US20250215543A1 - Steel sheet and enameled product - Google Patents

Steel sheet and enameled product Download PDF

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Publication number
US20250215543A1
US20250215543A1 US18/852,913 US202218852913A US2025215543A1 US 20250215543 A1 US20250215543 A1 US 20250215543A1 US 202218852913 A US202218852913 A US 202218852913A US 2025215543 A1 US2025215543 A1 US 2025215543A1
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Prior art keywords
steel sheet
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enameling
case
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US18/852,913
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English (en)
Inventor
Nobuo Yoshikawa
Hisayoshi Yatoh
Kazuhisa Kusumi
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Nippon Steel Corp
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Nippon Steel Corp
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Assigned to NIPPON STEEL CORPORATION reassignment NIPPON STEEL CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUSUMI, KAZUHISA, YATOH, HISAYOSHI, YOSHIKAWA, NOBUO
Publication of US20250215543A1 publication Critical patent/US20250215543A1/en
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    • 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
    • C22C38/60—Ferrous alloys, e.g. steel alloys containing lead, selenium, tellurium, or antimony, or more than 0.04% by weight of sulfur
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D1/00—General methods or devices for heat treatment, e.g. annealing, hardening, quenching or tempering
    • C21D1/74—Methods of treatment in inert gas, controlled atmosphere, vacuum or pulverulent material
    • C21D1/76—Adjusting the composition of the atmosphere
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0221—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the working steps
    • C21D8/0236—Cold rolling
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0257—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment with diffusion of elements, e.g. decarburising, nitriding
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0247—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips characterised by the heat treatment
    • C21D8/0273—Final recrystallisation annealing
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • C21D8/00—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment
    • C21D8/02—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips
    • C21D8/0278—Modifying the physical properties of ferrous metals or ferrous alloys by deformation combined with, or followed by, heat treatment during manufacturing of plates or strips involving a particular surface treatment 
    • C21D8/0284—Application of a separating or insulating coating
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21D—MODIFYING THE PHYSICAL STRUCTURE OF FERROUS METALS; GENERAL DEVICES FOR HEAT TREATMENT OF FERROUS OR NON-FERROUS METALS OR ALLOYS; MAKING METAL MALLEABLE, e.g. BY DECARBURISATION OR TEMPERING
    • 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
    • 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
    • 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
    • C22C38/001—Ferrous alloys, e.g. steel alloys containing N
    • 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
    • C22C38/004—Very low carbon steels, i.e. having a carbon content of less than 0,01%
    • 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
    • C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
    • 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
    • C22C38/02—Ferrous alloys, e.g. steel alloys containing 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
    • C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
    • 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
    • C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
    • 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
    • C22C38/20—Ferrous alloys, e.g. steel alloys containing chromium with copper
    • 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
    • C22C38/22—Ferrous alloys, e.g. steel alloys containing chromium with molybdenum or tungsten
    • 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
    • C22C38/32—Ferrous alloys, e.g. steel alloys containing chromium with boron

Definitions

  • the present invention relates to a steel sheet and an enameled product.
  • the C content is set to 0.0050% or less in consideration of a balance between cost and properties.
  • the C content is preferably 0.0040% or less, more preferably 0.0030% or less, and still more preferably 0.0020% or less.
  • the Si content may be 0%. However, since an excessive reduction in the Si content causes an increase in cost, the Si content may be set to 0.001% or more.
  • Mn is an element that generates inclusions containing oxygen and contributes to the improvement of enamel properties, and is also an element that has an action of preventing hot embrittlement caused by S.
  • the Mn content is set to 0.007% or more.
  • the Mn content is preferably 0.010% or more and more preferably 0.10% or more.
  • Mn is an element that has an action of lowering a transformation point of steel.
  • the Mn content is set to 1.00% or less from these viewpoints.
  • the Mn content is preferably 0.50% or less.
  • P is an element that has an action of increasing the strength of the steel sheet through solid solution strengthening.
  • the P content is set to 0.020% or more.
  • the P content is preferably 0.050% or more.
  • S is an element that has an effect of increasing pickling rate and roughening the surface of the steel sheet after pickling to improve enamel adhesion.
  • the S content is set to 0.005% or more.
  • the S content is preferably 0.010% or more.
  • the S content is set to 0.050% or less.
  • Al is a strong deoxidizing element.
  • the Al content exceeds 0.010%, it is difficult to retain a required amount of O (oxygen) in steel. As a result, it is difficult to control oxide effective for fish scaling resistance. For that reason, the Al content is set to 0.010% or less.
  • the Al content is preferably 0.005% or less.
  • a lower limit of the Al content does not need to be limited, but the Al content may be 0.001% or more from the viewpoint of controlling the amount of oxygen.
  • the O content is a constituent element of fine inclusions that capture hydrogen contained in steel to improve fish scaling resistance and is an important element in a steel sheet for vitreous enameling.
  • the O content is set to 0.0100% or more in order to ensure desired enamel properties. In a case where the O content is less than 0.0100%, inclusions are not sufficiently formed and fish scaling resistance is reduced.
  • the O content is preferably 0.0120% or more, more preferably 0.0150% or more, and still more preferably 0.0200% or more.
  • the O content is set to 0.1000% or less.
  • the O content is preferably 0.0800% or less.
  • Cu is an element that reduces pickling weight loss and forms fine irregularities on the surface of the steel sheet subjected to pickling and improves adhesion (enamel adhesion).
  • the Cu content is set to 0.010% or more.
  • the Cu content is preferably 0.015% or more, and more preferably 0.020% or more.
  • the Cu content is set to 0.060% or less.
  • the Cu content is preferably 0.050% or less.
  • Sn and Sb are elements that have an effect of increasing the strength of the steel sheet through solid solution strengthening and an effect of reducing pickling rate. For that reason, one or two of Sn and Sb are contained. However, in a case where each of the Sn content and the Sb content is less than 0.010% or the total content of Sn and Sb is less than 0.11%, an effect of increasing the strength of the steel sheet cannot be sufficiently obtained. For that reason, in a case where Sn and Sb are to be contained, each of the Sn content and the Sb content is set to 0.010% or more and the total content of Sn and Sb is set to 0.11% or more. Each of the Sn content and the Sb content is preferably 0.04% or more or 0.07% or more. The total content of Sn and Sb is preferably 0.14% or more.
  • each of the Sn content and the Sb content is set to 1.00% or less.
  • Each of the Sn content and the Sb content is preferably 0.80% or less.
  • An upper limit of the total content of Sn and Sb is 2.00%, which is the sum of upper limits of the Sn content and the Sb content.
  • N is an element that causes strain ageing. In a case where strain ageing is caused, the workability of the steel sheet is impaired. For that reason, the N content is preferably as low as possible. However, since N may be mixed as an impurity, a long treatment time in a steelmaking step is required and steelmaking cost is also increased in order to excessively reduce the N content. For that reason, the N content is set to 0.0050% or less in consideration of a balance between cost and properties. The N content is preferably 0.035% or less. From the viewpoint of steelmaking cost, the N content may be set to 0.0005% or more or 0.0010% or more.
  • Cr is an element that generates inclusions containing O and contributes to the improvement of fish scaling resistance. In a case where the Cr content is less than 0.010%, a sufficient effect cannot be obtained. For that reason, the Cr content is set to 0.010% or more.
  • the Cr content is preferably 0.03% or more.
  • temper rolling was performed with a rolling ratio of 0.5%, so that steel sheets (cold-rolled steel sheets) having a sheet thickness of 0.7 mm were obtained.
  • test pieces were collected in the rolling direction and a tensile test was performed in accordance with JIS Z2241:2011 to obtain a tensile strength (TS) and a yield stress (YS) or a 0.2% proof stress (0.2% PS).
  • TS tensile strength
  • YS yield stress
  • PS 0.2% proof stress
  • tensile properties and enamel properties were evaluated in the following manner.
  • the obtained steel sheets were subjected to a heat treatment simulating enameling at a furnace temperature of 860° C. for 5 minutes.
  • a No. 5 test piece was collected in the rolling direction from each of the steel sheets subjected to the heat treatment and a tensile test was performed in accordance with JIS Z2241:2011 to obtain a tensile strength (TS) and a yield stress (YS) or a 0.2% proof stress (0.2% PS).
  • TS tensile strength
  • YS yield stress
  • PS 0.2% proof stress
  • Samples having a size of 150 mm ⁇ 100 mm were collected from the obtained steel sheets and, as a pretreatment, the samples were subjected to alkaline degreasing, immersed in a 15 g/L nickel sulfate solution having a temperature of 70° C. for 7 minutes, and then subjected to a neutralization treatment.
  • both surfaces of the samples were glazed to 100 ⁇ m with a 102 #glaze manufactured by Ferro Enamels (Japan) Limited, and the samples were baked at 860° C. for 5 minutes in an atmosphere having a dew point of 35° C.
  • the baked samples were heated by being held at 150° C. for 20 hours, and the occurrence state of fish scaling was visually observed and evaluated.
  • Evaluation criteria were as follows: S was defined as “particularly excellent”, A was defined as “excellent”, B was defined as “normal”, and C was defined as “problematic” and determined to be a failure.
  • Samples having a size of 150 mm ⁇ 100 mm were collected from the obtained steel sheets and, as a pretreatment, the samples were subjected to alkaline degreasing, immersed in a 10% sulfuric acid solution having a temperature of 70° C. for 10 minutes, immersed in a 15 g/L nickel sulfate solution having a temperature of 70° C. for 7 minutes, and then subjected to a neutralization treatment.
  • both surfaces of the samples were glazed 100 ⁇ m with a 102 #glaze manufactured by Ferro Enamels (Japan) Limited, and the samples were baked at 860° C. for 5 minutes in an atmosphere having a dew point of 35° C.
  • a weight of 2 kg with a spherical head was dropped from a height of 1 m onto the baked sample, and the enamel peeling state of a deformed portion was measured with 169 tactile probes and was evaluated with the area ratio of an unpeeled portion.
  • Evaluation criteria were as follows: A was defined as “excellent”, B was defined as “normal”, and C was defined as “problematic” and determined to be a failure.
  • Samples having a size of 150 mm ⁇ 100 mm were collected from the steel sheets and, as a pretreatment, the samples were subjected to alkaline degreasing, immersed in a 15 g/L nickel sulfate solution having a temperature of 70° C. for 7 minutes, and then subjected to a neutralization treatment.
  • both surfaces of the samples were glazed to 100 ⁇ m with a 102 #glaze manufactured by Ferro Enamels (Japan) Limited, and the samples were baked at 860° C. for 5 minutes in an atmosphere having a dew point of 35° C.
  • the external appearance of the baked sample was visually observed, and the state of bubbles and black spots was evaluated.
  • a case where even one bubble or black spot was generated was evaluated as the generation of bubbles or black spots, and a case where no bubble or black spot was generated was evaluated as no problem.
  • this steel sheet in which high strength and excellent enamel properties (fish scaling resistance, adhesion, and external appearance) are obtained after an enameling treatment.
  • the tensile strength of this steel sheet subjected to the enameling treatment is higher than that of a steel sheet for vitreous enameling in the related art subjected to the enameling treatment.
  • this steel is suitable as a steel sheet for vitreous enameling that is a substrate of an enameled product to be applied to kitchen appliances, building materials, energy fields, and the like, and contributes to a reduction in the weight of the product.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Heat Treatment Of Sheet Steel (AREA)
US18/852,913 2022-04-11 2022-12-26 Steel sheet and enameled product Pending US20250215543A1 (en)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
JP2022-064917 2022-04-11
JP2022064917 2022-04-11
PCT/JP2022/047850 WO2023199555A1 (ja) 2022-04-11 2022-12-26 鋼板およびほうろう製品

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US20250215543A1 true US20250215543A1 (en) 2025-07-03

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US18/852,913 Pending US20250215543A1 (en) 2022-04-11 2022-12-26 Steel sheet and enameled product

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Country Link
US (1) US20250215543A1 (https=)
JP (1) JP7648978B2 (https=)
KR (1) KR20240163668A (https=)
CN (1) CN118974294A (https=)
MX (1) MX2024012450A (https=)
TW (1) TWI846235B (https=)
WO (1) WO2023199555A1 (https=)

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WO2026058872A1 (ja) * 2024-09-12 2026-03-19 日本製鉄株式会社 鋼板及びほうろう製品

Family Cites Families (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5831063A (ja) 1981-08-18 1983-02-23 Kawasaki Steel Corp ほうろう用高張力冷延鋼板
JPS61117246A (ja) 1984-11-13 1986-06-04 Nippon Kokan Kk <Nkk> 焼成後の強度が高く且つ耐爪とび性に優れたほうろう用熱延鋼板の製造方法
JP3348628B2 (ja) * 1997-06-13 2002-11-20 日本鋼管株式会社 深絞り性に優れたほうろう用冷延鋼板およびその製造方法
JP3421911B2 (ja) * 1998-08-21 2003-06-30 Ｊｆｅエンジニアリング株式会社 焼成後強度が低下しにくいほうろう用冷延鋼板
JP3643319B2 (ja) * 2000-12-22 2005-04-27 新日本製鐵株式会社 加工性、ほうろう密着性、耐泡・黒点性及び耐つまとび性に優れた連続鋳造ほうろう用鋼板及びその製造方法
WO2008038474A1 (fr) 2006-09-27 2008-04-03 Nippon Steel Corporation Tôle en acier pour émaillage présentant une très faible propension à l'écaillage et procédé pour la produire
JP5114749B2 (ja) * 2008-08-11 2013-01-09 新日鐵住金株式会社 耐爪飛び性に優れたほうろう用鋼板
CN102575308A (zh) * 2009-07-30 2012-07-11 塔塔钢铁艾默伊登有限责任公司 生产超低碳钢板坯、带材或片材的过程
CN102766822A (zh) * 2012-07-27 2012-11-07 宝山钢铁股份有限公司 一种搪玻璃用高强度钢板及其制造方法
CN108796380B (zh) * 2017-04-26 2020-06-23 宝山钢铁股份有限公司 烧成后屈服强度在210MPa以上的极低碳冷轧搪瓷用钢板及其制造方法
KR102504491B1 (ko) * 2018-05-17 2023-02-28 닛폰세이테츠 가부시키가이샤 강판 및 법랑 제품
CN113308647B (zh) * 2020-02-27 2022-06-28 宝山钢铁股份有限公司 一种搪瓷用冷轧钢板及其制造方法
WO2021193953A1 (ja) * 2020-03-27 2021-09-30 日本製鉄株式会社 鋼板およびほうろう製品

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TW202340492A (zh) 2023-10-16
MX2024012450A (es) 2024-11-08
WO2023199555A1 (ja) 2023-10-19
CN118974294A (zh) 2024-11-15
JP7648978B2 (ja) 2025-03-19
TWI846235B (zh) 2024-06-21
KR20240163668A (ko) 2024-11-19
JPWO2023199555A1 (https=) 2023-10-19

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