WO2016140286A1 - Tôle d'acier plaquée contenant des quasi-cristaux et procédé de production de tôle d'acier plaquée contenant des quasi-cristaux - Google Patents

Tôle d'acier plaquée contenant des quasi-cristaux et procédé de production de tôle d'acier plaquée contenant des quasi-cristaux Download PDF

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WO2016140286A1
WO2016140286A1 PCT/JP2016/056495 JP2016056495W WO2016140286A1 WO 2016140286 A1 WO2016140286 A1 WO 2016140286A1 JP 2016056495 W JP2016056495 W JP 2016056495W WO 2016140286 A1 WO2016140286 A1 WO 2016140286A1
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steel sheet
coating layer
metal coating
content
phase
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PCT/JP2016/056495
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English (en)
Japanese (ja)
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橋本　茂
悠人 福田
公平 ▲徳▼田
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新日鐵住金株式会社
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Priority to JP2016530267A priority Critical patent/JP6075513B1/ja
Publication of WO2016140286A1 publication Critical patent/WO2016140286A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/04—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the coating material
    • C23C2/06—Zinc or cadmium or alloys based thereon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/26—After-treatment
    • C23C2/28—Thermal after-treatment, e.g. treatment in oil bath
    • C23C2/29—Cooling or quenching
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C2/00—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor
    • C23C2/34—Hot-dipping or immersion processes for applying the coating material in the molten state without affecting the shape; Apparatus therefor characterised by the shape of the material to be treated
    • C23C2/36—Elongated material
    • C23C2/40—Plates; Strips

Definitions

  • the present invention relates to a quasicrystal-containing plated steel sheet and a method for producing a quasicrystal-containing plated steel sheet.
  • the quasicrystal is a crystal structure first discovered by Daniel Schuchman in 1982 and has an icosahedral atomic arrangement.
  • This bonded structure is a non-periodic crystal structure having a specific rotational symmetry (for example, five-fold symmetry) that cannot be obtained with a normal metal or alloy, and is a non-periodic crystal typified by a three-dimensional Penrose pattern. It is known as a crystal structure equivalent to the structure.
  • Patent Documents 1 and 2 disclose a high-strength Mg-based alloy and a method for producing the same. These Mg-based alloys are excellent in strength and elongation in which a hard quasicrystalline phase having a particle size of several tens to several hundreds of nanometers is dispersed and precipitated in a metal structure. In these patent documents 1 and patent documents 2, the characteristic that a quasicrystal is hard is used.
  • Patent Document 3 discloses a thermoelectric material using an Al reference crystal.
  • the characteristic that a quasicrystal is excellent in a thermoelectric characteristic is utilized.
  • Patent Document 4 discloses a heat-resistant catalyst using a quasicrystalline Al alloy (Al reference crystal) as a precursor and a method for producing the same.
  • the quasicrystal which does not have a periodic crystal structure utilizes the characteristic that it is brittle and easy to fracture. As described above, in the inventions so far, the quasicrystals are often dispersed as fine particles, or the quasicrystals that are fine particles are often solidified and molded.
  • Patent Document 5 discloses a metal coating for cooking utensils containing a quasicrystal.
  • the coating powder which is excellent in wear resistance and corrosion resistance to salt is imparted to the cooking utensil by plasma spraying an alloy powder containing a quasi-joint having excellent corrosion resistance made of Al, Fe or Cr. Yes.
  • the Mg reference crystal is used as a material having excellent strength
  • the Al reference crystal is used as a member having excellent strength, a thermoelectric material, a cooking utensil coating, and the like.
  • these uses are limited, and it cannot be said that quasicrystals are necessarily used in many fields.
  • Quasicrystals have excellent performance due to their unique crystal structure. However, its characteristics are only partially elucidated, and it cannot be said that it is a material that is currently widely used industrially. The inventor tried to improve the corrosion resistance by applying a quasicrystal that has not been industrially used yet to the metal coating layer of the plated steel sheet.
  • the steel plate is given a certain anticorrosion function by performing a surface treatment such as metal coating, coating treatment, chemical conversion treatment, or organic coating lamination.
  • a surface treatment such as metal coating, coating treatment, chemical conversion treatment, or organic coating lamination.
  • Many steel materials used in the fields of automobiles, home appliances, building materials, etc. are mainly subjected to metal coating treatment.
  • the metal coating layer By the metal coating layer, a barrier anticorrosive effect that shields the base iron (steel material) from the external environment and a sacrificial anticorrosive action that prevents the base iron by corroding preferentially over the base iron can be imparted at low cost.
  • a thermal spraying method or a hot dipping method is suitable.
  • a sputtering method, an ion plating method, a vapor deposition method, an electric method, A plating method is suitable.
  • the hot dipping method is widely used because it can mass-produce a steel material having a metal coating layer at low cost.
  • the electroplating method there are restrictions on the deposited metal, and there are restrictions on the elements constituting the metal coating layer.
  • the method of forming a metal coating layer using metal melting, evaporation, precipitation, solidification reaction, etc. such as thermal spraying and vapor deposition, theoretically uses the same metal coating layer as the hot dipping method. Can be formed.
  • the thermal spraying method and the vapor deposition method tend to cause separation between the chemical component of the alloy used and the chemical component of the formed metal coating layer.
  • the hot dipping method capable of forming a metal coating layer having a chemical component substantially equivalent to the chemical component of the alloy used in the hot dipping bath is a method for forming a metal coating layer having a target chemical component. Better than any other method.
  • the general surface-treated steel sheets that can be obtained on the market are mainly surface-treated steel sheets having a metal coating layer of a Zn-based alloy or a metal coating layer of an Al-based alloy.
  • the metal coating layer of this Zn-based alloy is a metal coating layer containing a small amount of elements such as Al and Mg in the main component Zn.
  • a metal structure of the metal coating layer in addition to the Zn phase, an Al phase, MgZn Two phases and the like are contained.
  • a metal coating layer of an Al-based alloy is a metal coating layer containing a small amount of elements such as Si and Fe in Al as a main component. Fe 2 Al 5 phase and the like are contained.
  • Mg-based alloy plated steel materials as disclosed in Patent Documents 6 to 8 have been proposed as plated steel materials having completely different plating alloy components from these general surface-treated steel sheets.
  • the present inventor has examined the further improvement of the corrosion resistance based on these plated steel materials and focusing on the quasicrystals that have hardly been considered for improving the corrosion resistance of the plating layer (metal coating layer). did.
  • Patent Documents 9 to 13 also disclose plated steel materials.
  • Patent Documents 14 to 15 also disclose quasicrystal-containing plated steel sheets in which the metal structure of the metal coating layer includes a quasicrystalline phase.
  • Patent Document 1 Japanese Patent Application Laid-Open No. 2005-113235 Patent Document 2: Japanese Patent Application Laid-Open No. 2008-69438 Patent Document 3: Japanese Patent Application Laid-Open No. 8-176762 Patent Document 4: Japanese Patent Application Laid-Open No. 2004-267878 Patent Document 5: Japan Special Table 2007-525596 Patent Document 6: Japan JP 2008-255464 JP Patent Document 7: Japan JP 2010-248541 JP Patent Document 8: Japan JP 2011 Patent Document 9: Japanese Patent Application Laid-Open No. 2008-255464 Patent Document 10: Japanese Patent Application Laid-Open No. 9-143659 Patent Document 11: Japanese Patent Application Laid-Open No. 5-320848 Patent Document 12: Japanese Special Japanese Patent Laid-Open No. 2014-205877 Patent Document 13: Japanese Patent Laid-Open No. 6-2096 Patent Document 14 Japanese Patent 5785335 Patent Document 15: Japanese Patent No. 5785336
  • the present invention has been made in view of the above circumstances.
  • the object of the present invention is to provide a quasi-crystal-containing plated steel sheet and a quasi-crystal-containing plating that have improved corrosion resistance and sacrificial corrosion resistance required when used in various fields such as building materials, automobiles, and home appliances. It is providing the manufacturing method of a steel plate.
  • the present inventor has focused on quasicrystals that have hardly been considered for increasing the corrosion resistance of the plating layer so far, and has clarified the structure of the metal structure with the highest improvement in corrosion resistance. As a result, a plated steel sheet having excellent corrosion resistance and sacrificial corrosion resistance has been completed. Specifically, regarding the quasicrystalline phase that has not been studied so far, the preferred existence form in the metal coating layer (plating layer) is clarified, and such a quasicrystalline phase is preferably formed in the metal coating layer. By clarifying the method, the corrosion resistance and sacrificial corrosion resistance of the plated steel sheet were successfully improved.
  • the present invention has been made on the basis of the above findings, and the gist thereof is as follows.
  • the chemical composition of the metal coating layer is atomic%, Zn: 20% to 60%, Al: 0.3% to 15.0% , Ca: 0% to 3.5%, Y: 0% to 3.5%, La: 0% to 3.5%, Ce: 0% to 3.5%, Si: 0% to 0.5% Ti: 0% to 0.5%, Cr: 0% to 0.5%, Fe: 0% to 2.0%, Co: 0% to 0.5%, Ni: 0% to 0.5% , V: 0% to 0.5%, Nb: 0% to 0.5%, Cu: 0% to 0.5%, Sn: 0% to 0.5%, Mn: 0% to 0.2% , Sr: 0% to 0.5%, Sb: 0% to 0.5%, Pb: 0% to 0.5%, with the balance being Mg and impurities, the chemical component of the metal coating layer
  • the zinc content and the aluminum content in the atomic% are 25% ⁇ n + Al is satisfied, and the metal structure of the metal coating layer includes
  • the quasicrystalline phase is present at the interface between the steel sheet and the metal coating layer, and has a minor axis of 0.2 ⁇ m to 2 ⁇ m Occupies 90% or more of the interface, and among the remaining quasicrystalline phases other than the quasicrystalline phase present at the interface between the steel sheet and the metal coating layer, the size of the quasicrystalline phase is 95% by number or more.
  • the calcium content, the yttrium content, the lanthanum content, and the cerium content in the chemical component of the metal coating layer satisfy 0.3 ⁇ Ca + Y + La + Ce ⁇ 3.5% in atomic%.
  • the silicon content, the titanium content, and the chromium content in the chemical component of the metal coating layer satisfy 0.005% ⁇ Si + Ti + Cr ⁇ 0.5% in atomic%, (1) or The quasicrystal-containing plated steel sheet according to (2).
  • the zinc content and the aluminum content in the chemical component of the metal coating layer are atomic%, 30% ⁇ Zn + Al ⁇ 50%, and 3.0 ⁇ Zn / Al ⁇ 12.0.
  • Chemical component is atomic%, Zn: 20% to 60%, Al: 0.3% to 15.0%, Ca: 0% to 3.5%, Y: 0% to 3.5% La: 0% to 3.5%, Ce: 0% to 3.5%, Si: 0% to 0.5%, Ti: 0% to 0.5%, Cr: 0% to 0.5% Fe: 0% to 2.0%, Co: 0% to 0.5%, Ni: 0% to 0.5%, V: 0% to 0.5%, Nb: 0% to 0.5% Cu: 0% to 0.5%, Sn: 0% to 0.5%, Mn: 0% to 0.2%, Sr: 0% to 0.5%, Sb: 0% to 0.5% , Pb: 0% to 0.5%, with the balance being Mg and impurities, and the zinc content and the aluminum content in the chemical component are atomic% and satisfy 25% ⁇ Zn + Al
  • the calcium content, the yttrium content, the lanthanum content, and the cerium content in the chemical component satisfy at least 0.3% ⁇ Ca + Y + La + Ce ⁇ 3.5% in atomic%.
  • the silicon content, the titanium content, and the chromium content in the chemical component are in atomic% and satisfy 0.005% ⁇ Si + Ti + Cr ⁇ 0.5%, according to (6) or (7)
  • a method for producing a quasicrystal-containing plated steel sheet (9)
  • the zinc content and the aluminum content in the chemical component are atomic% and satisfy 30% ⁇ Zn + Al ⁇ 50% and 3.0 ⁇ Zn / Al ⁇ 12.0. 6.
  • the plating step is a step of immersing the steel sheet in the molten plating alloy, an oxide in the molten plating alloy is 1 g / L or less, and the steel sheet is plated in the molten state.
  • the oxygen concentration in the atmosphere when immersed in the alloy is 100 ppm or less by volume, and the temperature of the molten plating alloy is 10 ° C. to 100 ° C. higher than the liquidus temperature of the plating alloy, 10.
  • the method for producing a quasi-crystal-containing plated steel sheet according to any one of (6) to (9), wherein the time immersed in the molten plated alloy is 1 second to 10 seconds.
  • the plating alloy in the molten state is brought into contact with at least one surface of the steel plate in a state where the surface temperature of the steel plate on which the plating alloy is disposed is higher than a center temperature, and the plating
  • the cooling step is a step of submerging cooling the plating alloy immediately after the reheating.
  • the quasi-crystal-containing plated steel sheet and the quasi-crystal-containing plated steel sheet having improved corrosion resistance and sacrificial corrosion resistance required when used in various fields such as building materials, automobiles, and home appliances. It is possible to provide a manufacturing method.
  • FIG. 3 is an explanatory view schematically showing a quasicrystalline phase at a steel plate-metal coating layer interface of the quasicrystal-containing plated steel plate according to the same embodiment.
  • the metal coating layer having a specific chemical component that is, the plating layer
  • the metal coating layer is simply referred to as a mother steel sheet (hereinafter simply referred to as a steel sheet) It is also called “steel plate”).
  • the steel plate that is the base material of the quasi-crystal-containing plated steel plate according to this embodiment is not particularly limited.
  • steel plates include various steel plates such as Al killed steel, extremely low carbon steel, high carbon steel, various high tensile steels, Ni, Cr-containing steel, and the like.
  • steel plate manufacturing conditions such as the base steel plate manufacturing method, steel strength, hot rolling method, pickling method, cold rolling method and the like. That is, there are no particular restrictions on the manufacturing conditions and materials of the steel sheet used as the base material of the quasicrystal-containing plated steel sheet.
  • the metal coating layer according to the present embodiment is an alloy that exhibits a thin film shape and secures adhesion to a steel plate, and has a role of preventing corrosion and imparting a function to the base steel plate.
  • the performance such as material strength and rigidity of the base steel plate is not impaired. That is, the quasicrystal-containing plated steel sheet according to the present embodiment is a composite material in which two kinds of metal alloy materials, ie, a steel sheet and a metal coating layer, are combined.
  • required by the metal coating layer of the plated steel plate which concerns on this embodiment first is demonstrated in detail.
  • the metal coating layer of the quasicrystalline plated steel sheet according to this embodiment is required to have excellent corrosion resistance. Corrosion resistance performance is divided into corrosion resistance and sacrificial corrosion resistance.
  • the corrosion resistance of the metal coating layer is generally the corrosion resistance of the metal coating layer itself, and is often evaluated by the weight loss of the metal coating layer after a certain period of time in various corrosion tests.
  • this corrosion weight loss is small, it means that the metal coating layer as a protective film for the base steel plate remains for a long time, that is, the corrosion resistance is excellent.
  • the corrosion resistance generally tends to be higher for Zn than Mg and higher for Al than Zn.
  • sacrificial anticorrosive property of the metal coating layer refers to the action of protecting the base steel plate by corroding the surrounding metal coating layer instead of the steel plate when the base steel plate is exposed to a corrosive environment for some reason. It is. When evaluated using a pure metal, the sacrificial anticorrosive property is high for metals that are electrically base and easily corroded, and generally tend to be higher in Zn than Al and higher in Mg than Zn.
  • the Zn—Mg alloy-plated steel sheet which is also focused on the quasi-crystal-containing plated steel sheet according to the present embodiment, is excellent in sacrificial corrosion resistance because it contains a large amount of Mg in the metal coating layer.
  • the subject of such Zn—Mg alloy-plated steel sheet is how to reduce the corrosion weight loss of the metal coating layer, that is, how to improve the corrosion resistance of the metal coating layer.
  • the present inventor examined the constituent phase of the metal structure of the metal coating layer in order to minimize the corrosion weight loss of the metal coating layer in the Zn—Mg alloy plated steel sheet. As a result, it has been found that when the quasicrystalline phase is contained in a predetermined form in the metal coating layer, the corrosion resistance is dramatically improved.
  • the main feature of the plated steel sheet according to this embodiment is the metal structure of the metal coating layer.
  • the metal coating layer of the quasicrystal-containing plated steel sheet according to the present embodiment contains the quasicrystalline phase as described above, the corrosion resistance is dramatically improved as compared with the metal coating layer not containing the quasicrystalline phase.
  • the metal coating layer of the quasicrystal-containing plated steel sheet according to the present embodiment contains a large amount of Mg, it also has excellent sacrificial anticorrosive properties for the steel sheet. That is, the quasicrystal-containing plated steel sheet according to this embodiment includes an ideal metal coating layer that is excellent in both corrosion resistance and sacrificial corrosion resistance.
  • an atomic ratio is used instead of a mass ratio.
  • the atomic ratio is used because attention is paid to the quasicrystalline phase. That is, in the following description, “%” indicating a chemical component means “atomic%” unless otherwise specified.
  • the quasicrystal-containing plated steel sheet according to this embodiment has a metal coating layer located on at least one surface of the steel sheet.
  • the chemical composition of the metal coating layer is atomic%, Zn: 20% to 60%, Al: 0.3% to 15.0%, Ca: 0% to 3.5%, Y: 0% -3.5%, La: 0% -3.5%, Ce: 0% -3.5%, Si: 0% -0.5%, Ti: 0% -0.5%, Cr: 0% 0.5%, Fe: 0% to 2.0%, Co: 0% to 0.5%, Ni: 0% to 0.5%, V: 0% to 0.5%, Nb: 0% -0.5%, Cu: 0% -0.5%, Sn: 0% -0.5%, Mn: 0% -0.2%, Sr: 0% -0.5%, Sb: 0% 0.5%, Pb: 0% to 0.5%, with the balance being Mg and impurities.
  • the Zn content of the metal coating layer is set to 20% to 60%.
  • the Zn content is less than 20%, a quasicrystalline phase cannot be generated in the metal coating layer.
  • Zn content exceeds 60%, a quasicrystalline phase cannot be produced
  • the Zn content may be 25% to 52%.
  • the Zn content is more preferably 30% to 45%.
  • the Zn content is preferably 33% or more.
  • the composition range is such that the quasicrystalline phase easily grows as the primary crystal, and the Mg phase becomes difficult to grow as the primary crystal. That is, the phase amount (area fraction) of the quasicrystalline phase in the metal coating layer can be increased, and the Mg phase that degrades the corrosion resistance can be reduced as much as possible.
  • the Zn content is more preferably 35% or more.
  • the metal coating layer has almost no Mg phase.
  • Al is an element that improves the performance of the plating layer. Specifically, the planar corrosion resistance of the plating layer can be improved by including Al in the plating layer. Al is an element that promotes the formation of a quasicrystalline phase. In order to obtain these effects, the Al content of the metal coating layer is set to 0.3% or more. On the other hand, when a large amount of Al is contained in the metal coating layer, red rust is likely to be generated, and a quasicrystalline phase is hardly generated, resulting in a decrease in corrosion resistance. Therefore, the upper limit of the Al content of the metal coating layer is set to 15.0%.
  • the Zn content is a small content within the above range, it is preferable to control the Zn content and the Al content together in order to preferably form a quasicrystalline phase in the metal coating layer.
  • the Zn content and the Al content in the chemical component of the metal coating layer satisfy 25% ⁇ Zn + Al and more preferably 28.5% ⁇ Zn + Al in atomic%.
  • the upper limit of Zn + Al is not particularly limited, but the upper limit is preferably 50%.
  • Zn content and Al content as follows. That is, the Zn content and the Al content in the chemical component of the metal coating layer satisfy 30% ⁇ Zn + Al ⁇ 50% in atomic% and 3.0 ⁇ Zn / Al ⁇ 12.0. It is preferable to do.
  • a quasicrystalline phase is preferentially generated in the cooling process, and a quasicrystalline phase is generated in a preferable area fraction in the metal coating layer.
  • a quasicrystalline phase is preferably generated in the metal coating layer in an area fraction of about 30 to 70% with respect to the entire metal coating layer.
  • the quasicrystalline phase in the present embodiment has a crystal structure mainly composed of Zn and Mg, and the substitution of Al with Zn promotes the generation of the quasicrystalline phase. It is considered that there is an optimum value for the Al substitution amount.
  • the quasicrystalline phase is preferably generated in the metal coating layer, the corrosion resistance particularly in the processed portion is improved, and the period until the red rust of the base iron is increased. This effect is presumed to be due to the quasicrystalline phase being preferably dispersed in the metal coating layer by strictly controlling the contents of Zn and Al.
  • Zn + Al indicates the total content of Zn content and Al content.
  • Zn / Al indicates the ratio of Zn content to Al content (Zn content / Al content).
  • Mg (magnesium) is a main element constituting the plating layer and is an element that further improves sacrificial corrosion resistance. Mg is an important element that promotes the formation of a quasicrystalline phase. In this embodiment, it is not necessary to prescribe
  • the Mg content may be more than 25% and less than 79.7%, preferably 30% or more and 65% or less.
  • the Mg content is 79.7% or more, an Mg phase is formed in the metal coating layer, and the corrosion resistance is lowered.
  • the Mg content is 25% or less, a product other than the quasicrystal can be generated, so that the amount of the quasicrystal phase is reduced and the corrosion resistance is lowered.
  • the metal coating layer (plating layer) of the quasicrystal-containing plated copper plate according to the present embodiment contains impurities.
  • an impurity is mixed from the raw materials of steel and a plating alloy, a manufacturing environment, etc., when manufacturing the quasi-crystal containing plated steel plate concerning this embodiment industrially, for example, C (carbon), N Meaning elements such as (nitrogen), O (oxygen), P (phosphorus), S (sulfur), Cd (cadmium). Even if these elements are contained as impurities by about 0.1%, the above effects are not impaired.
  • the metal coating layer of the plated steel sheet according to the present embodiment is replaced with a part of the remaining Mg, Ca, Y, La, Ce, Si, Ti, Cr, Fe, Co, Ni, V, Nb, Cu , Sn, Mn, Sr, Sb and Pb, at least one selected component may be further contained. What component should be included among these selected components may be appropriately determined according to the purpose. Therefore, it is not necessary to limit the lower limit of these selection components, and the lower limit may be 0%.
  • the Ca content of the metal coating layer may be 0% to 3.5%
  • the Y content may be 0% to 3.5%
  • the La content may be 0% to 3.5%
  • the Ce content may be 0% to 3.5%. More preferably, regarding the Ca content, the Y content, the La content, and the Ce content, the lower limit may be independently 0.3% and the upper limit may be 2.0%.
  • a plating bath having a high Mg content can be maintained without being oxidized in the atmosphere.
  • Ca, Y, La, and Ce are easily oxidizable elements and may adversely affect the corrosion resistance, so the upper limit of the content of Ca, Y, La, and Ce is 3. 5% is preferable. That is, it is preferable that the Ca content, the Y content, the La content, and the Ce content in the chemical component of the metal coating layer satisfy 0.3% ⁇ Ca + Y + La + Ce ⁇ 3.5% in atomic%.
  • “Ca + Y + La + Ce” indicates the total content of Ca content, Y content, La content, and Ce content.
  • the total content of Ca, Y, La, and Ce is preferably 0.3% or more and 2.0% or less. These elements are considered to be substituted for Mg constituting the quasicrystalline phase. However, when these elements are contained in a large amount, the generation of the quasicrystalline phase may be inhibited. By containing these elements in an appropriate content, the red rust suppressing effect of the quasicrystalline phase and other phases is improved. This effect is presumed to be caused by the elution timing of the quasicrystalline phase affecting the retention of white rust.
  • the above effects can be obtained relatively large by the inclusion of Ca, La, or Ce.
  • the above-mentioned effect obtained by the inclusion of Y is small as compared with Ca, La, and Ce. It is presumed that Ca, La, and Ce are more easily oxidized than Y and are related to highly reactive elements.
  • EDX Electronic X-ray Spectroscopy
  • Ca, La, and Ce tend to be detected from quasicrystals at a concentration higher than the concentration. That is, it is not always necessary to include Y in the metal coating layer. When Y is not contained in the metal coating layer, it may be 0.3% ⁇ Ca + La + Ce ⁇ 3.5%, or 0.3% ⁇ Ca + La + Ce ⁇ 2.0%. “Ca + La + Ce” indicates the total content of Ca content, La content, and Ce content.
  • the Al content, the Ca content, the La content, the Y content, and the Ce content in the chemical component of the metal coating layer satisfy 6.0% ⁇ Al + Ca + La + Y + Ce ⁇ 18.5% in atomic%. It is more preferable that 6.5% ⁇ Al + Ca + La + Y + Ce ⁇ 18.5% is further satisfied.
  • the total content of Al, Ca, La, Y, and Ce satisfies the above conditions, and further, at a cooling rate of 500 ° C./second or more and 2000 ° C./second or less from the molten state or the coexistence state of the precipitated phase and the liquid phase.
  • Si silicon: 0% to 0.5%
  • Ti titanium
  • Cr chromium
  • At least one element selected from Si, Ti, and Cr may be contained as necessary in order to preferably form a quasicrystalline phase in the plating layer.
  • Si is considered to be the starting point (nucleus) of the formation of a quasicrystalline phase by combining with Mg to form fine Mg 2 Si.
  • the Si content of the metal coating layer may be 0% to 0.5%
  • the Ti content may be 0% to 0.5%
  • the Cr content may be 0% to 0.5%. More preferably, regarding the Si content, Ti content, and Cr content, the lower limit may be independently 0.005% and the upper limit may be 0.1%.
  • Si + Ti + Cr indicates the total content of Si content, Ti content, and Cr content.
  • Co, Ni, V, and Nb are elements having effects equivalent to those of the above-described Si, Ti, and Cr.
  • the Co content is 0% to 0.5%
  • the Ni content is 0% to 0.5%
  • the V content is 0% to 0.5%
  • the Nb content is It may be 0% to 0.5%.
  • the lower limit may be 0.05% and the upper limit may be 0.1%.
  • these elements are less effective in improving the corrosion resistance than Si, Ti, and Cr.
  • an element constituting the steel plate may be mixed from the steel plate as the base material.
  • the metal coating layer may contain a certain amount of Fe.
  • Fe may be contained around 2.0% as a chemical component of the entire metal coating layer.
  • Fe that has diffused into the metal coating layer often reacts with Al or Zn near the interface between the steel sheet and the metal coating layer to produce an intermetallic compound. Therefore, the possibility that the contained Fe affects the corrosion resistance of the plating layer is small. Therefore, the Fe content of the metal coating layer may be 0% to 2.0%.
  • elements constituting the steel sheet diffused to the metal coating layer may affect the corrosion resistance of the plating layer. The nature is small.
  • the Cu content of the metal coating layer may be 0% to 0.5% and the Sn content may be 0% to 0.5%. More preferably, regarding the Cu content and the Sn content, the lower limit may be independently 0.005% and the upper limit may be 0.4%.
  • Mn (manganese): 0% to 0.2% high-strength steel (high-strength steel) has come to be used as a steel plate that is a base material of a quasicrystal-containing plated steel plate.
  • high-strength steel high-strength steel
  • elements such as Si and Mn contained in the high-tensile steel may diffuse into the metal coating layer.
  • Si and Mn Mn does not have the above-described effects of Si.
  • the Mn content of the metal coating layer may be 0% to 0.2%. More preferably, regarding the Mn content, the lower limit may be 0.005% and the upper limit may be 0.1%.
  • Sr, Sb, and Pb are elements that improve the plating appearance, and are effective in improving the antiglare property.
  • the Sr content of the metal coating layer may be 0% to 0.5%
  • the Sb content may be 0% to 0.5%
  • the Pb content is 0% to 0.00%. It may be 5%.
  • the lower limit may be independently 0.005% and the upper limit may be 0.4%.
  • the metal coating layer disclosed in the present embodiment has a metallic luster on the surface. However, by incorporating these elements in the above composition range, the metallic luster is lost and an antiglare effect can be obtained.
  • the chemical composition of the metal coating layer is ICP-AES (Inductively Coupled Plasma Atomic Emission Spectrometry) or ICP-MS (Inductively Coupled Plasma Mass). Measurement can be performed using a known analysis technique such as Spectrometry).
  • the quasicrystal-containing plated steel sheet is immersed in 10% hydrochloric acid to which an inhibitor is added for about 1 minute, the metal coating layer is peeled off, and a solution in which the metal coating layer is dissolved is prepared.
  • the obtained solution can be analyzed by ICP-AES, ICP-MS or the like to obtain the chemical component as the overall average of the metal coating layer.
  • a metal coating layer having a chemical component substantially equivalent to the chemical component of the hot dipping bath is formed. Therefore, for elements that can neglect the interdiffusion between the steel sheet and the metal coating layer, the chemical component of the plating bath used may be measured, and the obtained measurement value may be substituted as the chemical component of the metal coating layer.
  • a small ingot is collected from the plating bath, drill powder is collected, and a solution in which the drill powder is dissolved in an acid is prepared. The obtained solution is analyzed by ICP or the like to obtain the chemical components of the plating bath. You may use the measured value of the chemical component of the obtained plating bath as a chemical component of a metal coating layer.
  • the metal coating layer of the quasicrystal-containing plated steel sheet according to the present embodiment includes a quasicrystalline phase.
  • the metal coating layer is preferably composed of a quasicrystalline phase and a ternary eutectic phase.
  • the magnesium content, zinc content, and aluminum content contained in the quasicrystalline phase satisfy 0.50 ⁇ Mg / (Zn + Al) ⁇ 0.83 in atomic%.
  • a quasicrystalline phase is present at the interface between the steel sheet and the metal coating layer, and the quasicrystalline phase having a minor axis of 0.2 ⁇ m to 2 ⁇ m occupies 90% or more of the interface.
  • the size of 95% or more of the quasicrystalline phase is 0.2 ⁇ m to 5 ⁇ m in terms of the equivalent circle diameter. .
  • the quasicrystal-containing plated steel sheet according to the present embodiment is characterized in that the metal coating layer includes a quasicrystalline phase as a metal structure, as described in detail below. Therefore, in the following, the quasicrystalline phase will be described first.
  • the quasicrystalline phase is a quasicrystalline phase in which the Mg content, Zn content and Al content contained in the grains of the quasicrystalline phase satisfy 0.50 ⁇ Mg / (Zn + Al) ⁇ 0.83 in atomic%.
  • Mg: (Zn + Al) which is the ratio of Mg atoms to the sum of Zn atoms and Al atoms, is defined as a quasicrystalline phase of 3: 6 to 5: 6.
  • the chemical component of the quasicrystalline phase is quantitatively analyzed by TEM-EDX (Transmission Electron Microscope-Energy Dispersive X-ray Spectroscopy), or preferably by EPMA (Electron Probe Micro-Analyzer). Note that it is not easy to define a quasicrystal with an accurate chemical formula like an intermetallic compound. This is because the quasicrystalline phase cannot define a repetitive lattice unit like the unit lattice of a crystal, and furthermore, it is difficult to specify the atomic positions of Zn and Mg. For reference, when the quasicrystalline phase is measured by TEM-EDX, the quasicrystalline phase is detected in a state in which the Zn ratio is higher and the Mg ratio is lower than the Mg 51 Zn 20 phase.
  • TEM-EDX Transmission Electron Microscope-Energy Dispersive X-ray Spectroscopy
  • EPMA Electron Probe Micro-Analyzer
  • chemical components of the metal phase other than the quasicrystalline phase contained in the metal coating layer can also be identified by quantitative analysis using TEM-EDX, quantitative analysis using EPMA mapping, or the like.
  • the focused metal phase may be determined as a quasicrystalline phase from the measurement results of EPMA and EDX.
  • the configuration of the metal structure of the metal coating layer according to the present embodiment will be described in detail.
  • the metal structure of the metal coating layer further containing a ternary eutectic phase and a quasicrystalline phase and not containing an amorphous phase will be described.
  • the metal structure of the metal coating layer is a quasicrystalline phase. Including, the phase other than the quasicrystalline phase is not limited.
  • FIG. 1 is an optical micrograph of a metal coating layer of a quasicrystal-containing plated steel sheet according to the present embodiment, obtained by observing a cut surface whose cutting direction is parallel to the plate thickness direction of the quasicrystal-containing plated steel sheet. It is.
  • This cross-sectional structure photograph is a dark field image obtained by observing the cut surface with an optical microscope.
  • the quasicrystal-containing plated steel sheet 10 has a steel sheet 11 as a base material and a metal coating layer 13 located on the steel sheet 11.
  • a metal coating layer 13 shown in FIG. 1 when an electron beam diffraction image by TEM is taken for the portion of the alloy phase surrounded by the closed curve, a diffraction image as shown in FIG. 2 can be obtained.
  • FIG. 2 is an electron beam diffraction image obtained from the portion of the alloy phase surrounded by the closed curve in FIG. In the electron diffraction pattern shown in FIG.
  • the metal coating layer 13 has a quasicrystalline phase that exists as a region surrounded by a closed curve.
  • the portion other than the quasicrystalline phase is mainly a Zn / Al / MgZn 2 ternary eutectic phase, and no amorphous phase is present.
  • the presence of such a ternary eutectic phase could be confirmed by analyzing an electron beam diffraction image obtained from a portion of the metal coating layer 13 other than the quasicrystalline phase.
  • the presence of the ternary eutectic phase or the absence of the amorphous phase can be confirmed by the electron beam diffraction image as described above, but it is confirmed by XRD (X-Ray Diffractometer). It is also possible.
  • Mg may be blackened and impair the appearance when it is present in a moisture environment, it is preferable that no Mg phase is present in the metal coating layer 13.
  • FIG. 3 is an explanatory view schematically showing a quasicrystalline phase at the steel plate-metal coating layer interface of the quasicrystal-containing plated steel plate according to the present embodiment.
  • the quasicrystalline phase present at the interface is a quasicrystalline phase formed by submerging cooling the metal coating layer 13 in a molten state or a coexistence state of a precipitated phase and a liquid phase as described in detail below.
  • a rapid cooling process called submerged cooling creates a temperature gradient in the thickness direction, and the crystal grows from an energetically unstable interface as a starting point, resulting in a substantially rectangular fine crystal whose longitudinal direction is the thickness direction.
  • the substantially rectangular quasicrystalline phase has a minor axis of 0.2 ⁇ m to 2 ⁇ m.
  • the portion where the quasicrystalline phase having a minor axis of 0.2 ⁇ m to 2 ⁇ m is deposited occupies 90% or more of the interface.
  • This quasicrystalline phase is precipitated by a rapid cooling treatment, but the area of the interface where precipitation is possible is limited, so that the minor diameter of the crystal grains tends to be limited as described above. And the metal coating layer 13 will show the outstanding corrosion resistance because the ratio which occupies for the interface in the quasicrystalline phase of the short diameter of the said range among the quasicrystalline phases precipitated in the interface becomes the said range.
  • the ratio of the quasicrystalline phase in the interface is the cross-sectional structure observation as shown in FIG. 1, and the size of the interface in an arbitrary plurality of fields (10 fields) (that is, schematically shown in FIG. 3).
  • the length of the interface S in such a cross-sectional structure photograph), and the sum of the sizes of the interface where the quasicrystalline phase of the short diameter in the above range is precipitated in this field of view (S 1 + S 2 + S 3 in FIG. 3 ) Respectively.
  • the value obtained by ⁇ (S 1 + S 2 + S 3 ) / S ⁇ ⁇ 100 (%) is a quasicrystalline phase having a short diameter in the above range in this visual field.
  • the proportion of Such a process is similarly performed for a plurality of focused visual fields (10 visual fields), and the average of the obtained values is the ratio of the quasicrystalline phase having the short diameter in the above range at the interface in the present embodiment. .
  • the quasicrystalline phase having a minor axis size of less than 0.2 ⁇ m as shown in FIG. 3 is slightly generated even under the production conditions of the present embodiment, and there is no problem with the corrosion resistance and the like.
  • a quasicrystalline phase whose minor axis exceeds 2 ⁇ m is basically difficult to form at an interface having many precipitation start points at a cooling rate of 500 ° C./second or more.
  • the minor axis of the quasicrystalline phase on which the interface precipitates is preferably 0.5 ⁇ m to 2 ⁇ m. That is, it is preferable that the proportion of the quasicrystalline phase precipitated at the interface in the quasicrystalline phase having a minor axis of 0.5 ⁇ m to 2 ⁇ m is 90% or more.
  • the quasicrystalline phase since the quasicrystalline phase is present at the interface without any break, it becomes a final stage barrier that inhibits corrosion of the plating layer eroding from the surface.
  • the upper limit value of the ratio of the quasicrystalline phase having the short axis in the above range is not particularly defined at the interface, but is preferably 97% or less, for example, and more preferably as it is closer to 100%.
  • the quasicrystalline phase having a relatively small size is 95% by number or more of the number of remaining quasicrystalline phases excluding the quasicrystalline phase existing at the interface in the quasicrystalline phase existing in the metal coating layer 13. Occupy.
  • Such a relatively small quasicrystalline phase has an equivalent circle diameter (equivalent circle diameter) and a size of 0.2 ⁇ m to 5 ⁇ m. That is, among the remaining quasicrystalline phases, quasicrystalline phases having an equivalent circle diameter of 0.2 ⁇ m to 5 ⁇ m occupy 95% by number.
  • the quasicrystalline phase having an equivalent circle diameter of less than 0.2 ⁇ m is slightly generated even under the manufacturing conditions of this embodiment, and the corrosion resistance and the like are increased. There is no problem with the size.
  • the equivalent circle diameter of a relatively small quasicrystalline phase exceeds 5 ⁇ m, the surrounding liquid phase composition where the quasicrystalline phase is precipitated becomes Mg-rich, and an Mg phase that adversely affects corrosion resistance is likely to be generated. Therefore, it is not preferable.
  • the average equivalent circular diameter of the quasicrystalline phase having a relatively small size is preferably 0.5 ⁇ m to 3 ⁇ m. That is, among the remaining quasicrystalline phases, it is preferable that 95% by number of quasicrystalline phases having an equivalent circle diameter of 0.5 ⁇ m to 3 ⁇ m.
  • the method for measuring the equivalent circle diameter is not particularly limited, and can be measured by performing known image analysis when observing the cross-sectional structure.
  • the ratio of the number of quasicrystalline phases having a relatively small size having an equivalent circle diameter of 0.2 ⁇ m to 5 ⁇ m as described above is less than 95% by number of the remainder excluding the quasicrystalline phase present at the interface. In some cases, sufficient corrosion resistance cannot be obtained, which is not preferable.
  • the ratio of the number of quasicrystalline phases having a relatively small size is preferably 98% by number or more of the balance excluding the quasicrystalline phase present at the interface.
  • the upper limit of the ratio of the number of quasicrystalline phases having a relatively small size is not particularly limited, but is preferably 100% by number or less.
  • the ratio of the number of quasicrystalline phases having an equivalent circle diameter of 0.2 ⁇ m to 5 ⁇ m is obtained by performing cross-sectional structure observation and counting the number of remaining quasicrystalline phases excluding the quasicrystalline phase existing at the interface. Of these, the ratio of the number of quasicrystalline phases with the corresponding equivalent circle diameter is calculated. Such processing is performed in the same manner for a plurality of focused fields of view (10 fields of view), and the average of the obtained values is “a quasicrystal with an equivalent circle diameter of 0.2 ⁇ m to 5 ⁇ m in this embodiment. The ratio of the number of phases ”.
  • the coarse quasicrystalline phase located in the vicinity of the surface of the metal coating layer 13 and having an equivalent circle diameter (equivalent circle diameter) of more than 5 ⁇ m is not particularly limited.
  • the metal coating layer 13 according to the embodiment realizes excellent corrosion resistance.
  • the presence or absence of the Mg phase can be determined by TEM-EDX or SEM-EDX. Further, in the TEM diffraction image of the metal coating layer 13, if the fraction of the Mg phase crystal grains when sampling 100 or more arbitrary crystal grains is 3% or less, the metal structure of the metal coating layer 13 is Mg It can be said that the phase is not included.
  • the fraction of Mg phase crystal grains is more preferably less than 2%, and most preferably less than 1%.
  • the thickness of the metal coating layer 13 having the metal structure as described above is not particularly limited, and is generally 5 ⁇ m or more and 35 ⁇ m or less in many cases.
  • the metal structure of the metal coating layer 13 is composed of a polishing specimen, CP (Cross Section Polisher) processing, FIB (Focused Long Beam) processing, cross-sectional structure of the metal coating layer 13 by ion milling, an optical microscope, SEM, It can confirm by observing with TEM etc. and implementing various analysis processes.
  • the crystal grain size of the metal structure can be measured by SEM observation if it is a structure of 1 ⁇ m or more, but the structure and quasicrystalline phase finer than 1 ⁇ m are measured by TEM observation as described above. can do.
  • the kind of phase in the metal coating layer 13 can be confirmed by a known method such as an electron beam diffraction pattern of EPMA or TEM.
  • the metal structure of the metal coating layer 13 can be confirmed as follows. First, a quasicrystal-containing plated steel sheet is cut and a sample is taken so that a cut surface in which the plate thickness direction and the cutting direction are parallel to each other becomes an observation surface. The cut surface of the obtained sample is polished or CP processed. In the case of polishing, the polished cross section is subjected to nital etching. Thereafter, the cross section obtained with an optical microscope or SEM is observed, and a metal structure photograph is taken.
  • the chemical component of the constituent phase can be measured by analysis using EDX or EPMA as described above. It is possible to easily identify the constituent phase from the chemical analysis result.
  • the area ratio of the constituent phases can be measured by binarizing the obtained metal structure photograph by, for example, image analysis and measuring the area ratio of each part of the metal coating layer 13. Further, the equivalent circle diameter can be calculated from the areas of the obtained individual regions (constituent phases). Alternatively, the metal structure of the metal coating layer 13 may be observed by an EBSD (Electron Back Scattering Diffraction Pattern) method, the constituent phase may be identified, and the area ratio and equivalent circle diameter of the constituent phase may be obtained.
  • EBSD Electro Back Scattering Diffraction Pattern
  • the metal structure of the metal coating layer 13 is observed as follows. That is, the quasicrystal-containing plated steel sheet is cut and a thin piece sample is taken so that the cut surface in which the plate thickness direction and the cutting direction are parallel becomes the observation surface. The obtained thin piece sample is subjected to an ion milling method. Alternatively, the quasi-crystal-containing plated steel sheet is FIB-processed so that a cut surface in which the plate thickness direction and the cutting direction are parallel becomes an observation surface, and a thin piece sample is collected. A thin sample obtained using TEM is observed, and a metallographic photograph is taken. The constituent phase can be accurately identified by an electron diffraction image. Moreover, the area ratio and equivalent circle diameter of the constituent phases can be obtained by image analysis of the obtained metallographic photograph.
  • the metal coating layer 13 of the quasicrystal-containing plated steel sheet according to the present embodiment contains Zn at a certain concentration or more in the metal coating layer 13, it is possible to perform the same phosphorylation treatment, chromate treatment, and chromate-free treatment as the Zn-based plated steel sheet. It is. Furthermore, the coating on the chemical conversion treatment film formed by such chemical conversion treatment can also be carried out in the same manner as with the Zn-based plated steel sheet. Moreover, the quasicrystal-containing plated steel sheet according to the present embodiment can be used as an original sheet of a laminated steel sheet.
  • the formation of the metal coating layer is not particularly limited, and in addition to the hot dipping method, a thermal spraying method, a sputtering method, an ion plating method, a vapor deposition method, an electroplating method, and the like can be applied.
  • a thermal spraying method in order to form a metal coating layer having a thickness generally used in automobiles or the like, the hot dipping method is most preferable in terms of cost.
  • a temperature gradient is given during plating, only the hot dipping method can be applied.
  • a plurality of plating processes may be performed under different conditions.
  • the metal coating layer is subjected to a heat treatment described later to control the phase structure in the metal coating layer to form an appropriate quasicrystalline phase. It is also preferable because it is advantageous in terms of cost.
  • the hot dipping method is advantageous because it can utilize the cooling process of the molten plating alloy as a heat treatment.
  • a metal coating layer having a specific composition is formed on the steel sheet surface by vapor deposition or the like, and then the steel sheet is charged into a heating furnace and heated to melt only the surface metal coating layer. By performing the cooling process, it is possible to form a metal coating layer similar to the metal coating layer by the hot dipping method.
  • the chemical components are atomic%, Zn: 20% to 60%, Al: 0.3% to 15.0%, Ca: 0% to 3. 5%, Y: 0% to 3.5%, La: 0% to 3.5%, Ce: 0% to 3.5%, Si: 0% to 0.5%, Ti: 0% to 0. 5%, Cr: 0% to 0.5%, Fe: 0% to 2.0%, Co: 0% to 0.5%, Ni: 0% to 0.5%, V: 0% to 0. 5%, Nb: 0% to 0.5%, Cu: 0% to 0.5%, Sn: 0% to 0.5%, Mn: 0% to 0.2%, Sr: 0% to 0. 0.
  • the plating process may include the above chemical components on at least one surface of various steel plates such as Al killed steel, ultra-low carbon steel, high carbon steel, various high-tensile steels, Ni, Cr-containing steel, and the like. This is a step of disposing a molten plating alloy to be contained.
  • the plated alloy in the molten state is such that the calcium content, the yttrium content, the lanthanum content, and the cerium content in the chemical component are atomic%, and 0.3 ⁇ Ca + Y + La + Ce ⁇ 3. It is preferable to satisfy 5%. Moreover, it is preferable that the silicon content, the titanium content, and the chromium content in the chemical components satisfy 0.005% ⁇ Si + Ti + Cr ⁇ 0.5% in atomic%. Further, it is preferable that the zinc content and the aluminum content in the chemical component are 30% ⁇ Zn + Al ⁇ 50% and 3.0 ⁇ Zn / Al ⁇ 12.0 in atomic%.
  • the material of the plating alloy is produced, it is preferable to prepare using a pure metal (purity 99% or more) as the alloy material.
  • a predetermined amount of an alloy metal is mixed so as to have the above-mentioned plating layer composition, and completely melted using a high frequency induction furnace, an arc furnace, or the like in a vacuum or an inert gas replacement state to obtain an alloy.
  • the said alloy mixed with the predetermined component is melt
  • the means for disposing the molten plating alloy on at least one surface of the steel sheet is not particularly limited, and it is possible to use a known plating method as described above, It is preferable to use a hot dipping method.
  • the oxide in the molten plating alloy is 0 g / L to 1 g / L, and the steel sheet is immersed in the molten plating alloy.
  • the oxygen concentration in the atmosphere is 0 ppm to 100 ppm by volume
  • the temperature of the molten plating alloy is 10 ° C. to 100 ° C. higher than the liquidus temperature (so-called melting point) T melt of the plating alloy, and the steel plate is in the molten state
  • the time immersed in the plating alloy is preferably 1 to 10 seconds.
  • the oxide in the molten plating alloy is 1 g / L or less, a quasicrystal is more preferably generated in the metal structure of the metal coating layer.
  • the oxide in the molten plating alloy is more preferably 0.1 g / l or less.
  • oxygen concentration in the molten plating alloy is 100 ppm or less by volume, oxidation of the molten plating alloy can be more preferably suppressed. Such oxygen concentration is more preferably 50 ppm or less by volume ratio.
  • the metal coating layer is preferably formed on the surface of the steel plate. More preferably, the temperature of the molten plating alloy is higher by 30 ° C. to 50 ° C. than T melt . Further, when the time during which the steel sheet is immersed in the molten plating alloy is 1 to 10 seconds, the metal coating layer is more preferably formed on the surface of the steel sheet. The immersion time is more preferably 2 seconds to 4 seconds.
  • the plating tank for holding the molten plating alloy is preferably made of steel, and dross in the molten plating alloy is preferably discharged by a metal pump.
  • a metal pump When such a plating tank is made of steel, inclusions in the molten plating alloy (that is, the plating bath) are reduced, so that a quasicrystal is more preferably generated in the metal structure of the metal coating layer.
  • the plating tank is made of steel, the wear on the inner wall of the plating tank can be suppressed as compared with the case where the plating tank is made of ceramic.
  • the dross in the plating bath is discharged by a metal pump, inclusions in the plating bath are reduced, so that quasicrystals are more preferably generated in the metal structure of the metal coating layer.
  • the value of the liquidus temperature T melt of the plating alloy can be specified by a known method.
  • Liang et al. Liang, P., Tarfa, T., Robinson, J. et al. A., Wagner, S., Ochin, P., Harmelin, MG, Seifert, HJ, Lukas, HL, Aldinger, F., “Experimental Investigation and Thermodynamic Calculation -Zn System ", Thermochim. Acta, 314, 87-110 (1998)
  • the value of T melt can be almost estimated from the ratio of Zn, Al, and Mg contained in the metal coating layer.
  • the steel sheet having the molten plated alloy disposed on the surface is naturally cooled while being transported through the production line, but in the method for producing a quasicrystal-containing plated steel sheet according to the present embodiment, After the plating step as described above, a reheating step is performed.
  • Such a reheating step is a step of reheating the plating alloy disposed on the surface of the steel plate to a temperature of 400 ° C. or higher and 550 ° C. or lower.
  • the plating alloy disposed on the surface of the steel sheet is again in a molten state (complete liquid phase) or a coexistence state of a quasicrystalline phase and a liquid phase.
  • the complete liquid phase is most preferable, but even if it is not the complete liquid phase, it is higher than about 350 ° C where phases other than the quasicrystalline phase represented by the Mg phase coexist, and the remaining quasicrystalline phase is dispersed and refined. If it is 400 degreeC or more to do, there is no problem as a minimum temperature of reheating.
  • the temperature at which the plating alloy is reheated is less than 400 ° C.
  • the composition before reheating remains as it is, and it is not preferable because the structure shown in the present embodiment is not easily generated even when rapidly cooled.
  • the temperature at which the plating alloy is reheated exceeds 550 ° C.
  • an Fe—Al alloy is formed at the interface between the steel sheet and the plating layer (metal coating layer), which is not preferable.
  • the temperature at which the plating alloy is reheated is more preferably 430 ° C. to 510 ° C.
  • the plating alloy mainly composed of Mg and Zn is completely different from the melting point of the plating alloy mainly composed of Mg and Zn and the melting point of the steel plate as the base material, so those skilled in the art can optimize the temperature and time. It is possible to implement easily. By heating at the above temperature, the plating alloy mainly composed of Mg and Zn is completely melted, and the base material is not melted.
  • a cooling step is performed following the reheating step.
  • This cooling step is a step in which the reheated plating alloy is submerged and cooled at a cooling rate of 500 ° C./second or more and 2000 ° C./second or less from a molten state or a coexistence state of a precipitation phase and a liquid phase. .
  • a metal coating layer having a metal structure as shown in FIG. 1 can be formed.
  • the cooling rate is less than 500 ° C./second, the plating alloy is not sufficiently cooled, and the metal coating layer according to this embodiment cannot be formed.
  • a cooling rate exceeding 2000 ° C./second is not adopted in this embodiment because the amorphous phase starts to form.
  • the cooling rate in the cooling step is more preferably 800 ° C./second to 1500 ° C./second.
  • immediately after reheating for example, 0.1 seconds to 0.5 seconds (preferably 0.1 seconds after reheating).
  • the plating alloy is preferably submerged and cooled within a second to 0.3 second).
  • FIG. 4 is a cross-sectional structure photograph of a metal coating layer obtained when a plated alloy in a molten state or a coexistence state of a precipitation phase and a liquid phase is cooled by gas cooling instead of submerged cooling.
  • gas cooling rather than submerged cooling, the cooling rate as described above is not realized and cooling becomes insufficient.
  • FIG. 4 a very large structure is generated in the metal coating layer, and the metal coating layer including a fine quasicrystalline phase as shown in FIG. 1 is not formed.
  • FIG. 5 is a cross-sectional structure photograph of a metal coating layer obtained when a plating alloy in a molten state or a coexistence state of a precipitation phase and a liquid phase is cooled by submerging cooling after gas cooling.
  • a quasicrystalline phase exceeding 5 ⁇ m is generated, or the particle size is unevenly distributed depending on the position.
  • the metal coating layer containing a fine quasicrystalline phase as shown in 1 is not formed.
  • the metal coating layer according to this embodiment as shown in FIG. 1 is formed only by submerging cooling the reheated plating alloy from the molten state or the coexistence state of the precipitated phase and the liquid phase. It becomes possible to do.
  • the method for producing a quasicrystal-containing plated steel sheet according to the present embodiment by performing at least one of the methods shown in 1) and 2) below, fine, elongated and many quasicrystalline phases are obtained,
  • the metal coating layer according to the present embodiment is easily formed.
  • 1) In the cooling step a method of cooling the reheated plating alloy in a state where the surface temperature of the steel sheet is higher than the center temperature (for example, a method in which the surface temperature of the steel sheet is higher than the center temperature immediately before cooling).
  • the plating step in a state where the surface temperature of the steel sheet on which the plating alloy is disposed is higher than the center temperature, at least one surface of the steel sheet is brought into contact with the molten plating alloy to form a plating alloy (metal coating layer).
  • Method of disposing for example, a method in which the surface temperature of the steel sheet is higher than the central temperature immediately before contacting the molten plated alloy
  • the center temperature of a steel plate shows the temperature of the center part of a plate
  • the method 1) is an effective method for generating the metal coating layer according to this embodiment.
  • a temperature gradient with the maximum temperature at the interface between the steel sheet and the plating alloy (metal coating layer) occurs due to cooling from the outside of the metal coating layer and cooling from the center of the steel sheet,
  • the crystal grows starting from the interface that is unstable in terms of energy, it tends to be a fine crystal having a substantially rectangular shape whose longitudinal direction is the plate thickness direction. For this reason, when the method 1) is performed, the metal coating layer according to the present embodiment is easily formed.
  • the method 2) is an auxiliary method compared to the method 1).
  • the method of 2) although there is an unclear part in the mechanism, when the molten plating alloy is brought into contact with the surface of the steel sheet, the surface temperature of the steel sheet is set to a state higher than the center temperature so that the steel sheet and the plating are plated.
  • the alloy metal coating layer
  • the metal coating layer according to the present embodiment is easily formed.
  • the surface temperature of the steel plate provided with the plating alloy is 10 ° C. to 50 ° C. higher than the center temperature in the range of 0.2 mm to 3.2 mm which is the thickness of a normal steel plate. It is preferably 25 ° C. to 45 ° C. higher than the center temperature. If the temperature difference between the surface of the steel sheet and the central part is less than 10 ° C, the cooling from the surface of the plating alloy (metal coating layer) becomes too strong, and the temperature difference between the steel plate and the plating alloy (metal coating layer) is reduced. Crystal phase formation may be suppressed.
  • the quasicrystalline phase generation rate at the interface between the steel sheet and the plating alloy may be reduced.
  • a heating facility having a high temperature raising capability is required, which may increase the equipment cost. Therefore, when the temperature difference between the surface and the center of the steel sheet is in the range of 10 ° C. to 50 ° C., a large amount of quasicrystalline phase is generated at the interface, and the quasicrystalline phase is included in the above form in the metallographic structure of the plating layer. It becomes easy to become.
  • the surface temperature of the steel plate on which the plating alloy is disposed is 10 ° C. to 50 ° C. higher than the center temperature in the range of 0.2 mm to 3.2 mm which is the thickness of a normal steel plate. Preferably, it is 15 to 25 ° C. higher than the center temperature. If the temperature difference between the surface of the steel sheet and the center is less than 10 ° C, it is difficult to suppress the formation of iron-aluminum alloy that is initially formed at the interface between the steel sheet and the plating alloy (metal coating layer). Many grain boundaries that are quasi-crystal formation base points may be blocked.
  • the temperature difference between the surface of the steel sheet and the central part exceeds 50 ° C., as described above, it passes through the entry part (for example, the snout part) to the bath with the low temperature from the annealing furnace, and the temperature of the entry part space is It may decrease, and it may easily cause troubles such as fume generation.
  • a heating facility having a high temperature raising capability is required, which may increase the equipment cost. For this reason, when the temperature difference between the surface and the center of the steel sheet is in the range of 10 ° C. to 50 ° C., a large amount of quasicrystalline phase is generated, and the quasicrystalline phase in the metal structure of the plating alloy (metal coating layer) It becomes easy to be included in the form.
  • a method for generating a temperature difference in which the surface temperature of the steel plate is higher than the center temperature is not particularly limited. For example, only the surface region of the steel plate is preferentially heated. Then, a method of setting the surface temperature of the steel sheet to be higher than the center temperature may be adopted. Specifically, for example, a method of heating only the very surface of the steel sheet with an induction heating device (IH) may be employed. At this time, if a high-frequency induction heating device (IH) is used, a temperature difference is more easily generated. For example, when a carbon steel base steel plate is heated to 400 ° C.
  • an induction heating device IH
  • only the surface of about 30 ⁇ m at 10 kHz and about 10 ⁇ m at 200 kHz can be heated.
  • the temperature is raised in a very short time, and contact with the plating alloy in the submerged or molten state (for example, immersion of the plating alloy bath) is performed immediately after heating the surface of the steel sheet. (That is, the surface temperature of the steel plate should be higher than the center temperature immediately before cooling the plating alloy or immediately before bringing the molten plating alloy into contact with the steel plate).
  • the temperature is raised to a predetermined steel plate surface temperature within 0.5 seconds (preferably within 0.4 seconds), and the surface temperature of the steel plate is higher than the center temperature.
  • Plating alloy reheated within 0.1 to 0.5 seconds (preferably 0.1 to 0.3 seconds) after causing temperature difference (specifically after heating is stopped) It is preferable to cool (submerged cooling). Further, in the method 2), the temperature is raised to a predetermined steel plate surface temperature within 0.5 seconds (preferably within 0.4 seconds), and the target temperature at which the surface temperature of the steel plate is higher than the center temperature. After the difference is produced (specifically, after heating is stopped), the plated alloy in a molten state is applied to the steel sheet within 0.1 second to 0.4 second (preferably 0.1 second to 0.2 second). It is good to contact.
  • a heating region in a high temperature atmosphere is provided.
  • a method of passing the steel plate there is also a method of passing the steel plate there.
  • a method of heating with an induction heating device is preferable.
  • a contact-type thermocouple K-type
  • the average temperature of the entire plated alloy can be monitored at all times.
  • the temperature of the entire plating alloy at that point in the manufacturing conditions It becomes possible to monitor almost accurately. This makes it possible to precisely control the reheating process in the reheating process.
  • the surface temperature of the plating alloy may be measured by a non-contact type radiation thermometer.
  • the relationship between the surface temperature of the plating alloy and the average temperature of the entire plating alloy may be obtained by a simulation that performs heat conduction analysis. Specifically, the preheating temperature of the steel plate, the temperature of the hot dipping bath, the pulling speed of the steel plate from the plating bath, the thickness of the steel plate, the thickness of the plating alloy, the heat exchange heat between the plating alloy and the manufacturing equipment, the release of the plating alloy Based on various production conditions such as the amount of heat, the surface temperature of the plating alloy and the average temperature of the entire plating alloy are obtained. Then, what is necessary is just to obtain
  • the reheating process in the reheating process can be precisely controlled.
  • a corrosion acceleration test such as a combined cycle corrosion test or a hot water spray test can be used. By evaluating the corrosion weight loss and red rust prevention period, the superiority or inferiority of the corrosion resistance can be determined.
  • a corrosion acceleration test using a high concentration (for example, around 5%) NaCl aqueous solution.
  • a NaCl aqueous solution having a low concentration for example, 1% or less
  • Oxide in plating bath 1 g / L or less ⁇ Atmospheric oxygen concentration when steel sheet is immersed in plating bath: 100 ppm or less ⁇ Material of plating tank: steel ⁇ Plating bath immersion time: 3 seconds ⁇ Metal pump dross discharge: Existence ⁇ Reheating method: induction heater method
  • the plating bath as described above was prepared by dissolving a predetermined amount of each pure metal ingot. After covering the plating bath with a sealing box, the atmosphere was replaced with Ar gas to control the atmospheric oxygen concentration as described above.
  • a hot rolled steel sheet (carbon content: 0.2% by mass) having a thickness of 0.8 mm was used as a plated steel sheet (a steel sheet serving as a base material for the plated steel sheet).
  • the hot-rolled steel sheet was used after being cut into a size of 100 mm ⁇ 200 mm.
  • the hot-dip plating prepared as described above was formed on a hot-rolled steel plate as a base material using a batch hot-dip plating test apparatus.
  • the temperature of the plated steel plate during manufacture was measured by monitoring the surface temperature and the center temperature of the steel plate with a thermocouple at the center of the steel plate.
  • the surface of the steel sheet heated to 800 ° C. was reduced with N 2 -5% H 2 gas in a furnace with controlled oxygen concentration. After this steel sheet was air-cooled with N 2 gas and the surface temperature of the steel sheet became equal to or lower than the plating bath temperature, in some of the examples, it was rapidly heated by an induction heating device (IH) to a maximum of about 70 ° C. Was immersed in the plating bath for a predetermined time. After immersion in the plating bath, the steel sheet was pulled up at a pulling speed of 100 m / sec.
  • IH induction heating device
  • a high pressure N 2 gas or a mixed gas of H 2 and N 2 whose flow outlet was rectified by a parallel slit was sprayed to control the amount of plating adhesion (that is, the thickness of the metal coating layer).
  • the surface temperature of the steel plate was in the state 20 degreeC higher than center temperature. And in this state, the steel plate was immersed in the plating bath.
  • the plated steel sheet is moved into the induction heating device (IH) to raise the temperature up to the reheating temperature at a rate of 10 ° C./second to 200 ° C./second.
  • the temperature difference between the surface and the center was set to a predetermined temperature (indicated as “temperature difference in the reheated steel sheet” in the table).
  • the plated steel plate was immediately submerged in the water tank filled with water.
  • Samples having a plate width direction of 20 mm and a rolling direction of 15 mm were collected from arbitrary 10 locations in the manufactured plated steel sheet. These samples were immersed in a 10% aqueous HCl solution for 1 second to remove the oxide film.
  • the metallographic structure of the cut surface of each sample is observed by SEM, and the quasicrystalline phase having a minor axis of 0.2 ⁇ m to 2 ⁇ m is formed between the steel sheet and the metal coating layer.
  • Percentage at the interface (indicated in the table as “interface occupancy ratio of the short quasicrystalline phase of 0.2-2 ⁇ m”), the proportion of the quasicrystalline phase present at the interface, the quasicrystal present at the interface between the steel sheet and the metal coating layer Of the remaining quasicrystalline phase other than the phase, the proportion of the quasicrystalline phase with an equivalent circle diameter of 0.2 ⁇ m to 5 ⁇ m (represented as “the remaining occupancy ratio of the quasicrystalline phase with an equivalent diameter of 0.2 to 5 ⁇ m” in the table) was measured.
  • the equivalent circle diameter was obtained by image analysis.
  • the chemical component of the phase which comprises a metal coating layer was measured by the analysis by EPMA.
  • the metal structure was observed with an optical microscope ( ⁇ 1000 times), and a Vickers trace was given to the target portion.
  • An 8 mm square sample was cut out based on the Vickers trace. From each cut out sample, a sample for TEM observation was prepared by a cryo ion milling method.
  • the electron diffraction pattern of the main crystal grains observed was analyzed by TEM, and the quasicrystalline phase contained in the metal structure was distinguished from the other phases.
  • a structure having no specific electron diffraction image was an amorphous phase.
  • Corrosion weight loss was evaluated by a corrosion accelerated test (Combined cycle Corrosion Test: CCT) based on the JASO (M609-91) cycle. Specifically, for corrosion weight loss evaluation, a sample having a plate width direction of 50 mm and a rolling direction of 100 mm was cut out from the manufactured plated steel sheet and subjected to a corrosion acceleration test. A corrosion acceleration test (CCT) was performed using a 0.5% NaCl aqueous solution to evaluate the weight loss after 150 cycles.
  • CCT corrosion acceleration test
  • a plated steel sheet with a corrosion weight loss of less than 20 g / m 2 is judged as “Excellent”, and a plated steel sheet with a corrosion weight loss of less than 20 g / m 2 to less than 30 g / m 2 is judged as “Good”.
  • a plated steel sheet having a thickness of 30 g / m 2 or more was judged as “Poor”. “Excellent” represents the most excellent corrosion weight loss evaluation.
  • the occurrence of red rust was evaluated by the above-described corrosion acceleration test (CCT). Specifically, a corrosion acceleration test (CCT) using a 5% NaCl aqueous solution was performed using the manufactured plated steel sheet, and the number of test cycles in which a red rust of 5% or more in area% was generated on the flat portion of the plated steel sheet was investigated.
  • CCT corrosion acceleration test
  • red rust As an evaluation of occurrence of red rust, a plated steel sheet in which the red rust is not confirmed after 300 cycles is judged as “Excellent”, a plated steel sheet in which the red rust is not confirmed after 150 cycles is judged as “VeryGood”, and the red rust is not confirmed after 100 cycles. The steel plate was judged as “Good”, and the plated steel plate in which the red rust was confirmed in less than 100 cycles was judged as “Poor”. “Excellent” represents the most excellent evaluation of occurrence of red rust.
  • Tables 1 to 6 show the conditions of the plating process, the reheating process, and the cooling process, and the obtained evaluation results.
  • the blanks of chemical components shown in Tables 1 and 2 indicate that the corresponding alloy elements are not intentionally added.
  • “Mg / (Zn + Al)” indicates the relationship among the magnesium content, zinc content, and aluminum content contained in the quasicrystalline phase.
  • Example No. 1-No. No. 25 is a plated steel sheet that satisfies the conditions of the present invention and has excellent corrosion resistance.
  • Comparative Example No. 1-No. No. 9 did not satisfy the conditions of the present invention, and some of the results were excellent in red rust evaluation, but the corrosion weight loss was not sufficient.
  • Comparative Example No. Nos. 8 to 9 are Nos. No. 1 and No. 2 plated with a Ni pre-plated original plate described in paragraph 0140 (Table 9) of Japanese Patent Application Laid-Open No. 2008-255464. 26-No.

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Abstract

La présente invention concerne une tôle d'acier plaquée contenant des quasi-cristaux, comprenant une couche de revêtement métallique disposée sur au moins une surface d'une tôle d'acier, les composants chimiques dans la couche de revêtement métallique contenant du Mg, du Zn et de l'Al, la teneur en zinc et la teneur en aluminium en termes de % atomique parmi les composants chimiques de la couche de revêtement métallique satisfaisant la relation 25 % ≤ Zn + Al, la structure métallique dans la couche de revêtement métallique contenant des phases quasi-cristallines, la teneur en magnésium, la teneur en zinc et la teneur en aluminium en termes de % atomique dans les phases quasi-cristallines satisfaisant la relation 0,50 ≤ Mg/ (Zn + Al) ≤ 0,83, les phases quasi-cristallines étant présentes à la limite entre la tôle d'acier et la couche de revêtement métallique, les phases quasi-cristallines ayant un diamètre de petit axe de 0,2 à 2 µm représentant 90 % ou plus desdites limites, et 95 % ou plus en nombre des phases quasi-cristallines restantes autres que les phases quasi-cristallines qui sont présentes à la limite entre la tôle d'acier et la couche de revêtement métallique présentant des diamètres de cercle équivalent de 0,2-5 µm.
PCT/JP2016/056495 2015-03-04 2016-03-02 Tôle d'acier plaquée contenant des quasi-cristaux et procédé de production de tôle d'acier plaquée contenant des quasi-cristaux WO2016140286A1 (fr)

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CN111690894A (zh) * 2019-03-15 2020-09-22 宝山钢铁股份有限公司 一种附着强度优异的真空镀钢板及其制造方法
CN113195795A (zh) * 2018-12-27 2021-07-30 日本制铁株式会社 镀Ni钢板、及镀Ni钢板的制造方法
WO2021190610A1 (fr) * 2020-03-25 2021-09-30 深圳市合元科技有限公司 Récepteur pour dispositif de génération d'aérosol, et dispositif de génération d'aérosol

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* Cited by examiner, † Cited by third party
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CN109439989B (zh) * 2019-01-08 2019-10-15 苏州大学 一种镁合金及其制备方法

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JP2009537701A (ja) * 2006-05-24 2009-10-29 ブルースコープ・スティール・リミテッド Ａｌ／Ｚｎベースの合金被覆製品の処理

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NZ597077A (en) * 2009-05-28 2014-04-30 Bluescope Steel Ltd Metal-coated steel strip

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JP2009537701A (ja) * 2006-05-24 2009-10-29 ブルースコープ・スティール・リミテッド Ａｌ／Ｚｎベースの合金被覆製品の処理

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113195795A (zh) * 2018-12-27 2021-07-30 日本制铁株式会社 镀Ni钢板、及镀Ni钢板的制造方法
CN111690894A (zh) * 2019-03-15 2020-09-22 宝山钢铁股份有限公司 一种附着强度优异的真空镀钢板及其制造方法
WO2021190610A1 (fr) * 2020-03-25 2021-09-30 深圳市合元科技有限公司 Récepteur pour dispositif de génération d'aérosol, et dispositif de génération d'aérosol

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