剰に添加すると非金属介在物の粗大化を招き、製品の疵発生の起点になる恐れもある。そのため、上限値を0.80%とした。下限値は特に設定する必要はないが、Alの除去には手間がかかることから、経済的観点からその下限は0.01%以上としても良い。望ましくは下限を0.01%とし、上限を0.80%とすることである。さらに望ましくは下限を0.03%とし、上限を0.5%とすることである。Al: 0.80% or less Al is an element that does not need to be contained, but is useful as a deoxidizing element like Si, and also has the effect of controlling the composition of non-metallic inclusions and refining the structure. . However, if it is added excessively, the non-metallic inclusions become coarse, which may be the starting point for product wrinkles. Therefore, the upper limit is set to 0.80%. The lower limit value does not need to be set in particular. However, since it takes time to remove Al, the lower limit value may be 0.01% or more from an economic viewpoint. Desirably, the lower limit is 0.01% and the upper limit is 0.80%. More desirably, the lower limit is 0.03%, and the upper limit is 0.5%.
Ti:0.60%以下
Tiは、一般にはフェライト系ステンレス鋼の溶接部においてC、Nを固定することで、粒界腐食を抑制させ、加工性を向上させる重要な元素である。しかしながら過剰な添加は製造時の表面疵の原因となるため、その範囲を0.60%以下とした。下限値は0.03%以上であってもよい。0.05%以上が望ましく、より望ましくは0.08%以上である。望ましくは、下限を0.08とし、上限を0.30%とすることである。より望ましくは、下限を0.08%とし、上限を0.20%とすることである。Ti: 0.60% or less Ti is an important element that generally suppresses intergranular corrosion and improves workability by fixing C and N in a weld zone of ferritic stainless steel. However, excessive addition causes surface flaws during production, so the range was made 0.60% or less. The lower limit may be 0.03% or more. 0.05% or more is desirable, and more desirably 0.08% or more. Desirably, the lower limit is 0.08 and the upper limit is 0.30%. More desirably, the lower limit is 0.08% and the upper limit is 0.20%.
Nb:0.60%以下
Nbは、Tiと同様にC、Nを固定し、溶接部の粒界腐食を抑制し加工性を向上させる上で非常に重要な元素である。また、炭化物または窒化物として析出すると、金属組織を硬化させる働きをもち、研磨時の研削量を抑える。ただし過剰な添加は、過剰な析出によって靭性低下を引き起こし、加工性を低下させるため、添加する場合は、0.60%以下とするのが良い。下限値を0.03%以上に設定してもよい。前記下限値は、0.05%が望ましく、より望ましくは0.08%である。望ましい範囲は下限を0.10%とし、上限を0.30%とすることである。より望ましい範囲は、下限を0.10%とし、上限を0.20%とすることである。なお、TiとNbの一方を含有していれば、他方を含有していなくてもよい。Nb: 0.60% or less Nb is an extremely important element for fixing C and N like Ti, suppressing intergranular corrosion of the welded portion, and improving workability. Moreover, when it precipitates as a carbide | carbonized_material or nitride, it has a function which hardens a metal structure and suppresses the grinding amount at the time of grinding | polishing. However, excessive addition causes a decrease in toughness due to excessive precipitation and decreases workability. Therefore, when added, the content is preferably made 0.60% or less. The lower limit value may be set to 0.03% or more. The lower limit is preferably 0.05%, more preferably 0.08%. A desirable range is to set the lower limit to 0.10% and the upper limit to 0.30%. A more desirable range is to set the lower limit to 0.10% and the upper limit to 0.20%. In addition, as long as one of Ti and Nb is contained, the other may not be contained.
さらに本発明で必要に応じて選択的に含有させることのできる他の化学組成について以下に詳しく説明する。 Further, other chemical compositions that can be selectively contained as required in the present invention will be described in detail below.
Sn:0.005〜1.0%
SnはSiと同様に金属組織を硬化するため、研磨時の研削量を低減することができ、結果として研磨熱を抑制し、酸化物形成を抑える重要な元素である。同時に、腐食速度を抑制し、研磨後の耐流れさび性を向上させるのに重要な元素である。0.005%以上で効果を発現するので、下限値を0.005%とした。0.05%以上が望ましく、さらに0.08%以上が望ましい。過剰な添加は製造性及びコストを悪化させるため、上限は1.0%とし、望ましくは0.5%とした。さらに望ましいSnの上限は、0.4%である。したがって、Snの範囲は、下限を0.005%とし、上限を1.0%とすることである。望ましくは下限を0.05%とし、上限を0.5%とすることである。より望ましくは、下限を0.08%とし、上限を0.4%とすることである。Sn: 0.005-1.0%
Since Sn hardens the metal structure like Si, it can reduce the amount of grinding during polishing, and as a result, is an important element that suppresses polishing heat and suppresses oxide formation. At the same time, it is an important element for suppressing the corrosion rate and improving the flow rust resistance after polishing. Since the effect is manifested at 0.005% or more, the lower limit is set to 0.005%. 0.05% or more is desirable, and further 0.08% or more is desirable. Excessive addition deteriorates manufacturability and cost, so the upper limit was made 1.0%, preferably 0.5%. A more desirable upper limit of Sn is 0.4%. Therefore, the Sn range is to set the lower limit to 0.005% and the upper limit to 1.0%. Desirably, the lower limit is 0.05% and the upper limit is 0.5%. More desirably, the lower limit is 0.08% and the upper limit is 0.4%.
Cu:1.5%以下
Cuは、必須ではないが、スクラップを原料として用いた場合に不可避不純物として0.01%以上含まれ得る。一般に、Cuは腐食速度を抑制するため、Snと同様に研磨後の耐流れさび性を向上するために必要に応じて添加する。0.05%以上添加すると良い。望ましくは、0.09%以上であり、更に望ましくは0.15%以上である。しかし、過剰な添加は製造性及びコストを悪化させるため、上限は1.5%とした。望ましい上限は、1.0%である。より望ましい上限は0.50%である。従って、Cuの望ましい範囲は、下限を0.05%とし、上限を1.0%とすることであり、より望ましくは下限を0.09%とし、上限を0.50%とすることである。Cu: 1.5% or less Cu is not essential, but may be contained in an amount of 0.01% or more as an inevitable impurity when scrap is used as a raw material. In general, Cu suppresses the corrosion rate, and is added as necessary to improve the flow rust resistance after polishing in the same manner as Sn. It is good to add 0.05% or more. Desirably, it is 0.09% or more, and more desirably 0.15% or more. However, excessive addition deteriorates manufacturability and cost, so the upper limit was made 1.5%. A desirable upper limit is 1.0%. A more desirable upper limit is 0.50%. Therefore, the desirable range of Cu is to set the lower limit to 0.05% and the upper limit to 1.0%, and more preferably to set the lower limit to 0.09% and the upper limit to 0.50%. .
Ni:0.50%以下
Niは、必須ではないが、含有すれば活性溶解速度を抑制させ、かつ不働態化に非常に効果がある。しかし、過剰な添加は、加工性を低下させ、フェライト組織を不安定にするだけでなくコストも悪化するため、0.50%以下とした。望ましくは0.35%未満とした。下限は0.05%が良い。従って、Niの望ましい範囲は、0.05%以上、0.35%未満である。Ni: 0.50% or less Ni is not essential, but if contained, it suppresses the active dissolution rate and is very effective for passivation. However, excessive addition reduces workability and not only destabilizes the ferrite structure but also deteriorates the cost, so it was made 0.50% or less. Desirably, it was made into less than 0.35%. The lower limit is preferably 0.05%. Therefore, the desirable range of Ni is 0.05% or more and less than 0.35%.
Mo:3.0%以下
Moは、不働態皮膜の補修に効果があり、耐食性を向上させるのに非常に有効な元素で特にCrとの組み合わせで耐孔食性を向上させる効果がある。しかし、Moを増加させると耐食性は向上するが、加工性を低下させ、またコストが高くなるため上限を3.0%とする。より望ましくは、下限を0.30%とし、上限を2.00%とすることである。Mo: 3.0% or less Mo is effective in repairing the passive film, and is an element that is very effective for improving the corrosion resistance. In particular, Mo is effective in improving the pitting corrosion resistance in combination with Cr. However, when Mo is increased, the corrosion resistance is improved, but the workability is lowered and the cost is increased, so the upper limit is made 3.0%. More desirably, the lower limit is 0.30% and the upper limit is 2.00%.
B:0.003%以下
Bは二次加工脆性改善に有効な粒界強化元素であるため、必要に応じて添加することができる。しかし、過度の添加はフェライトを固溶強化して延性低下の原因になる。このため下限を0.0001%とする。上限は0.003%とする。より望ましくは、下限を0.0002%とし、上限を0.0020%とすることである。B: 0.003% or less B is a grain boundary strengthening element effective for improving secondary work brittleness, and can be added as necessary. However, excessive addition causes the solid solution strengthening of ferrite and causes a decrease in ductility. Therefore, the lower limit is made 0.0001%. The upper limit is 0.003%. More desirably, the lower limit is 0.0002% and the upper limit is 0.0020%.
V:1.0%以下
Vは耐銹性や耐すき間腐食性を改善し、Cr、Moの使用を抑えてVを添加すれば優れた加工性も担保することができるため、必要に応じて添加することができる。下限は0.03%が良い。ただしVの過度の添加は加工性を低下させる上、耐食性向上効果も飽和するため、上限を1.0%とする。より望ましくは、下限を0.05%とし、上限を0.50%とすることである。V: 1.0% or less V improves the weather resistance and crevice corrosion resistance, and can suppress the use of Cr and Mo and add V to ensure excellent workability. Can be added. The lower limit is preferably 0.03%. However, excessive addition of V reduces workability and also saturates the effect of improving corrosion resistance, so the upper limit is made 1.0%. More desirably, the lower limit is 0.05% and the upper limit is 0.50%.
Sb:0.001〜0.3%
Sbは耐食性の向上に有効であり、必要に応じて0.3質量%以下の量で添加してもよい。特に隙間腐食性の観点からSb量を添加する場合、Sb量の下限を0.001質量%とする。さらに、製造性やコストの観点からSb量を0.01質量%以上とすることが好ましい。コストの点からSb量の上限は0.1質量%が好ましい。Sb: 0.001 to 0.3%
Sb is effective in improving the corrosion resistance, and may be added in an amount of 0.3% by mass or less as necessary. In particular, when adding the amount of Sb from the viewpoint of crevice corrosion, the lower limit of the amount of Sb is set to 0.001% by mass. Furthermore, it is preferable that the amount of Sb is 0.01% by mass or more from the viewpoint of manufacturability and cost. From the viewpoint of cost, the upper limit of the amount of Sb is preferably 0.1% by mass.
Ga:0.0002〜0.1%
Gaは、耐食性向上や水素脆化の抑制のため、0.1質量%以下の量で添加してもよい。硫化物や水素化物の形成の観点からGa量の下限を0.0002質量%とする。さらに、製造性やコストの観点からGa量は0.0020質量%以上が好ましい。Ga: 0.0002 to 0.1%
Ga may be added in an amount of 0.1% by mass or less in order to improve corrosion resistance and suppress hydrogen embrittlement. From the viewpoint of the formation of sulfides and hydrides, the lower limit of Ga content is 0.0002% by mass. Furthermore, the amount of Ga is preferably 0.0020% by mass or more from the viewpoint of manufacturability and cost.
Ta:0.50%以下
Taは高温強度を向上させる元素であり、必要に応じて添加することができる。しかし、過度の量のTaの添加は、常温延性の低下や靭性の低下を招くため、0.50質量%をTa量の上限とする。高温強度と延性・靭性を両立させるためには、Ta量は0.05質量%以上、0.5質量%以下が好ましい。Ta: 0.50% or less Ta is an element that improves high-temperature strength, and can be added as necessary. However, addition of an excessive amount of Ta causes a decrease in normal temperature ductility and a decrease in toughness, so 0.50% by mass is made the upper limit of the Ta amount. In order to achieve both high temperature strength and ductility / toughness, the Ta content is preferably 0.05% by mass or more and 0.5% by mass or less.
W:0.50%以下
Wは、高温強度の向上に有効であり、必要に応じて0.01%以上で添加する。また、0.50%を超えて添加すると固溶強化が大きすぎて機械的性質が低下するため、下限を0.01%とし、上限を0.50%とする範囲で添加する。製造コストや熱延板靭性を考慮すると、下限を0.02%とし、上限を0.15%とすることが望ましい。W: 0.50% or less W is effective in improving the high-temperature strength, and is added at 0.01% or more as necessary. Further, if added over 0.50%, the solid solution strengthening is too large and the mechanical properties are lowered, so the lower limit is made 0.01% and the upper limit is made 0.50%. Considering the manufacturing cost and hot-rolled sheet toughness, it is desirable that the lower limit is 0.02% and the upper limit is 0.15%.
Co:0.50%以下
Coは、耐摩耗性の向上や高温強度の向上に有効であり、必要に応じて0.01%以上で添加する。また、0.50%を超えて添加してもその効果は飽和し、固溶強化による機械的性質の劣化を生じるため、下限を0.01%とし、上限を0.50%とする範囲内で添加する。製造コストや高温強度の安定性の点から、下限を0.05%とし、上限を0.20%とする範囲内で添加することが望ましい。Co: 0.50% or less Co is effective for improving wear resistance and high-temperature strength, and is added at 0.01% or more as necessary. Moreover, even if added over 0.50%, the effect is saturated, and mechanical properties are deteriorated due to solid solution strengthening. Therefore, the lower limit is set to 0.01% and the upper limit is set to 0.50%. Add in. From the viewpoint of manufacturing cost and stability of high temperature strength, it is desirable to add in a range where the lower limit is 0.05% and the upper limit is 0.20%.
Mg:0.01%以下
Mgは、製鋼工程における凝固組織の微細化に有効な元素であり、必要に応じて0.0003%以上で添加する。また、0.01%を超えて添加してもその効果は飽和し、Mgの硫化物や酸化物に起因する耐食性の低下を生じ易くなるため、下限を0.0003%とし、上限を0.01%とする範囲内で添加する。製鋼工程におけるMg添加はMgの酸化燃焼が激しく歩留まりが低くなりコストの増加が大きいことを考慮すると、下限を0.0005%とし、上限を0.0015%とすることが望ましい。Mg: 0.01% or less Mg is an element effective for refining the solidified structure in the steel making process, and is added in an amount of 0.0003% or more as necessary. Further, even if added over 0.01%, the effect is saturated, and the corrosion resistance due to Mg sulfide or oxide is likely to be lowered. Therefore, the lower limit is set to 0.0003%, and the upper limit is set to 0.00. Add within the range of 01%. In consideration of the fact that the Mg addition in the steelmaking process causes oxidative combustion of Mg and the yield decreases and the cost increases greatly, the lower limit is preferably 0.0005% and the upper limit is preferably 0.0015%.
Ca:0.0030%以下
Caは、製鋼工程における重要な脱硫元素であり、脱酸素効果も有するため、必要に応じて0.0003%以上で添加する。また、0.0030%を超えて添加してもその効果は飽和し、Caの粒化物に起因する耐食性の低下や、酸化物に起因する加工性劣化を生じるため、下限を0.0003%とし、上限を0.0030%とする範囲内で添加する。スラグ処理等の製造性を考慮すると、下限を0.0005%とし、上限を0.0015%とすることが望ましい。Ca: 0.0030% or less Ca is an important desulfurization element in the steel making process, and also has a deoxygenating effect, so is added at 0.0003% or more as necessary. Moreover, even if added over 0.0030%, the effect is saturated, and the corrosion resistance is reduced due to Ca granulated material and the workability is deteriorated due to oxide. Therefore, the lower limit is made 0.0003%. The upper limit is added within a range of 0.0030%. Considering manufacturability such as slag treatment, it is desirable that the lower limit is 0.0005% and the upper limit is 0.0015%.
Zr:0.30%以下
Zrは、NbやTiなどと同様に炭窒化物を形成してCr炭窒化物の形成を抑制し耐食性を向上させるため、必要に応じて0.01%以上で添加する。また、0.30%を超えて添加してもその効果は飽和し、大型酸化物の形成により表面疵の原因にもなるため、下限を0.01%とし、上限を0.30%とする範囲内で添加する。Ti,Nbに較べると高価な元素でありため製造コストを考慮すると、下限を0.02%とし、上限を0.05%とすることが望ましい。Zr: 0.30% or less Zr is added in an amount of 0.01% or more as necessary in order to form a carbonitride and suppress the formation of Cr carbonitride and improve the corrosion resistance like Nb and Ti. To do. Moreover, even if added over 0.30%, the effect is saturated and the formation of large oxides can cause surface defects. Therefore, the lower limit is set to 0.01% and the upper limit is set to 0.30%. Add within range. Since it is an expensive element compared with Ti and Nb, considering the manufacturing cost, it is desirable that the lower limit is 0.02% and the upper limit is 0.05%.
REM(希土類元素):0.20%以下
REMは、耐酸化性の向上に有効であり、必要に応じて0.001%以上で添加する。また、0.20%を超えて添加してもその効果は飽和し、REMの粒化物による耐食性低下を生じるため、下限を0.001%とし、上限を0.20%とする範囲内で添加する。製品の加工性や製造コストを考慮すると、下限を0.002%とし、上限を0.05%とすることが望ましい。なお、REM(希土類元素)は、一般的な定義に従い、スカンジウム(Sc)、イットリウム(Y)の2元素と、ランタン(La)からルテチウム(Lu)までの15元素(ランタノイド)の総称を指す。単独で添加してもよいし、混合物であってもよい。REM (rare earth element): 0.20% or less REM is effective in improving oxidation resistance, and is added at 0.001% or more as necessary. Moreover, even if added over 0.20%, the effect is saturated, and the corrosion resistance is reduced by the REM granulated material. Therefore, the lower limit is set to 0.001% and the upper limit is added to 0.20%. To do. Considering the workability and manufacturing cost of the product, it is desirable that the lower limit is 0.002% and the upper limit is 0.05%. Note that REM (rare earth element) refers to a generic name of two elements of scandium (Sc) and yttrium (Y) and 15 elements (lanthanoid) from lanthanum (La) to lutetium (Lu) according to a general definition. It may be added alone or as a mixture.
その他の成分について、本実施形態では特に規定されないが、本実施形態においては、Hf、Bi等を必要に応じて、0.001〜0.1質量%の量で添加してもかまわない。なお、As、Pb等の一般的に有害な元素や不純物元素の量はできるだけ低減することが好ましい。 Although it does not prescribe | regulate especially in this embodiment about another component, in this embodiment, you may add Hf, Bi, etc. in the quantity of 0.001-0.1 mass% as needed. Note that the amount of generally harmful elements such as As and Pb and impurity elements is preferably reduced as much as possible.
本発明のステンレス鋼板は、表面の算術平均粗さRaは特に限定されないが、Ra0.45〜5.0μmとなるような研磨目を有することが望ましい。Raが0.45μm以上では特許文献2に記載の方法でも鋼板表面の耐食性の低下を防止することができず、本発明ではじめて鋼板表面の研磨による耐食性の低下を防止することができる。 The arithmetic mean roughness Ra of the surface of the stainless steel plate of the present invention is not particularly limited, but it is desirable that the stainless steel plate has a polishing eye such that Ra is 0.45 to 5.0 μm. When Ra is 0.45 μm or more, the method described in Patent Document 2 cannot prevent the corrosion resistance of the steel sheet surface from being lowered, and for the first time in the present invention, it is possible to prevent the corrosion resistance from being degraded by polishing the steel sheet surface.
本発明の研磨後のステンレス鋼板は、Siの組成が鋼板の0.15〜3.0%であるにも関わらず、Si濃度が鋼板の5%以上含有する表面層、いわゆるSiO2リッチの酸化物の表面層が形成されていることを特徴としている。前記したような表面層でのSiの濃化は、研磨を施す際の発熱によって表面が酸化されることによって生じる。そこで、本発明のRaの下限を0.45μmとした。一方、厨房機器などの製品の外装への用途においてRaが5.0μmを超えるような研磨が施される例はほとんどないため、Raの上限を5.0μmとした。The stainless steel plate after polishing according to the present invention has a surface layer containing 5% or more of the steel sheet, so-called SiO 2 rich oxidation, even though the Si composition is 0.15 to 3.0% of the steel plate. It is characterized in that a surface layer of an object is formed. The concentration of Si in the surface layer as described above occurs when the surface is oxidized by heat generation during polishing. Therefore, the lower limit of Ra of the present invention is set to 0.45 μm. On the other hand, since there are almost no examples in which Ra exceeds 5.0 μm in applications such as kitchen appliances, the upper limit of Ra is set to 5.0 μm.
本発明のステンレス鋼板は、表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、O及びNを除いた元素の割合の平均質量濃度で、Siが5%以上、Feが75%以下含むものである。Siは酸素親和性が高いので、高温下で優先的に酸化される。そのため、表面の元素濃度をこの範囲とすることにより、表面上の赤さびの発生が抑制されて表面の審美性が損なわれることを防止することができる。また、本発明の鋼成分、特にSi含有量を本発明範囲とするとともに、下記のように圧下率が0.5%以上5.0%以下の調質圧延を行うことによってはじめて、Raが0.45μm以上の研磨目を有する研磨を行った場合においても、表面の元素濃度をSiが5%以上、Feが75%以下とすることが可能となる。 The stainless steel plate of the present invention has an average ratio of elements excluding C, O and N at a depth of 10 nm from the surface when the element concentration on the surface is measured by glow discharge optical emission spectrometry (GD-OES). In terms of mass concentration, Si contains 5% or more and Fe contains 75% or less. Since Si has a high oxygen affinity, it is preferentially oxidized at a high temperature. Therefore, by setting the element concentration on the surface within this range, it is possible to prevent the occurrence of red rust on the surface and prevent the surface aesthetics from being impaired. In addition, the steel component of the present invention, particularly the Si content, is within the scope of the present invention, and Ra is 0 only after temper rolling with a rolling reduction of 0.5% to 5.0% as described below. Even in the case of polishing having a polishing mesh of .45 μm or more, the elemental concentration of the surface can be 5% or more for Si and 75% or less for Fe.
本発明のステンレス鋼板は、表面の明度L*値が70以上の値をとることを特徴とする。L*が70未満の場合、上述した表面から10nmまでの範囲におけるSi濃度が5%以下となるからである。尚、本発明では、明度L*値とは、JIS Z 8729 に規定する L*a*b*表色系におけるCIE明度を意味する。The stainless steel plate of the present invention is characterized in that the surface brightness L * value is 70 or more. This is because when L * is less than 70, the Si concentration in the range from the surface to 10 nm is 5% or less. In the present invention, the lightness L * value means the CIE lightness in the L * a * b * color system defined in JIS Z 8729.
次に、本発明に係るステンレス鋼板の製造方法について説明する。 Next, the manufacturing method of the stainless steel plate which concerns on this invention is demonstrated.
上述した適正な成分組成を有する鋼を公知の方法で溶製し、連続鋳造等公知の方法でスラブとし、当該スラブを1100〜1200℃に再加熱後、仕上げ温度を700〜900℃とする熱間圧延をおこない、熱延鋼帯とする。ついで、この熱延鋼帯を800〜1100℃の温度で焼鈍し、酸洗し、その後冷間圧延を行ない仕上げ厚さを6.0mm以下の冷延鋼帯とする。この冷延鋼帯を、必要に応じて、コークス炉燃焼ガス雰囲気下で、例えば、950℃×60秒程度の焼鈍を施し、その後、ソルト処理したのち、硝弗酸溶液への浸漬処理、または中性塩中での電解処理を施す。 The above-described steel having the proper composition is melted by a known method, and is made into a slab by a known method such as continuous casting. After the slab is reheated to 1100 to 1200 ° C., the finishing temperature is 700 to 900 ° C. Perform hot rolling to obtain a hot-rolled steel strip. Subsequently, this hot-rolled steel strip is annealed at a temperature of 800 to 1100 ° C., pickled, and then cold-rolled to obtain a cold-rolled steel strip having a finished thickness of 6.0 mm or less. If necessary, the cold-rolled steel strip is annealed in a coke oven combustion gas atmosphere, for example, at about 950 ° C. for about 60 seconds, and then subjected to a salt treatment, followed by a dipping treatment in a nitric hydrofluoric acid solution, or Electrolytic treatment in neutral salt.
この冷延鋼帯に、0.5%以上5.0%以下の圧下率の調質圧延をおこなうことにより、表面硬化させる。5.0%超の圧下率で圧延することは設備の能力限界及び表面疵の発生に繋がる可能性があるため適用する場合には設備面や表面疵対策を講じる必要がある。 The cold-rolled steel strip is subjected to temper rolling with a rolling reduction of 0.5% or more and 5.0% or less to harden the surface. Rolling at a rolling reduction of more than 5.0% may lead to the capacity limit of the equipment and the occurrence of surface flaws, so it is necessary to take measures for equipment and surface flaws when applying.
一般的にステンレス鋼では熱間圧延や冷間圧延の際に、金属の結晶粒が圧延によって微細化して大きな加工硬化が生じ、それゆえ、焼鈍工程を要する。これに対して、前記調質圧延は、あくまで表面の輝度や粗さを調整する目的でおこなうために、焼鈍を行わないことが前提となり、それゆえ加工硬化がそれほど生じない範囲でのみ操業され、通常の調質圧延では圧下率は0.5%未満である。これに対して、本発明において調質圧延は、通常の調質圧延よりも大きい圧下率にて行われ、本発明においては、0.5%以上の圧下率において、Si含有量を0.15〜3.0%とすることと相まって、表面を硬質化する効果が認められた。調質圧延の圧下率は1%以上が望ましい。前記の設備能力や表面疵を考慮すると、上限は4%が望ましい。この硬化によって、表面を研磨する際の発熱を抑制することができる。 In general, in stainless steel, during hot rolling or cold rolling, metal crystal grains are refined by rolling to cause large work hardening, and therefore an annealing process is required. On the other hand, the temper rolling is performed only for the purpose of adjusting the brightness and roughness of the surface, and therefore it is premised that annealing is not performed, and therefore is operated only in a range where work hardening does not occur so much. In normal temper rolling, the rolling reduction is less than 0.5%. In contrast, in the present invention, temper rolling is performed at a rolling reduction larger than that of normal temper rolling, and in the present invention, the Si content is 0.15 at a rolling reduction of 0.5% or more. Combined with -3.0%, the effect of hardening the surface was recognized. The rolling reduction of temper rolling is desirably 1% or more. In consideration of the facility capacity and surface defects, the upper limit is preferably 4%. This curing can suppress heat generation when the surface is polished.
本発明における調質圧延による表面硬化は、調質圧延前の焼鈍済み冷延鋼帯の硬さ(以降Hvs値とする)と圧下率に依存して変化する。例えば、Hvsが170である時、圧下率が0.5%、1.0%、4.0%、5.0%では、それぞれの調質圧延後の硬さ(以後Hv値とする)は172、174、184、188となる。この後に示す研磨目の付与をおこなった後の耐食性評価の結果、研磨後の耐食性を十分に得るために必要な調質圧延後のHv値は175以上であることを知見した。望ましくは180以上であり、さらに望ましくは182以上である。尚、調質圧延後の表面硬さの上限は特に限定されないが、生産性の観点および効果が飽和することからHv値の上限を195とすることが望ましい。The surface hardening by temper rolling in the present invention varies depending on the hardness (hereinafter referred to as Hv s value) and the reduction rate of the annealed cold-rolled steel strip before temper rolling. For example, when Hv s is 170, the hardness after temper rolling (hereinafter referred to as Hv value) when the rolling reduction is 0.5%, 1.0%, 4.0%, 5.0% Becomes 172, 174, 184, 188. As a result of the corrosion resistance evaluation after the application of the polishing eyes shown below, it was found that the Hv value after temper rolling required to sufficiently obtain the corrosion resistance after polishing was 175 or more. It is desirably 180 or more, and more desirably 182 or more. The upper limit of the surface hardness after the temper rolling is not particularly limited, but the upper limit of the Hv value is desirably 195 because the viewpoint of productivity and the effect are saturated.
次に表面に意匠性として研磨目を付与するため、ステンレス鋼板の製品板または加工後の製品に対して、算術平均粗さRaが0.45〜5.0μmとなる研磨をおこなう。研磨に使用する研磨ベルトに付着している砥粒のサイズは、使用によって細かくなっていく。すなわち同じベルト部位が継続して使用され、ベルトに付着した砥粒が摩耗または脱落していくと、新品の状態と比較して砥粒のサイズが細かくなっていく。一般的にこれは「目殺し」と呼ばれ、使用している研磨ベルトの実質的な番手或いは粒度番号は大きくなっていく。そのため、仕上げ時の表面粗さが0.45〜5.0μmの範囲内で任意のRaとなるように研磨ベルトの番手と砥粒のサイズを、研磨ベルトの使用状態によって細かく変化させても良い。 Next, in order to give a polished surface as a design property to the surface, the product plate of the stainless steel plate or the processed product is subjected to polishing with an arithmetic average roughness Ra of 0.45 to 5.0 μm. The size of the abrasive grains adhering to the polishing belt used for polishing becomes finer by use. That is, when the same belt portion is continuously used and the abrasive grains adhering to the belt are worn or dropped, the size of the abrasive grains becomes finer than that in a new state. In general, this is called “blindness”, and the actual count or the particle size number of the polishing belt used increases. Therefore, the count of the polishing belt and the size of the abrasive grains may be finely changed according to the use state of the polishing belt so that the surface roughness at the time of finishing is arbitrary Ra within the range of 0.45 to 5.0 μm. .
さらに表面の元素濃度をGD−OESで測定した際に、表面から10nmまでの深さにおいて、CおよびOを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含む表面となるようにするため、Si添加量を0.3〜3.0%とし、上記に規定の調質圧延をおこなって表面硬化を施すことによって、比較的粗い研磨をおこなったとしても研磨時に研削量を低減させることで、昇温を抑制し、Siを優先的に酸化させ、さらに表面のFe酸化物の形成を抑制する。また、表面硬化によって研削量が低減され、さらにSiの優先的な酸化が生じた場合、Fe酸化物の形成が抑制されることによって、表面の明度L*値が70以上の値をとる。 Further, when the surface element concentration was measured by GD-OES, Si was 5% or more and Fe was 75% or less at an average mass concentration of elements excluding C and O at a depth of 10 nm from the surface. Even if a relatively rough polishing is performed by setting the Si addition amount to 0.3 to 3.0% and performing the temper rolling specified above to perform surface hardening so that the surface is included. By reducing the amount of grinding sometimes, temperature rise is suppressed, Si is preferentially oxidized, and formation of Fe oxide on the surface is further suppressed. Further, when the amount of grinding is reduced by surface hardening and preferential oxidation of Si occurs, the formation of Fe oxide is suppressed, and the surface brightness L * value takes a value of 70 or more.
表2−1に示す成分組成を有する本発明鋼の記号A1〜A34、および表2−2に示す比較鋼B1〜B19を真空溶解炉で溶製し、鋳造して30kgの鋼塊を得、この鋼塊を1150℃に加熱し、1150〜900℃の温度範囲で熱間圧延をおこない、板厚が3mmの熱延板とした。ついで、これらの熱延板を950℃で焼鈍したのち冷間圧延と焼鈍を繰り返して、板厚が1.0mmの冷延板とした。その後、表面のスケールを除去するために、ソルト処理したのち、硝弗酸溶液への浸漬処理、または中性塩中での電解処理を施した。この冷延板を表面硬化させるために、表3に示すように最大5.0%の圧下率で調質圧延をおこなった。 Inventive steels A1 to A34 having the composition shown in Table 2-1 and comparative steels B1 to B19 shown in Table 2-2 were melted in a vacuum melting furnace and cast to obtain a 30 kg steel ingot. The steel ingot was heated to 1150 ° C. and hot-rolled in a temperature range of 1150 to 900 ° C. to obtain a hot rolled sheet having a thickness of 3 mm. Subsequently, these hot rolled sheets were annealed at 950 ° C., and then cold rolling and annealing were repeated to obtain cold rolled sheets having a sheet thickness of 1.0 mm. Thereafter, in order to remove the scale on the surface, after a salt treatment, an immersion treatment in a nitric hydrofluoric acid solution or an electrolytic treatment in a neutral salt was performed. In order to harden the surface of this cold-rolled sheet, as shown in Table 3, temper rolling was performed at a maximum reduction of 5.0%.
次に表面に算術平均粗さRaが0.45〜5.0μmの範囲となるような任意の砥粒サイズを有した研磨ベルトで研磨をおこなった。RaはJIS B0601に準じて、測定長さ5mm、測定速度0.60mm/s、カットオフ波長0.8mmで測定した。表3にRaを示す。 Next, the surface was polished with a polishing belt having an arbitrary abrasive grain size such that the arithmetic average roughness Ra was in the range of 0.45 to 5.0 μm. Ra was measured according to JIS B0601 at a measurement length of 5 mm, a measurement speed of 0.60 mm / s, and a cutoff wavelength of 0.8 mm. Table 3 shows Ra.
上記のようにして得た各種ステンレス鋼の表面を、明度測定、GD−OES分析、および耐食性評価をおこなった。また、各種評価は下記の要領でおこなった。 The surface of various stainless steels obtained as described above was subjected to lightness measurement, GD-OES analysis, and corrosion resistance evaluation. Various evaluations were performed as follows.
<GD−OES分析>
サンプルを30mm×30mmのサイズに切断し、スパッタ径φ4mm、スパッタリング間隔2.5msec.、高周波法で、Spectruma Analytik GmbH製のGDA−750HPを用いて各元素の100nmまでの深さ方向の分析をおこなった。Si濃度は、表面から10nmまでの範囲における、軽元素C、O、Nを除いた元素の質量割合で算出した。<GD-OES analysis>
The sample was cut into a size of 30 mm × 30 mm, the sputtering diameter was 4 mm, and the sputtering interval was 2.5 msec. Then, analysis of each element in the depth direction up to 100 nm was performed by a high-frequency method using GDA-750HP manufactured by Spectrum Analyz GmbH. The Si concentration was calculated by the mass ratio of elements excluding the light elements C, O, and N in the range from the surface to 10 nm.
<明度測定>
JIS Z8730に準じて、測定面積φ10mmで、コニカミノルタ社製のCR−200bを用いて、n数3回の平均値を算出した。数値はL*a*b*表色系を用い、CIE明度を表すL*を指標として用いた。L*が70未満の場合、上述した表面から10nmまでの範囲におけるSi濃度が5%以下となった。<Lightness measurement>
According to JIS Z8730, the average value of n times 3 times was calculated using CR-200b manufactured by Konica Minolta, Inc. with a measurement area of 10 mm. The numerical values used the L * a * b * color system, and L * representing CIE brightness was used as an index. When L * was less than 70, the Si concentration in the range from the surface to 10 nm was 5% or less.
<耐食性試験>
耐食性は、上記研磨後のサンプルを用いて、JIS Z2371に規定される塩水噴霧試験(SST)により評価した。塩水噴霧試験の条件は、5質量%の塩化ナトリウム水溶液を、温度35℃で96時間噴霧し続けた。<Corrosion resistance test>
The corrosion resistance was evaluated by the salt spray test (SST) defined in JIS Z2371 using the sample after polishing. The condition of the salt spray test was that a 5 mass% sodium chloride aqueous solution was continuously sprayed at a temperature of 35 ° C. for 96 hours.
<耐食性評価>
耐食性評価は表面のさび発生程度に基づいておこない、A〜Gの7段階で評価結果を示す。耐食性評価結果は、Aが最も良く、Gが最も悪い結果を示し、段階Cを合格下限とした。塩水噴霧試験は、5%の塩化ナトリウム水溶液を35℃で96時間噴霧し続けた。具体的な耐食性の評価基準を表1に示す。<Corrosion resistance evaluation>
Corrosion resistance evaluation is performed based on the degree of rust generation on the surface, and the evaluation results are shown in seven stages A to G. As for the corrosion resistance evaluation result, A is the best, G is the worst result, and stage C is set as the lower limit of acceptance. In the salt spray test, a 5% sodium chloride aqueous solution was continuously sprayed at 35 ° C. for 96 hours. Specific evaluation criteria for corrosion resistance are shown in Table 1.
調質圧延の圧下率、表面のRa、明度測定によるL*値、表面から10nmの厚さの範囲のSi、Feの質量濃度、および耐食性評価結果を表3に示す。 Table 3 shows the rolling reduction of temper rolling, the surface Ra, the L * value by brightness measurement, the mass concentration of Si and Fe in the thickness range of 10 nm from the surface, and the corrosion resistance evaluation results.
また図1には、研磨後に表面10nmの厚さに含まれるSiの質量濃度(mass%)と、色差計で測定するL*値の関係おける、塩水噴霧試験後の耐食性評価値による判定についてのグラフを示す。 In addition, FIG. 1 shows the determination by the corrosion resistance evaluation value after the salt spray test in the relationship between the mass concentration (mass%) of Si contained in the thickness of 10 nm after polishing and the L * value measured with a color difference meter. A graph is shown.
表2−1及び表3のA1〜A34は本発明例である。これらの発明例は、本発明範囲の成分を含有し、本発明で規定する表面の算術平均粗さRa、表面のSi、Fe濃度、表面の明度L*値を具備しており、結果として研磨後に優れた表面耐食性を実現している。 A1 to A34 in Table 2-1 and Table 3 are examples of the present invention. These invention examples contain components within the scope of the present invention, and have the surface arithmetic mean roughness Ra, surface Si, Fe concentration, surface brightness L * value specified in the present invention, and as a result, polishing Later, excellent surface corrosion resistance was achieved.
表2−2及び表3のB1〜B19は比較例である。 B1 to B19 in Table 2-2 and Table 3 are comparative examples.
B1およびB19はSi添加量が少ないため、表面のSi濃度が低く、十分にSiO2を表面に形成させることができない。さらに、硬さが小さく、研磨量が多くなることで発熱が増し、酸化を促進する。そのため、耐食性評価で劣位を示す。B2、B4はN添加量が多いため、粒界腐食が進展し易く、耐食性評価で劣位を示す。特にB2ではCr添加量が少ないため、酸化皮膜中のFeの濃化を十分に抑制することができず、B4よりも耐食性の低下が著しい。Since B1 and B19 have a small Si addition amount, the Si concentration on the surface is low, and SiO 2 cannot be sufficiently formed on the surface. Furthermore, since the hardness is small and the polishing amount is increased, heat generation is increased and oxidation is promoted. Therefore, it is inferior in the corrosion resistance evaluation. Since B2 and B4 have a large N addition amount, intergranular corrosion is likely to progress, and inferior in corrosion resistance evaluation. In particular, since the amount of Cr added is small in B2, the concentration of Fe in the oxide film cannot be sufficiently suppressed, and the corrosion resistance is significantly lower than that in B4.
B3はC添加量が多いため、N添加量が多い場合と同じように粒界腐食が進展し易く、耐食性評価で劣位を示す。B5はB2と同様にCr添加量が少ないため、酸化皮膜中のFeの濃化を十分に抑制することができず、耐食性は劣位を示す。B6またはB7はMnまたはS添加量が多いため、腐食の起点となるMnSを生成し易くなり、耐食性は劣位を示す。 Since B3 has a large amount of C added, intergranular corrosion is likely to proceed as in the case where the amount of N added is large, and inferior in corrosion resistance evaluation. B5, like B2, has a small amount of Cr added, so it cannot sufficiently suppress the concentration of Fe in the oxide film, and the corrosion resistance is inferior. Since B6 or B7 has a large amount of Mn or S added, it becomes easy to generate MnS as a starting point of corrosion, and the corrosion resistance is inferior.
B8またはB9はAlまたはTi添加量が多いため、非金属介在物を粗大化させ、表面疵の発生が認められたため、本発明には不適切である。B10またはB11、B12、B13、B14、B15、B18はCrまたはNb、V、Cu、Sn、Ni、Si添加量が多いため、加工性および製造性を低下させ、さらにコスト増となるため、本発明には不適切である。また、B17は、P>0.04%にてPを含有するために、加工性が低下し、SST評価も低かった。 Since B8 or B9 has a large amount of Al or Ti, nonmetallic inclusions are coarsened and surface flaws are observed, which is inappropriate for the present invention. Since B10 or B11, B12, B13, B14, B15, B18 has a large amount of Cr or Nb, V, Cu, Sn, Ni, Si added, the workability and manufacturability are reduced, and the cost is further increased. It is inappropriate for the invention. Moreover, since B17 contains P at P> 0.04%, the workability was lowered and the SST evaluation was also low.
B16は、調質圧延圧下率が0.5%未満であったため、表面の硬度が不十分であり、その耐食性は劣位を示す。 Since B16 had a temper rolling reduction ratio of less than 0.5%, the surface hardness was insufficient and its corrosion resistance was inferior.
本発明のフェライト系ステンレス鋼板は、厨房機器、家電製品、電子機器、器物などの製品のうち人目に触れ易い外装や日用品への使用が好適である。 The ferritic stainless steel plate of the present invention is suitable for use in exteriors and daily necessities that are easy to touch among products such as kitchen equipment, home appliances, electronic equipment, and articles.
Claims (9)
C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、残部はFeおよび不可避的不純物であり、
表面硬さHvが175以上195以下であって、
表面に算術平均粗さRaが0.45〜5.0μmの研磨目を付与した時に、表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み、さらに表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。% By mass
C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less Cr: 12 to 22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less, the balance being Fe and inevitable impurities,
The surface hardness Hv is 175 or more and 195 or less,
Depth from the surface to 10 nm when the elemental concentration on the surface was measured by glow discharge optical emission spectrometry (GD-OES) when an arithmetic mean roughness Ra was applied to the surface with an abrasive roughness of 0.45 to 5.0 μm. The average mass concentration of the elements excluding C, O, and N includes Si of 5% or more and Fe of 75% or less, and the surface brightness L * value is 70 or more. Ferritic stainless steel with excellent surface corrosion resistance after polishing.
C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、残部はFeおよび不可避的不純物であり、
表面硬さHvが175以上195以下であって、
表面に算術平均粗さRaが0.45〜5.0μmの研磨目を有し、
さらに表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。% By mass
C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less Cr: 12 to 22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less, the balance being Fe and inevitable impurities,
The surface hardness Hv is 175 or more and 195 or less,
The surface has an arithmetic mean roughness Ra of 0.45 to 5.0 μm,
Furthermore, when the elemental concentration of the surface was measured by glow discharge optical emission spectrometry (GD-OES), at a depth of 10 nm from the surface, Si was an average mass concentration of the ratio of elements excluding C, O and N. A ferritic stainless steel excellent in surface corrosion resistance after polishing, characterized by having a surface lightness L * value of 70% or more, containing 5% or more and Fe of 75% or less.
C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、
さらに質量%で、Sn:0.005〜1.0%、Ni:0.50%以下、Cu:1.50%以下、Mo:3.0%以下、V:1.0%以下、B:0.003%以下、Sb:0.001〜0.3%、Ga:0.0002〜0.1%、及びTa:0.50%以下のうち1種以上を含有し、
残部はFeおよび不可避的不純物であり、
表面硬さHvが175以上195以下であって、
表面に算術平均粗さRaが0.45〜5.0μmの研磨目を付与した時に、表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み、さらに表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。% By mass
C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less Cr: 12-22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less,
Further, by mass%, Sn: 0.005 to 1.0%, Ni: 0.50% or less, Cu: 1.50% or less, Mo: 3.0% or less, V: 1.0% or less, B: 0.003% or less, Sb: 0.001-0.3%, Ga: 0.0002-0.1%, and Ta: 0.50% or less contains one or more,
The balance is Fe and inevitable impurities,
The surface hardness Hv is 175 or more and 195 or less,
Depth from the surface to 10 nm when the elemental concentration on the surface was measured by glow discharge optical emission spectrometry (GD-OES) when an arithmetic mean roughness Ra was applied to the surface with an abrasive roughness of 0.45 to 5.0 μm. The average mass concentration of the elements excluding C, O, and N includes Si of 5% or more and Fe of 75% or less, and the surface brightness L * value is 70 or more. Ferritic stainless steel with excellent surface corrosion resistance after polishing.
C:0.030%以下、N:0.030%以下、Si:0.15〜3.0%、Mn:1.5%以下、P:0.04%以下、S:0.01%以下、Cr:12〜22.5%、Nb:0.60%以下、Ti:0.60%以下、Al:0.80%以下を含有し、
さらに質量%で、Sn:0.005〜1.0%、Ni:0.50%以下、Cu:1.50%以下、Mo:3.0%以下、V:1.0%以下、B:0.003%以下、Sb:0.001〜0.3%、Ga:0.0002〜0.1%、及びTa:0.50%以下のうち1種以上を含有し、残部はFeおよび不可避的不純物であり、
表面硬さHvが175以上195以下であって、
表面に算術平均粗さRaが0.45〜5.0μmの研磨目を有し、さらに表面の元素濃度をグロー放電発光分析法(GD−OES)で測定した際に、表面から10nmまでの深さにおいて、C、OおよびNを除いた元素の割合の平均質量濃度で、Siを5%以上、Feを75%以下含み表面の明度L*値が70以上の値をとることを特徴とする、研磨後の表面耐食性に優れるフェライト系ステンレス鋼。% By mass
C: 0.030% or less, N: 0.030% or less, Si: 0.15-3.0%, Mn: 1.5% or less, P: 0.04% or less, S: 0.01% or less Cr: 12-22.5%, Nb: 0.60% or less, Ti: 0.60% or less, Al: 0.80% or less,
Further, by mass%, Sn: 0.005 to 1.0%, Ni: 0.50% or less, Cu: 1.50% or less, Mo: 3.0% or less, V: 1.0% or less, B: Contains 0.003% or less, Sb: 0.001 to 0.3%, Ga: 0.0002 to 0.1%, and Ta: 0.50% or less, with the balance being Fe and inevitable Impurities,
The surface hardness Hv is 175 or more and 195 or less,
The surface has an arithmetic mean roughness Ra of 0.45 to 5.0 μm, and when the element concentration of the surface is measured by glow discharge optical emission spectrometry (GD-OES), the depth from the surface to 10 nm Here, the average mass concentration of the ratio of elements excluding C, O, and N is characterized in that Si is 5% or more and Fe is 75% or less, and the surface brightness L * value is 70 or more. Ferritic stainless steel with excellent surface corrosion resistance after polishing.
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KR20190121761A (en) * | 2017-02-23 | 2019-10-28 | 닛테츠 스테인레스 가부시키가이샤 | Black Ferritic Stainless Steel Sheet |
KR102384703B1 (en) * | 2017-02-23 | 2022-04-07 | 닛테츠 스테인레스 가부시키가이샤 | Black ferritic stainless steel sheet |
US11326236B2 (en) | 2017-02-23 | 2022-05-10 | Nippon Steel Stainless Steel Corporation | Black ferrite-based stainless steel sheet |
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CN105074035B (en) | 2018-02-16 |
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