WO2016167304A1 - めっき鋼板およびその製造方法 - Google Patents
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- WO2016167304A1 WO2016167304A1 PCT/JP2016/061955 JP2016061955W WO2016167304A1 WO 2016167304 A1 WO2016167304 A1 WO 2016167304A1 JP 2016061955 W JP2016061955 W JP 2016061955W WO 2016167304 A1 WO2016167304 A1 WO 2016167304A1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/48—After-treatment of electroplated surfaces
- C25D5/50—After-treatment of electroplated surfaces by heat-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B15/00—Layered products comprising a layer of metal
- B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
- B32B15/013—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium
- B32B15/015—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of an iron alloy or steel, another layer being formed of a metal other than iron or aluminium the said other metal being copper or nickel or an alloy thereof
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C19/00—Alloys based on nickel or cobalt
- C22C19/03—Alloys based on nickel or cobalt based on nickel
- C22C19/05—Alloys based on nickel or cobalt based on nickel with chromium
- C22C19/058—Alloys based on nickel or cobalt based on nickel with chromium without Mo and W
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- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/06—Alloys based on chromium
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- C22C30/00—Alloys containing less than 50% by weight of each constituent
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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
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- 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
- C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
- C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/023—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material only coatings of metal elements only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
- C23C28/028—Including graded layers in composition or in physical properties, e.g. density, porosity, grain size
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
Definitions
- the present invention relates to a plated steel sheet and a manufacturing method thereof.
- stainless steel sheets have been used for a wide range of heat resistance applications.
- stainless steel is used in an exhaust system of an automobile that requires corrosion resistance in a high temperature corrosive environment. Since stainless steel is expensive, replacement with aluminum plating, which is cheaper and excellent in heat resistance, has been attempted, but aluminum plating does not provide sufficient corrosion resistance in environments exposed to NOX and SOX such as mufflers. Most remain stainless.
- the present inventors have proposed heat resistance using Ni or Cr that does not dissolve in nitric acid or sulfuric acid for the purpose of providing a replaceable material from stainless steel that is inexpensive and has high temperature corrosion resistance and excellent corrosion resistance in NOX and SOX environments. Worked on the development of Ni-Cr alloy plating.
- Patent Document 1 discloses that 18-8 stainless steel is obtained by first heat-treating a steel plate in a non-oxidizing atmosphere at 600 ° C. to 910 ° C. for 60 seconds to 20 hours after Cr plating on the steel plate and Ni plating thereon. To obtain a component similar to In Patent Document 2, after applying Cr plating and Ni plating on a steel plate, the steel plate is heat-treated in a molten salt bath at 750 to 900 ° C. for 1 to 4 hours to obtain components similar to 18-8 stainless steel. It is described.
- Patent Document 3 describes that a Cr-plating is first performed on a steel plate, and then Ni plating is performed thereon, and then the steel plate is heat-treated to form a Ni-Cr alloy and a Cr-Fe-Ni alloy layer. ing.
- Patent Documents 1 and 2 have a problem that productivity is low because long-time heat treatment is required to obtain a target composition. Furthermore, since the thermal diffusion is performed for a long time, Fe diffuses to the surface of the plating, and therefore, when exposed to a high-temperature oxidizing atmosphere, oxidation starts from the Fe diffused on the surface.
- Patent Document 2 describes that Cr is first coated with a plating thickness of 4 to 15 ⁇ m by an electroplating method.
- Cr is first coated with a plating thickness of 4 to 15 ⁇ m by an electroplating method.
- the amount of Cr plating deposited by the method described in Patent Document 3 is as small as 0.01 to 0.2 g / m 2, and there is no problem of equipment cost or productivity.
- the amount of Cr is small and it does not deposit uniformly on the steel sheet, Fe—Ni is generated at the plating interface in addition to Cr—Fe, and this Fe—Ni plated part is peeled off in a high temperature oxidizing atmosphere, or Fe It has the disadvantage that it diffuses on the plating surface and oxidation proceeds from there.
- an object of the present invention is to provide a plated steel sheet excellent in heat resistance and productivity and a method for producing the same.
- a steel plate and an alloy plating layer formed on the surface of the steel plate are provided, and the alloy plating layer is 5% by mass and Cr is 5 to 91. %, Fe 0.5 to 10%, the balance being Ni and inevitable impurities, the Ni concentration in the alloy plating layer gradually decreases from the outermost surface of the alloy plating layer toward the steel plate side, In the region of 300 nm or more from the surface, the ratio of Ni concentration to Cr concentration is Ni / Cr> 1, and the Fe concentration in the alloy plating layer gradually decreases from the steel plate side toward the outermost surface of the alloy plating layer, Fe concentration on the outermost surface is 0.5% or less, formed in the alloy plating layer, the total thickness of the alloy layer containing Cr and Fe is 500 to 2000 nm, and the total adhesion amount of the alloy plating layer to the steel sheet is 4 .5-55.5 g / m 2 A plated steel sheet is provided.
- the Cr plating adhesion amount in the alloy plating layer is 3.5 to 28.8 g / m 2
- the Ni plating adhesion amount in the alloy plating layer is 3.0 to 26.7 g / m 2.
- the Cr / Ni plating adhesion ratio in the plating layer may be 0.9 to 5.0.
- the Cr plating adhesion amount of the Cr plating layer is greater than 3.5 g / m 2 and not more than 28.8 g / m 2 .
- the component in the region from the outermost surface of the alloy plating layer to the depth of 10 nm may be mass%, Cr may be 0 to 35%, Ni may be 65 to 100%, and Fe may be 0.5% or less.
- the alloy plating layer may have a Ni—Cr alloy layer.
- the alloy plating layer may have a Ni layer on top of the Ni—Cr alloy layer.
- the total thickness of the Cr—Fe containing alloy layer may be 300 nm or more.
- a method of manufacturing a plated steel sheet for manufacturing the above-described plated steel sheet wherein Cr plating is performed on one or both surfaces of the steel sheet with a surface density of 1.5 to 28.8 g / m 2.
- Ni plating is performed on one or both surfaces of the steel sheet with a surface density of 1.5 to 28.8 g / m 2.
- the Cr plating adhesion amount of the Cr plating layer is 3.5 to 28.8 g / m 2
- the Ni plating adhesion amount of the Ni plating layer is 3.0 to 26.7 g / m 2
- Cr / Ni The plating adhesion ratio may be 0.9 to 5.0.
- the Cr plating adhesion amount of the Cr plating layer is greater than 3.5 g / m 2 and not more than 28.8 g / m 2 .
- the plated steel sheet according to the present invention is excellent in heat resistance and productivity.
- the plated steel plate according to the present embodiment includes a steel plate and an alloy plating layer formed on the steel plate.
- the steel plates that can be used in the present embodiment are not particularly limited, and generally known steel plates such as hot rolled steel plates and cold rolled steel plates can be used.
- the steel type may also be Al killed steel, ultra-low carbon steel added with Ti, Nb or the like, and high-tensile steel added with elements such as P, Si, or Mn.
- the steel plate is preferably a cold rolled steel plate.
- the alloy plating layer has the characteristic configuration described below. For this reason, the plated steel plate according to the present embodiment has high heat resistance and productivity.
- the alloy plating layer contains 5 to 91% of Cr and 10% or less of Fe by mass%, and the balance is made of Ni and inevitable impurities.
- concentration of each component means mass% unless otherwise specified. Further, the concentration of each component means the concentration of the component existing throughout the thickness direction of the alloy plating layer unless otherwise specified.
- concentration of each component can be measured by a glow discharge analysis (GDS: Glow Discharge Spectroscopy).
- the alloy plating layer has such components, a Ni—Cr alloy layer excellent in heat resistance and a Cr—Fe alloy layer excellent in adhesion to a steel plate are formed in the alloy plating layer.
- the alloy plating layer has these alloy layers and further satisfies the conditions described later.
- the plated steel plate which concerns on this embodiment expresses the outstanding heat resistance and corrosion resistance.
- the plated steel sheet is excellent in productivity because the time required for heat treatment, that is, the holding time is short. The heat treatment will be described later.
- the Cr concentration in the alloy plating layer is less than 5%, the Ni—Cr alloy layer is not sufficiently formed in the alloy plating layer. For this reason, the target heat resistance cannot be obtained. Further, if the Cr concentration exceeds 91%, it is difficult to secure a region where Ni / Cr> 1 is 300 nm or more, so that there is a possibility of causing problems described later. Further, when the Fe concentration in the alloy plating layer exceeds 10%, the oxidation of the alloy plating layer proceeds starting from Fe in the alloy plating layer, so that the heat resistance and corrosion resistance of the plated steel sheet are lowered.
- the Ni concentration in the alloy plating layer gradually decreases from the outermost surface (exposed surface) of the alloy plating layer toward the steel plate side. Furthermore, in the region of 300 nm or more from the outermost surface of the alloy plating layer, the ratio of Ni concentration to Cr concentration is Ni / Cr> 1.
- the alloy plating layer has the above-described configuration, oxidation of the plated steel sheet at a high temperature is suppressed. That is, heat resistance is improved.
- the thickness of the region where Ni / Cr> 1 is less than 300 nm, Cr is likely to be exposed on the outermost surface of the alloy plating layer. Then, Cr exposed on the outermost surface can absorb oxygen and nitrogen in the atmosphere at high temperatures and become brittle. That is, Cr exposed on the outermost surface may impair the heat resistance of the plated steel sheet.
- the thickness of the region where Ni / Cr> 1 is preferably 1000 nm or more, more preferably 2000 nm or more.
- the thickness of the region where Ni / Cr> 1 is larger than 5000 nm, it is not economical because it is necessary to deposit a large amount of Ni plating in the manufacturing process or to require heating for a long time. .
- the thickness of the region is preferably 5000 nm or less.
- the Fe concentration (% by mass) in the alloy plating layer gradually decreases from the steel plate side toward the outermost surface of the alloy plating layer. Furthermore, the Fe concentration on the outermost surface of the alloy plating layer is 0.5% or less. Specifically, the Fe concentration in a depth range of 10 nm from the outermost surface of the alloy plating layer is 0.5% or less. If Fe exceeds 0.5% on the outermost surface of the alloy plating layer, the oxidation of the alloy plating layer proceeds starting from the outermost surface Fe, which may reduce the corrosion resistance and heat resistance of the plated steel sheet. is there.
- the Fe concentration on the outermost plating surface is more preferably 0.1% or less.
- an alloy layer containing Cr and Fe (hereinafter also referred to as “Cr—Fe-containing alloy layer”) is formed in the alloy plating layer.
- the Cr—Fe containing alloy layer is formed in the vicinity of the interface between the alloy plating layer and the steel plate.
- Examples of the Cr—Fe containing alloy layer include a Cr—Fe alloy layer and a Ni—Cr—Fe alloy layer. Any of these may be formed in the alloy plating layer, or both may be formed in the alloy plating layer.
- the total thickness of the Cr—Fe containing alloy layer (when a plurality of types of Cr—Fe containing alloy layers are formed, the total thickness) is 500 nm or more and 2000 nm or less.
- the Cr—Fe containing alloy layer can enhance the adhesion between the steel sheet and the alloy plating layer.
- the thickness of the Cr—Fe-containing alloy layer is less than 500 nm, the adhesion between the alloy plating layer and the steel sheet is not sufficient.
- the Cr—Fe-containing alloy layer is too thick, Fe in the alloy plating layer is likely to diffuse to the outermost surface of the alloy plating layer in a heat-resistant environment.
- the diffusion of Fe is mitigated by increasing the Cr concentration in the alloy plating layer.
- increasing the Cr concentration is economically and environmentally undesirable. Therefore, the total thickness of the Cr—Fe-containing alloy layer needs to be 2000 nm or less from the viewpoints of ensuring stable heat resistance performance, economy, and environment.
- the total adhesion amount of the alloy plating layer to the steel sheet (hereinafter also referred to as “alloy plating adhesion amount”) is 4.5 to 55.5 g / m 2 .
- the alloy plating adhesion amount is less than 4.5 g / m 2, it is difficult to ensure sufficient heat resistance.
- the amount of alloy plating attached is more preferably 10 g / m 2 or more. If the amount of alloy plating deposition exceeds 55.5 g / m 2 , only a decrease in productivity and an increase in cost are observed, and no improvement in performance is observed. Further, it is preferable that Cr is contained at a concentration of 0 to 35%, Ni of 65 to 100%, and Fe of 0.5% or less in the region from the outermost surface of the alloy plating layer to a depth of 10 nm.
- the concentration of each plating component in the above region is preferably 0 to 15% for Cr, 85 to 100% for Ni, and 0.1% for Fe, and more preferably 0 to Cr. 4%, Ni is 96-100%, and Fe is 0%.
- Ni or Ni-Cr alloy is excellent in stability in a high temperature atmosphere, but when only Ni or Ni-Cr alloy is plated on a steel sheet, the plating layer is at the interface between the plating layer and the steel sheet in a high temperature oxidizing atmosphere. It peels off with the generated scale. For this reason, in this embodiment, a large amount of Cr is contained in the vicinity of the interface between the alloy plating layer and the steel plate. Thereby, the adhesiveness in the high temperature environment of an alloy plating layer and a steel plate is improved. From this viewpoint, it is preferable that a Cr—Fe alloy layer is formed with a thickness of 300 nm or more in the vicinity of the interface between the alloy plating layer and the steel plate.
- the composition of the plating is in the order of a combination where heat resistance is preferable, 1.
- Ni layer, Ni—Cr alloy layer, Cr layer, Cr—Fe alloy layer from the outermost surface of the alloy plating layer (see FIG. 1) 2.
- Ni layer, Ni—Cr alloy layer, Ni—Cr—Fe alloy layer from the outermost surface of the alloy plating layer Ni—Cr alloy layer, Cr layer, Cr—Fe alloy layer from the outermost surface of the alloy plating layer, 6).
- a Ni—Cr alloy layer is included. That is, in this embodiment, the presence of the Ni—Cr alloy layer is important, and desired heat resistance and the like are realized by the Ni—Cr alloy layer.
- concentration of each component in an alloy plating layer can be measured by a glow discharge analysis (GDS: Glow Discharge Spectroscopy).
- GDS Glow Discharge Spectroscopy
- the concentration distribution of each component in the thickness direction can be specified.
- An example of measurement data is shown in FIG.
- the horizontal axis represents the distance (depth) ( ⁇ m) from the outermost surface of the alloy plating layer, and the vertical axis represents the concentration (mass%) of each component.
- the plated steel sheet which shows the result of FIG. 2 is produced in the following steps. That is, Cr plating was performed on the cold-rolled steel sheet with an adhesion amount of 7.2 g / m 2 .
- Ni plating was performed on the Cr plating layer with an adhesion amount of 10 g / m 2 .
- the cold-rolled steel sheet on which the Cr plating layer and the Ni plating layer were formed was put into an annealing furnace.
- the internal temperature of the annealing furnace was raised to 820 ° C. in 82 seconds, and the cold-rolled steel sheet was held for 20 seconds.
- a plated steel sheet was obtained by the above process.
- the measurement conditions are as shown in Table 1. Also in the Example mentioned later, the density
- this inventor earnestly examined about the composition of the alloy plating layer required in order to improve the heat resistance in the long time of a plated steel plate.
- the composition of the alloy plating layer required in order to improve the heat resistance in the long time of a plated steel plate.
- it is necessary to form a Ni—Cr layer in the alloy plating layer.
- the extent to which the Cr—Ni layer is formed in the alloy plating layer depends on the Cr plating adhesion amount (g / m 2 ), the Ni plating adhesion amount (g / m 2 ), and the Cr / Ni plating in the alloy plating layer. Depends on the adhesion amount ratio.
- the present inventors have found that the Cr plating adhesion amount (g / m 2 ), the Ni plating adhesion amount (g / m 2 ), and the Cr / Ni plating adhesion amount ratio in the alloy plating layer are important.
- the Cr plating adhesion amount means the mass of Cr contained in the entire unit area and thickness direction of the alloy plating layer
- the Ni plating adhesion amount is the entire unit area and thickness direction of the alloy plating layer. It means the mass of Ni contained.
- the Cr / Ni plating adhesion amount ratio is a value obtained by dividing the Cr plating adhesion amount by the Ni plating adhesion amount. The Cr plating adhesion amount and the Ni plating adhesion amount can be calculated based on the Cr concentration and the Ni concentration in the alloy plating layer.
- the Cr plating adhesion amount in the alloy plating layer is 3.5 to 28.8 g / m 2
- the Ni plating adhesion amount in the alloy plating layer is 3.0 to 26.7 g / m 2 .
- the Cr / Ni plating adhesion ratio in the alloy plating layer is preferably 0.9 to 5.0. In this case, the heat resistance for a long time is further improved.
- the Cr / Ni plating adhesion ratio exceeds 5.0, when the plated steel sheet is exposed to a high temperature for a long time, Cr absorbs nitrogen and oxygen and becomes brittle.
- the Cr / Ni plating adhesion ratio is less than 0.9, a large amount of Ni is alloyed with Fe. The Ni—Fe alloy is easily peeled off from the steel sheet when oxidized. Therefore, the heat resistance of the alloy plating layer is lowered.
- the Cr plating adhesion amount is preferably larger than 3.5 g / m 2 .
- the Ni plating adhesion amount is more preferably 3.0 to 15.0 g / m 2 , and more preferably 5.0 to 10.0 g / m 2 .
- the Cr / Ni plating adhesion ratio is more preferably 1.2 to 3.0. In this case, the heat resistance for a long time is further improved.
- the Cr plating adhesion amount (g / m 2 ), the Ni plating adhesion amount (g / m 2 ), and the Cr / Ni plating adhesion amount ratio satisfy the following conditions (a) and (b). .
- the heat resistance for a long time is further improved.
- Cr coating weight is greater 28.8 g / m 2 or less than 3.5 g / m 2.
- condition (b) the condition that the Ni plating adhesion amount is 5.0 to 10.0 g / m 2 and the condition that the Cr / Ni plating adhesion ratio is 1.2 to 3.0. More preferably, both of these are satisfied.
- the method for producing the plated steel sheet is as follows. First, Cr plating is formed on one or both surfaces of a steel sheet by performing Cr plating on one or both surfaces of the steel sheet with an adhesion amount of 1.5 to 28.8 g / m 2 . Next, the Ni plating layer is formed on the Cr plating layer by performing Ni plating on the Cr plating layer with an adhesion amount of 3 to 26.7 g / m 2 . Next, the steel sheet on which the Cr plating layer and the Ni plating layer are formed is held in a non-oxidizing atmosphere or a reducing atmosphere at a temperature of 600 ° C. to 900 ° C. for a time longer than 0 seconds and not longer than 60 seconds. The plated steel sheet concerning this embodiment is produced according to the above process. The details of the manufacturing method are as follows.
- the steel sheet is degreased and pickled.
- Cr plating is performed on one or both surfaces of the steel plate with an adhesion amount of 1.5 to 28.8 g / m 2 .
- a Cr plating layer is formed on the steel plate.
- the method of Cr plating is not particularly limited, but may be an electrolytic method, for example.
- manufacturing conditions such as plating bath conditions are not particularly limited.
- the Cr plating adhesion amount is less than 1.5 g / m 2 , it is not possible to sufficiently form a Cr—Fe-containing alloy layer effective for adhesion of the alloy plating layer in a high temperature environment. For this reason, it becomes difficult to form the total thickness of the Cr—Fe-containing alloy layer to 300 nm or more. Further, when the Cr plating adhesion amount is more than 28.8 g / m 2 , the cost required for the Cr plating process increases due to the prolonged plating process. For this reason, it is not economical. In addition, workability such as bending also decreases.
- the Cr plating adhesion amount is preferably 2.0 to 15.0 g / m 2 , and more preferably 3.5 to 6 g / m 2 .
- the Cr plating adhesion amount is preferably larger than 3.5 g / m 2 .
- the Ni plating layer is formed on the Cr plating layer by performing Ni plating on the Cr plating layer.
- the Ni plating method is not particularly limited, but when a Ni plating layer is formed on the Cr plating layer, a Ni strike bath having a low pH may be used.
- the conditions for the Ni strike bath are not particularly limited.
- the underlying Cr cannot be sufficiently covered with the Ni plating layer.
- the Ni—Cr alloy layer after heat treatment is thin and non-uniform.
- a heat-resistant alloy plating layer cannot be obtained.
- the purity of the Cr plating layer remains high even after firing.
- the Cr plating layer is not sufficiently covered with the Ni plating layer.
- the high purity Cr plating layer is not only easily embrittled at room temperature, but also absorbs oxygen and nitrogen at a higher temperature and is more likely to be embrittled. Also in this point, the heat resistance is lowered.
- the Ni plating adhesion amount is larger than 26.7 g / m 2 , the cost required for the Ni plating process increases due to an increase in Ni plating process cost, a longer plating process, and the like. For this reason, it is not economical. Furthermore, the adhesion between the Ni plating layer and the Cr plating layer also decreases. For this reason, a part of the alloy plating layer easily peels off at the interface between these layers (specifically, the interface between Ni> Cr and Ni ⁇ Cr) by bending or the like. From the above viewpoint, the Ni plating adhesion amount is preferably 3.0 to 15.0 g / m 2 , and more preferably 5.0 to 10.0 g / m 2 .
- the Cr plating adhesion amount and the Ni adhesion amount are adjusted so that the Cr concentration in the alloy plating layer is 5 to 91%. Then, the following heat processing is performed, and the alloy plating layer which satisfy
- the steel sheet on which the Cr plating layer and the Ni plating layer are formed is heat treated. Specifically, the steel sheet is held in a non-oxidizing atmosphere or a reducing atmosphere at a temperature of 600 ° C. to 900 ° C. for a time greater than 0 seconds and 60 seconds or less.
- the heat treatment of the steel sheet on which the Cr plating layer and the Ni plating layer are formed is performed in a non-oxidizing atmosphere in order to prevent oxidation of the Cr plating layer from the end face of the Cr plating layer or the pinhole in the Ni plating layer.
- it is performed in a reducing atmosphere.
- examples of the non-oxidizing atmosphere or reducing atmosphere include N 2 gas, Ar gas, H 2 gas, or a mixed gas atmosphere thereof.
- the heating method is not particularly limited, and furnace heating, energization heating, induction heating, etc. may be used.
- each component in the steel plate, the Ni plating layer, and the Cr plating layer is diffused.
- Cr in the Cr plating layer diffuses into the Ni plating layer
- Ni in the Ni plating layer diffuses into the Cr plating layer.
- Fe in the steel sheet diffuses into the Cr plating layer and the Ni plating layer.
- the temperature increase rate is not particularly limited, and may be a temperature increase rate comparable to the heat treatment performed in the conventional plated steel plate production line. However, if a time longer than 120 seconds elapses until the target temperature is reached, the time for thermal diffusion becomes longer, which is not economical, and Fe may diffuse to the surface. For this reason, it is preferable that the time required to reach the target temperature is 120 seconds or less.
- the diffusion rate of each component is proportional to the square root of the diffusion coefficient.
- the diffusion coefficient of ⁇ Fe having a high temperature is smaller than that of ⁇ Fe having a low temperature.
- the heat treatment temperature is 900 ° C. or lower, that is, Fe is diffused in the state of ⁇ Fe.
- the heat treatment temperature is less than 600 ° C., the diffusion rate is slow even with ⁇ Fe. For this reason, a long time is required for diffusion, and productivity is inferior. Accordingly, the heat treatment temperature, that is, the holding temperature is 600 to 900 ° C.
- the holding time after the temperature rise is greater than 0 seconds and not more than 60 seconds. Preferably, it is 1 to 30 seconds.
- the concentration ratio of Ni and Cr on the outermost surface of the alloy plating layer may be Ni / Cr ⁇ 1. In particular, this possibility increases as the Ni plating deposition amount decreases. Further, since the Cr—Fe layer becomes thicker than 2000 nm and Fe diffuses to the outermost surface of the alloy plating layer, the heat resistance is lowered.
- the holding temperature and holding time are adjusted within the above ranges according to the Cr plating adhesion amount and the Ni plating adhesion amount. That is, the holding temperature and the holding time are adjusted so that an alloy plating layer that satisfies the above-described requirements is formed on the steel plate.
- the cooling rate is not particularly limited, and may be a cooling rate comparable to the cooling treatment performed in the conventional plated steel plate production line.
- the present inventor has intensively studied heat treatment conditions necessary for improving the heat resistance (particularly, heat resistance for a long time) of the plated steel sheet. If Ni diffuses too much into the alloy plating layer during the heat treatment, the Ni—Fe layer peels from the steel sheet in a high-temperature oxidizing atmosphere. The extent to which Ni diffuses in the alloy plating layer depends not only on the holding temperature and holding time but also on the Cr plating adhesion amount. As a result, the present inventors have found that there is a strong correlation between the Cr plating adhesion amount and the holding temperature and holding time. Specific heat treatment conditions are as follows. In addition, when heat processing conditions satisfy
- the holding temperature is preferably 600 ° C., and the holding time is preferably as short as possible (for example, less than 1 second).
- the holding temperature is 600 ⁇ 800 ° C.
- the lower limit of the holding time is preferably 10 seconds or longer.
- T kT 0 (1)
- T 0 ⁇ 0.15 * (H ⁇ 600) +50 (2)
- T is a reference temperature
- T 0 is a reference time when the Cr plating adhesion amount is 6 g / m 2 .
- k is a correction coefficient, and is a value obtained by dividing the Cr plating adhesion amount (g / m 2 ) of the Cr plating layer to be fired by 6 g / m 2 (that is, the maximum adhesion amount).
- H is a holding temperature.
- the holding temperature is 650 ⁇ 800 ° C.
- the lower limit of the holding time is preferably 10 seconds or longer.
- T kT 0 (3)
- T 0 ⁇ 0.13 * (H ⁇ 600) +50 (4)
- T is a reference temperature
- T 0 is a reference time when the Cr plating adhesion amount is 15.0 g / m 2 .
- k is a correction coefficient, and is a value obtained by dividing the Cr plating adhesion amount (g / m 2 ) of the Cr plating layer to be fired by 15.0 g / m 2 (that is, the maximum adhesion amount).
- H is a holding temperature.
- the holding temperature is 700 ⁇ 900 ° C.
- the lower limit of the holding time is preferably 10 seconds or longer.
- T kT 0 (5)
- T 0 ⁇ 0.12 * (H ⁇ 600) +60 (6)
- T is a reference temperature
- T 0 is a reference time when the Cr plating adhesion amount is 28.8 g / m 2 .
- k is a correction coefficient, and is a value obtained by dividing the Cr plating adhesion amount (g / m 2 ) of the fired Cr plating layer by 28.8 g / m 2 (that is, the maximum adhesion amount).
- H is a holding temperature.
- the heat resistance is improved at least in a short time.
- the Cr plating adhesion amount, Ni plating adhesion amount, and Cr / Ni plating adhesion ratio satisfy the above-mentioned requirements, not only the heat resistance in a short time but also the long time Heat resistance is improved.
- the plated steel sheet according to this embodiment is excellent not only in heat resistance but also in corrosion resistance and adhesion. Furthermore, according to the manufacturing method of a plated steel plate, since holding time is short, the plated steel plate which concerns on this embodiment can be produced with high productivity.
- Example 1 In Experimental Example 1, the following experiment was performed in order to confirm that the plated steel sheet according to the present embodiment has high heat resistance. First, a cold-rolled steel plate (thickness: 0.8 mm) was prepared as a steel plate. Next, the wet wettability of the cold-rolled steel sheet was sufficiently ensured by subjecting the cold-rolled steel sheet to alkaline degreasing and sulfuric acid pickling. Subsequently, Cr plating was formed on the cold-rolled steel sheet by performing Cr plating on the cold-rolled steel sheet. Cr plating was performed by an electrolytic method. The plating conditions are shown in (A) below. Table 2 shows the amount of Cr plating adhesion.
- Ni plating was formed on the Cr plating layer by performing Ni plating on the Cr plating layer.
- Ni plating was also performed by an electrolytic method, and a strike bath was used as a plating bath.
- the plating conditions are shown in (B) below. Further, Table 2 shows the Ni plating adhesion amount.
- Electrolytic Cr plating (1) Plating bath component-Sargent bath chromic acid-250 g / l Sulfuric acid-3g / l (2) Electrolysis condition temperature -50 °C Current density-30A / dm 2
- Electrolytic Ni plating / Strike bath (1) Plating bath components Nickel chloride-240 g / l Hydrochloric acid 125ml / l (2) Electrolysis conditions pH -1.0 to 1.5 Temperature-Room temperature (25 ° C) Current density -4 A / dm 2 -Watt bath (1) Plating bath component Nickel sulfate-240 g / l Nickel chloride-45 g / l Boric acid-30g / l (2) Electrolysis conditions pH -3.5 to 4.5 Temperature-50 ° C Current density -5A / dm 2
- the cold-rolled steel sheet on which the Cr plating layer and the Ni plating layer were formed was put into an annealing furnace.
- the atmosphere inside the annealing furnace was 2% by volume H 2 -98% by volume N 2 .
- the internal temperature of the annealing furnace was increased to a holding temperature shown in Table 2 at 10 ° C./sec.
- the holding temperature was then maintained for the holding time shown in Table 2.
- the plated steel sheet was rapidly cooled to 200 ° C. using N 2 gas.
- the cooling rate at this time was 70 ° C./sec. Thereafter, the plated steel sheet was allowed to cool.
- a plated steel sheet sample was prepared by the above process.
- Example 1 a plurality of types of samples (levels) were prepared by variously changing the Cr plating adhesion amount, the Ni plating adhesion amount, and the heat treatment conditions.
- the composition of each sample is summarized in Table 2.
- concentration of each component in an alloy plating layer was measured by the glow discharge analysis (GDS: Glow Discharge Spectroscopy). The measurement conditions are shown in Table 1.
- Table 2 also shows preferred ranges of the respective components. Numerical values outside the preferred range are underlined.
- the “plating layer structure” shown in Table 2 indicates a classification of the layer structure of the alloy plating layer.
- Table 3 shows the correspondence between each section and the layer structure.
- Example 2 In Experimental Example 2, the effects of the Cr plating adhesion amount, the Ni plating adhesion amount, the Cr / Ni plating adhesion amount ratio, and the heat treatment conditions on heat resistance, particularly heat resistance over a long period of time were examined in more detail.
- a plurality of types of samples (plated steel sheets) having different Cr plating adhesion amount, Ni plating adhesion amount, Cr / Ni plating adhesion amount ratio, and heat treatment conditions were produced.
- Table 4 shows the plating adhesion amount and heat treatment conditions of each sample. Table 4 also shows preferred ranges such as the amount of plating adhesion. In the sample corresponding to the example, it was confirmed that the parameters shown in Table 2 satisfy the requirements of this embodiment.
- the surface oxidation state in each heat test was evaluated according to the following criteria.
- the generation area of Fe-derived red rust is 80% or more with respect to the entire surface of the alloy plating layer, or when the plating is peeled off during air cooling, the heat resistance is evaluated as B (Bad).
- the red rust generation area is 30% or more and less than 80% with respect to the entire surface of the alloy plating layer (when the generation of red rust is at a level where there is no practical problem)
- the heat resistance evaluation is G (Good).
- region of red rust became less than 30% with respect to the whole surface of an alloy plating layer, or there was much roughness, evaluation of heat resistance was evaluated as VG (Very Good).
- the plated steel sheet according to the present embodiment has high heat resistance.
- the Cr plating adhesion amount, the Ni plating adhesion amount, the Cr / Ni plating adhesion amount ratio, and the heat treatment conditions satisfy the predetermined conditions, it has been clarified that the heat resistance in a long time is also improved.
- the results in the bending test were slightly worse.
- the heat treatment conditions include conditions for satisfying heat resistance for a long time. And when heat processing conditions satisfy
- the preferable holding temperature is 650 to 800 ° C.
- the reference time for the holding time is 50 seconds. For this reason, no. The holding temperature and holding time of 18 are both lower than the preferred range.
- No. 2 in Experimental Example 2 was obtained. According to 20, 21, and 27, it was also found that when at least one of the holding temperature and the holding time is larger than the preferred range, the heat resistance in a long time decreases.
- the plated steel sheet according to the present invention is excellent in heat resistance and adhesion after a high temperature test, and can be widely applied as a member in a high temperature environment.
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Abstract
Description
例えば、特許文献1には鋼板上にまずCrめっき、その上にNiめっきをした後に、600℃~910℃の非酸化性雰囲気下で60秒~20時間鋼板を熱処理することで18-8ステンレスに類似させた成分を得ることが記載されている。また特許文献2では鋼板上にCrめっきとNiめっきを施した後に、750~900℃の溶融塩浴中で1~4時間鋼板を熱処理することで、18-8ステンレスに類似させた成分を得ることが記載されている。更に特許文献3では鋼板上にまずCrめっき、その上にNiめっきをしたのちに、鋼板を熱処理することでNi-Cr合金、およびCr-Fe-Ni合金層を持つめっきとすることが記載されている。
(a)前記Crめっき層のCrめっき付着量は3.5g/m2より大きく28.8g/m2以下である。
(b)Niめっき層のNiめっき付着量が5.0~10.0g/m2であるという条件、及びCr/Niめっき付着量比が1.2~3.0であるという条件のうち、少なくとも一方が満たされる。
(a)前記Crめっき層のCrめっき付着量は3.5g/m2より大きく28.8g/m2以下である。
(b)Niめっき層のNiめっき付着量が5.0~10.0g/m2であるという条件、及びCr/Niめっき付着量比が1.2~3.0であるという条件のうち、少なくとも一方が満たされる。
本実施形態に係るめっき鋼板は、鋼板と、鋼板上に形成された合金めっき層とを備える。本実施形態で使用可能な鋼板は特に制限されず、熱延鋼板、冷延鋼板など一般に公知の鋼板を用いることができる。鋼種もAlキルド鋼、Ti、Nbなどを添加した極低炭素鋼、及び、これらにP、Si、Mnなどの元素を添加した高張力鋼でもよい。なお、鋼板は冷延鋼板であることが好ましい。合金めっき層は、以下に説明する特徴構成を有する。このため、本実施形態に係るめっき鋼板は、高い耐熱性及び生産性を有する。
つぎに、本実施形態に係る合金めっき層の構成について詳細に説明する。合金めっき層は、質量%で、Crを5~91%、Feを10%以下含有し、残部がNi及び不可避不純物からなる。なお、以下の説明では、特に断りがない限り、各成分の濃度は質量%を意味するものとする。また、各成分の濃度は、特に断りがない限り、合金めっき層の厚み方向の全域に存在する成分の濃度を意味するものとする。また、各成分の濃度は、グロー放電分析(GDS:Glow Discharge Spectroscopy)により測定可能である。合金めっき層がこのような成分を有するので、合金めっき層内には、耐熱性に優れるNi-Cr合金層、及び鋼板との密着性に優れるCr-Fe合金層が形成される。合金めっき層は、これらの合金層を有し、さらに後述する条件を満足する。これにより、本実施形態に係るめっき鋼板は、優れた耐熱性と耐食性を発現する。さらに、めっき鋼板は、熱処理に要する時間、すなわち保持時間が短いので、生産性にも優れる。熱処理については後述する。
1.合金めっき層の最表面からNi層、Ni-Cr合金層、Cr層、Cr-Fe合金層(図1参照)
2.合金めっき層の最表面からNi層、Ni-Cr合金層、Cr-Fe合金層
3.合金めっき層の最表面からNi層、Ni-Cr合金層、Ni-Cr-Fe合金層、Cr-Fe合金層
4.合金めっき層の最表面からNi層、Ni-Cr合金層、Ni-Cr-Fe合金層
5.合金めっき層の最表面からNi-Cr合金層、Cr層、Cr-Fe合金層、
6.合金めっき層の最表面からNi-Cr合金層、Ni-Cr-Fe合金層、Cr-Fe合金層、
7.合金めっき層の最表面からNi-Cr合金層、Cr-Fe合金層
8.合金めっき層の最表面からNi-Cr合金層、Ni-Cr-Fe合金層である。
(a)Crめっき付着量は3.5g/m2より大きく28.8g/m2以下である。
(b)Niめっき付着量が5.0~10.0g/m2であるという条件、及びCr/Niめっき付着量比が1.2~3.0であるという条件のうち、少なくとも一方が満たされる。
次に、本実施形態に係るめっき鋼板の製造方法について述べる。めっき鋼板の製造方法は概略以下の通りである。まず、鋼板の片面若しくは両面に、1.5~28.8g/m2の付着量でCrめっきを行うことで、鋼板の片面若しくは両面にCrめっき層を形成する。ついで、Crめっき層の上に3~26.7g/m2の付着量でNiめっきをすることで、Crめっき層の上にNiめっき層を形成する。ついで、Crめっき層及びNiめっき層が形成された鋼板を非酸化性雰囲気又は還元性雰囲気中、600℃~900℃の温度で0秒より大きく60秒以下の時間保持する。以上の工程により、本実施形態に係るめっき鋼板を作製する。製造方法の詳細は以下の通りである。
T=kT0 (1)
T0=-0.15*(H-600)+50 (2)
ここで、数式(1)、(2)中、Tは基準温度であり、T0はCrめっき付着量が6g/m2となる際の基準時間である。kは補正係数であり、焼成対象のCrめっき層のCrめっき付着量(g/m2)を6g/m2(すなわち、最大付着量)で除算した値である。Hは保持温度である。
T=kT0 (3)
T0=-0.13*(H-600)+50 (4)
ここで、数式(3)、(4)中、Tは基準温度であり、T0はCrめっき付着量が15.0g/m2となる際の基準時間である。kは補正係数であり、焼成対象のCrめっき層のCrめっき付着量(g/m2)を15.0g/m2(すなわち、最大付着量)で除算した値である。Hは保持温度である。
T=kT0 (5)
T0=-0.12*(H-600)+60 (6)
ここで、数式(5)、(6)中、Tは基準温度であり、T0はCrめっき付着量が28.8g/m2となる際の基準時間である。kは補正係数であり、焼成対象のCrめっき層のCrめっき付着量(g/m2)を28.8g/m2(すなわち、最大付着量)で除算した値である。Hは保持温度である。
実験例1では、本実施形態に係るめっき鋼板が高い耐熱性を有することを確認するために、以下の実験を行った。まず、鋼板として、冷延鋼板(厚み:0.8mm)を準備した。ついで、冷延鋼板にアルカリ脱脂および硫酸酸洗を施すことで、冷延鋼板の水濡れ性を十分確保した。ついで、冷延鋼板にCrめっきを行うことで、冷延鋼板の上にCrめっき層を形成した。Crめっきは、電解法により行った。めっき条件は下記(A)に示す。また、Crめっき付着量を表2に示す。ついで、Crめっき層の上にNiめっきを施すことで、Crめっき層の上にNiめっき層を形成した。Niめっきも電解法によって行い、めっき浴としてストライク浴を使用した。めっき条件を下記(B)に示す。また、Niめっき付着量を表2に示す。
(1)めっきの浴成分―サージェント浴
クロム酸-250g/l
硫酸-3g/l
(2)電解条件
温度-50℃
電流密度-30A/dm2
・ストライク浴
(1)めっき浴成分
塩化ニッケル-240g/l
塩酸 125ml/l
(2)電解条件
pH-1.0~1.5
温度-室温(25℃)
電流密度-4A/dm2
・ワット浴
(1)めっき浴成分
硫酸ニッケル-240g/l
塩化ニッケル-45g/l
ほう酸-30g/l
(2)電解条件
pH-3.5~4.5
温度-50℃
電流密度-5A/dm2
作製した試料(めっき鋼板)の耐熱性を評価するために、試料を600℃の大気雰囲気中に120時間曝露した。その後、試料を大気中で放冷してその表面の酸化状態を調査した。
作製試料の加工性を評価するために、JISH8504めっきの密着性試験法のうち(j)曲げ試験法を行った。ただし、JIS記載の曲げ戻しは行わず、曲げた状態のまま、その後さらに(g)引きはがし試験方法のうち(1)テープ試験方法をJISZ 1522粘着テープを用いて行い、試料のめっき密着性を評価した。
実験例2では、Crめっき付着量、Niめっき付着量、Cr/Niめっき付着量比、及び熱処理条件が耐熱性、特に長時間での耐熱性に与える影響についてさらに詳細に検討した。まず、実施例1と同様の方法で、Crめっき付着量、Niめっき付着量、Cr/Niめっき付着量比、及び熱処理条件が異なる複数種類の試料(めっき鋼板)を作製した。各試料のめっき付着量及び熱処理条件を表4に示す。表4には、めっき付着量等の好ましい範囲も併記した。なお、実施例に相当する試料では、表2に示すパラメータが本実施形態の要件を満たすことを確認できた。
作製した試料の耐熱性を評価するために、試料を600℃の大気雰囲気中に120時間暴露した。ついで、試料を大気中で放冷してその表面の酸化状態を調査した(耐熱試験 短)。なお、以下の評価基準でG(Good)以上となる試料をさらに280時間(すなわち、合計400時間)曝露した(耐熱試験 長)。ついで、試料を大気中で放冷してその表面の酸化状態を調査した。
Claims (10)
- 鋼板と、
前記鋼板の表面に形成された合金めっき層と、を有し、
前記合金めっき層は、質量%で、Crを5~91%、Feを0.5~10%含有し、残部がNi及び不可避不純物であり、
前記合金めっき層中のNi濃度が前記合金めっき層の最表面から鋼板側に向かって漸減し、
前記合金めっき層の最表面から300nm以上の領域においてNi濃度とCr濃度の比がNi/Cr>1であり、
前記合金めっき層中のFe濃度が鋼板側から前記合金めっき層の最表面に向かって漸減し、
前記合金めっき層の最表面におけるFe濃度が0.5%以下であり、
前記合金めっき層中に形成され、Cr及びFeを含むCr-Fe含有合金層の総厚みが500~2000nmとなり、
前記合金めっき層の前記鋼板への全付着量が4.5~55.5g/m2であることを特徴とするめっき鋼板。 - 前記合金めっき層中のCrめっき付着量は3.5~28.8g/m2であり、
前記合金めっき層中のNiめっき付着量は3.0~26.7g/m2であり、
前記合金めっき層中のCr/Niめっき付着量比は、0.9~5.0であることを特徴とする、請求項1記載のめっき鋼板。 - 以下の条件(a)、(b)が満たされることを特徴とする、請求項2記載のめっき鋼板。
(a)前記Crめっき層のCrめっき付着量は3.5g/m2より大きく28.8g/m2以下である。
(b)前記合金めっき層中のNiめっき付着量が5.0~10.0g/m2であるという条件、及び前記合金めっき層中のCr/Niめっき付着量比が1.2~3.0であるという条件のうち、少なくとも一方が満たされる。 - 前記合金めっき層の最表面から深さ10nmまでの領域に質量%でCrが0~35%、Niが65~100%、Feが0.5%以下の濃度で含まれることを特徴とする請求項1~3の何れか1項に記載のめっき鋼板。
- 前記合金めっき層が、Ni-Cr合金層を有していることを特徴とする請求項1~4の何れか1項に記載のめっき鋼板。
- 前記合金めっき層がNi-Cr合金層の上層にNi層を有することを特徴とする請求項1~5のいずれか1項に記載のめっき鋼板。
- 前記Cr-Fe含有合金層の総厚みが300nm以上であることを特徴とする、請求項1~6のいずれか1項に記載のめっき鋼板。
- 請求項1~7の何れか1項に記載のめっき鋼板を製造するめっき鋼板の製造方法であって、
鋼板の片面若しくは両面に、1.5~28.8g/m2の付着量でCrめっきを行うことで、前記鋼板の片面若しくは両面にCrめっき層を形成する工程と、
前記Crめっき層の上に3~26.7g/m2の付着量でNiめっきをすることで、前記Crめっき層の上にNiめっき層を形成する工程と、
前記Crめっき層及びNiめっき層が形成された前記鋼板を非酸化性雰囲気又は還元性雰囲気中、600℃~900℃の温度で0秒より大きく60秒以下の時間保持する工程と、を含むことを特徴とする、めっき鋼板の製造方法。 - 前記Crめっき層のCrめっき付着量は3.5~28.8g/m2であり、
前記Niめっき層のNiめっき付着量は3.0~26.7g/m2であり、
Cr/Niめっき付着量比は、0.9~5.0であることを特徴とする、請求項8記載のめっき鋼板の製造方法。 - 以下の条件(a)、(b)が満たされることを特徴とする、請求項9記載のめっき鋼板の製造方法。
(a)前記Crめっき層のCrめっき付着量は3.5g/m2より大きく28.8g/m2以下である。
(b)前記Niめっき層のNiめっき付着量が5.0~10.0g/m2であるという条件、及びCr/Niめっき付着量比が1.2~3.0であるという条件のうち、少なくとも一方が満たされる。
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WO2021107161A1 (ja) * | 2020-03-03 | 2021-06-03 | 日本製鉄株式会社 | Niめっき鋼板、及びその製造方法 |
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