Classifications

• • 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
• • 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
  • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
  • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
  • C23C18/31—Coating with metals
  • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
  • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
  • C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D21/00—Processes for servicing or operating cells for electrolytic coating
  • C25D21/12—Process control or regulation
• • 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
• • 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
• • 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
  • C25D5/16—Electroplating with layers of varying thickness
• • 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
  • C25D5/34—Pretreatment of metallic surfaces to be electroplated
  • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
• • 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
• • 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
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
• • 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
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/615—Microstructure of the layers, e.g. mixed structure
  • C25D5/617—Crystalline layers
• • 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
  • C25D5/60—Electroplating characterised by the structure or texture of the layers
  • C25D5/623—Porosity of the layers
• • 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
  • C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D7/00—Electroplating characterised by the article coated
• • C—CHEMISTRY; METALLURGY
  • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
  • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
  • C25D7/00—Electroplating characterised by the article coated
  • C25D7/06—Wires; Strips; Foils
  • C25D7/0614—Strips or foils

Definitions

• the present invention relates to a nickel-plated metal material.
• PTL 1 discloses a roughened nickel-plated sheet, the lightness and 85°-gloss of a surface of a roughened nickel layer of which are specified to provide the roughened nickel-plated sheet with excellent adhesion with another member while allowing the plating layer to hold adhesion with a base material.
• PTL 2 discloses a roughened nickel-plated sheet improved in liquid penetration resistance when joined with another member, in addition to the adhesion of a plating layer to a base material and adhesion with another member.
• a roughened nickel metal sheet is industrially and continuously manufactured or in a continuous manufacturing step using a roughened nickel metal sheet such as stacking it with another member such as, for example, a molten resin
• loads are applied from multiple directions to a roughened nickel layer.
• a plated metal sheet having a roughened nickel layer to have a roughened shape with durability to such loads from multiple directions (hereinafter also called "shear durability").
• the present invention has been made with a view to solving such a problem, and has, as an object thereof, the provision of a nickel-plated metal sheet including a roughened nickel layer having shear durability to loads from multiple directions.
• a nickel-plated metal material in the present embodiment is (1) a nickel-plated metal material including a base material made of metal, and a roughened nickel layer formed on at least one side on the base material.
• a root mean square height Rq is 0.29 ⁇ m or greater and 0.90 ⁇ m or smaller, and a maximum height Sz is greater than 3.5 ⁇ m and 10.0 ⁇ m or smaller.
• (2) Sdr (Developed Interfacial Area Ratio) on the surface on the side of the roughened nickel layer is preferably 16% to 75%.
• a relative load length ratio Rmr on the surface on the side of the roughened nickel layer is preferably 33% to 95%.
• a root mean square slope R ⁇ q on the surface on the side of the roughened nickel layer is preferably 15 to 50 degrees.
• a ten-point mean roughness Rzjis on the surface on the side of the roughened nickel layer is preferably 1.0 to 6.0 ⁇ m.
• a deposition amount of nickel in the roughened nickel layer is preferably 3.5 to 19.0 g/m 2 .
• the nickel-plated metal material preferably has an iron-nickel alloy layer and/or a nickel layer between the base material and the roughened nickel layer.
• a total deposition amount of nickel in the roughened nickel layer and the nickel layer is preferably 4.8 to 32.8 g/m 2 .
• a total deposition amount of nickel in the roughened nickel layer, the nickel layer, and the iron-nickel alloy layer is preferably 4.5 to 55.1 g/m 2 .
• the roughened nickel layer is preferably formed on an outermost surface.
• (11) preferably including, on the roughened nickel layer, a coating metal layer formed of zinc, tin, or chromium, or an alloy thereof.
• a nickel-plated metal sheet which includes a roughened nickel layer having shear durability even to loads from multiple directions, can be provided.
• FIG. 1 is a view schematically depicting an embodiment of a nickel-plated metal material 100 of the present invention.
• the nickel-plated metal material 100 of the present embodiment is used for collectors of positive electrodes or negative electrodes in secondary batteries and the like, electronic related devices, and the like.
• the nickel-plated metal material 100 can be suitably used also for members required to have high adhesion with other members (active materials, resins, and the like) such as battery members, members constituting electric/electronic related devices, interior members for automobiles and constructions, automobile members such as gaskets, and sliding members.
• the nickel-plated metal material 100 of the present embodiment includes a base material 20 made of metal, and a roughened nickel layer 50 formed on the base material 20.
• a metal sheet made of a pure metal selected from Fe, Al, or Ni or a metal sheet made of an alloy containing, as a base, one selected from Fe, Al, or Ni is preferred.
• a steel sheet is particularly preferred, and as the steel sheet, a steel sheet containing iron as a base and smaller than 1.0 wt% of Cr and other additive metal elements is preferred.
• low-carbon steel (carbon content: 0.01 to 0.15 wt%) represented by low-carbon aluminum-killed steel, ultralow-carbon steel having a carbon content of lower than 0.01 wt%, or non-aging ultralow-carbon steel prepared by adding Ti, Nb, and/or the like to ultralow-carbon steel is suitably used.
• a low-carbon steel sheet or ultralow-carbon steel sheet is preferred from the viewpoint of electrical conductivity.
• a surface-treated steel sheet including an iron-nickel diffusion layer or an iron-nickel diffusion layer and a nickel layer on a surface thereof or a zinc-plated steel sheet can also be used, although details will be mentioned later.
• the thickness of the base material 20 for use in the nickel-plated metal material 100 of the present embodiment a range of 0.01 to 0.5 mm is suited. If used as a current collector in a battery with a focus placed on the viewpoints of volumetric and gravimetric energy densities, the thickness of the base material 20 is more preferably 0.01 to 0.3 mm, and still more preferably 0.025 to 0.1 mm from the viewpoint of strength, the viewpoint of a desired battery capacity, and the like.
• a thickness measurement by a cross-sectional observation under an optical microscope or scanning electron microscope (SEM) is suitably applied.
• a thickness measurement before the surface treatment specifically before the formation of the roughened nickel layer 50, on the other hand, a thickness measurement by a micrometer, or the like can be applied.
• the roughened nickel layer 50 may be formed on a surface on one side of the nickel-plated metal material 100 as depicted in FIG. 1 , or may be formed on both sides although not depicted in any of the figures.
• the roughened nickel layer 50 is formed with nickel.
• the roughened nickel layer 50 includes protruding shapes that protrude in a thickness direction of the base material 20. Describing regarding the protruding shapes, they are characterized in that a root mean square height Rq, which is a surface texture parameter of the surface of the roughened nickel layer 50 in the present embodiment, is 0.29 ⁇ m or greater and 0.90 ⁇ m or smaller. By specifying as described above, the protrusions of the roughened nickel layer 50 can bear even loads from multiple directions.
• surface texture parameters on the surface of the roughened nickel layer 50 can be measured by a known laser microscope or the like following Japanese Industrial Standard (JIS) B0601-2013 and International Organization for Standardization (ISO) 25178-2:2012.
• JIS Japanese Industrial Standard
• ISO International Organization for Standardization
• the roughened nickel layer 50 includes protrusions that protrude in the thickness direction of the base material 20. Focusing on the individual protrusions, the deposition and granule growth of the granular nickel plating are prioritized in a height direction, in other words, in the thickness direction of the plating metal material, than in the horizontal direction after precipitation nuclei have been formed apart from one another upon formation of protrusions with the roughened nickel plating, whereby the plurality of protrusions grow respectively.
• the heights and thicknesses of the protrusions and the sizes of clearances between the protrusions are not absolutely the same exactly.
• Sa, Ra, and Rzjis are mentioned as surface texture parameters that have been considered to contribute to the adhesion strength with another member.
• parameters such as Sa and Ra are each averaged, and Sa and Ra alone do not have any close relation with the presence or absence of protrusions or with another member.
• Rzjis has been considered to have a close relation with the adhesion strength with another member. Assuming, for example, that 100 protrusions are formed side by side, those which are reflected to Rzjis are however the heights of 10 protrusions at most, and no attention has been paid concerning variations in height.
• the present inventors have diligently studied to further improve the shear durability in nickel-plated metal materials having plating adhesion and adhesion with other members. As a result, it has been found that shear durability can be improved by reducing height differences among protrusions and optimizing the clearances between the protrusions. Further, by controlling the root mean square height Rq of the surface, on which the roughened nickel layer 50 is formed, to 0.29 ⁇ m or greater and 0.90 ⁇ m or smaller, a roughened shape can be formed in which, while the formation of protrusions of extraordinary heights is decreased, individual protrusions have a sufficient height and sufficient clearances are included, as recesses in the surface shape, between the protrusions.
• the upper limit of the root mean square height Rq is preferably controlled to 0.70 ⁇ m or smaller.
• the lower limit of the root mean square height Rq is preferably controlled to 0.30 ⁇ m or greater from the viewpoint that shear durability can be improved more stably, and more preferably to 0.31 ⁇ m or greater from the viewpoint that adhesion with another member can be obtained more stably.
• the nickel-plated metal material in the present embodiment is also characterized in that, on a surface thereof on the side of the roughened nickel layer 50, a maximum height Sz as a surface texture parameter is greater than 3.5 ⁇ m and 10.0 ⁇ m or smaller. If Sz is excessively high, there is a possibility that protrusions of an extraordinary height may have been formed. From the viewpoint of improvement in shear durability, the maximum height Sz is therefore preferably 10.0 ⁇ m or smaller, more preferably 8.0 ⁇ m or smaller. From the viewpoint of assurance of stable adhesion with another member, Sz is preferably greater than 4.0 ⁇ m, more preferably 4.3 ⁇ m or greater. Nonetheless, the maximum height Sz is a parameter that represents the maximum value of height, that is, only one point, and Sz, if taken alone, has neither correlation to the adhesion with another member nor correlation to shear durability.
• Sdr Developed Interfacial Area Ratio
• Sdr Developed Interfacial Area Ratio
• Sdr Developed Interfacial Area Ratio
• Sdr is preferably 17% or greater, more preferably 18% or greater, particularly preferably 20% or greater. From the viewpoint of improvement in shear durability, on the other hand, Sdr is more preferably 70% or smaller, and still more preferably 65% or smaller.
• a relative load length ratio Rmr is preferably 30% to 95% on the surface on the side of the roughened nickel layer 50.
• the control of the relative load length ratio Rmr to 30% or greater can stabilize the roughened shape of the core region, and can improve its shear durability.
• Rmr is controlled to 33% or greater.
• the shear durability can be improved.
• the control of Sdr (Developed Interfacial Area Ratio) to 16% or greater can improve the adhesion with another member even when the shear durability is improved by increasing Rmr.
• Rmr is more preferably 33% or greater, still more preferably 50% or greater, and particularly preferably 65% or greater. No upper limit is imposed in particular, but 95% or smaller is preferred because there is a concern that the clearances, into which another member are supposed to penetrate, could be narrowed if Rmr is excessively great.
• a root mean square slope R ⁇ q is preferably 15 to 50 degrees on the surface on the side of the roughened nickel layer 50.
• the lower limit of the root mean square slope R ⁇ q is more preferably 20 degrees or greater, and still more preferably 25 degrees or greater.
• Sdq (Root Mean Square Gradient) on the surface on the side of the roughened nickel layer 50 is preferably 0.50% or greater from the viewpoint of improvement in the adhesion with another member, and is preferably 1.80% or smaller from the viewpoint of improvement in shear durability.
• Sdq (Root Mean Square Gradient) is a value when the slopes of surface recesses and protrusions of the nickel-plated metal material are perceived over the entirety of the surface. It can be said that the protrusions and recesses on the surface are gentler as the value is smaller and are steeper as the value is greater.
• Sdq falls in the above-described range, improvement in shear durability is considered to be possible because the recesses and protrusions when perceived over the surface are relatively gentle despite the protrusions having heights.
• a shape formed by aggregation of plating granules on the tip of each protrusion is adequately rounded, and as a result, it is considered possible to control Sdq to 1.80% or smaller and to improve the shear durability.
• Sdq is preferably 0.50% or greater, more preferably 0.65% or greater, because the adhesion with another member may become insufficient if Sdq is excessively small.
• Sdq Root Mean Square Gradient
• Sdq is preferably 0.50% to 1.80% on the surface on the side of the roughened nickel layer 50 from the viewpoints of improvement in shear durability and the adhesion with another member.
• a ten-point mean roughness Rzjis is preferably 1.0 to 6.0 ⁇ m. More preferably, the ten-point mean roughness Rzjis is 1.5 to 4.9 ⁇ m, with 1.5 to ⁇ m being still more preferred.
• the arithmetical mean roughness Sa is preferably 0.2 to 0.7 ⁇ m on the surface on the side of the roughened nickel layer 50.
• the deposition amount of nickel in the roughened nickel layer 50 is preferably 3.5 to 19.0 g/m 2 from the viewpoints of improvement in shear durability and assurance of adhesion with another member. More preferred is 4.5 to 14.5 g/m 2 , and still more preferred is 5.5 to 13.9 g/m 2 .
• the method described in PCT Patent Publication No. WO2020/017655 or PCT Patent Publication No. WO2021/020338 , or the like can be appropriately adopted, for example.
• the nickel deposition amount can be determined by measuring the total nickel amount with respect to the nickel-plated metal material 100 using X-ray fluorescence (XRF) analysis or the like.
• the thickness of the entirety of the nickel-plated metal material 100 in the present embodiment A description will be made regarding the thickness of the entirety of the nickel-plated metal material 100 in the present embodiment.
• a thickness measurement by a cross-sectional observation under an SEM or a thickness measurement by a micrometer can be also applied.
• the thickness of the entirety of the nickel-plated metal material 100 in the present embodiment a range of 0.02 to 0.51 mm is preferred. Further, the thickness of the entirety of the nickel-plated metal material 100 is more preferably 0.02 to 0.31 mm, and still more preferably 0.035 to 0.11 mm, for example, from the viewpoint of strength, the viewpoint of a desired battery capacity, and the like.
• the nickel-plated metal material 100 in the present embodiment can be provided as a nickel-plated metal material that includes a roughened nickel layer having shear durability to loads from multiple directions.
• a nickel-plated metal material 200 As a second embodiment, a nickel-plated metal material 200 in the present embodiment is different from the above-mentioned first embodiment in that, as depicted in FIG. 2 , an intermediate metal layer 40 formed between the base material 20 and the roughened nickel layer 50 is included. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted. It is to be noted that, in this second embodiment, the root mean square height Rq and maximum height Sz on the surface on the side of the roughened nickel layer are also 0.29 ⁇ m or greater and 0.90 ⁇ m or smaller, and greater than 3.5 ⁇ m and 10.0 ⁇ m or smaller, respectively.
• the nickel-plated metal material 200 of the present embodiment is also used for collectors of positive electrodes or negative electrodes in secondary batteries and the like, electronic related devices, and the like. Without being limited to such collectors and electronic related devices, the nickel-plated metal material 200 can be suitably used also for members required to have high adhesion with other members (active materials, resins, and the like) such as battery members, members constituting electric/electronic related devices, interior members for automobiles and constructions, automobile members such as gaskets, and sliding members.
• other members active materials, resins, and the like
• a nickel layer, a nickel alloy layer, a layer with nickel and another metal stacked together, or the like is exemplified.
• the nickel alloy layer an iron-nickel alloy layer is exemplified.
• a layer with a nickel layer and an iron-nickel alloy layer stacked together can be exemplified.
• the formation of a nickel layer as the intermediate metal layer 40 is effective in that the adhesion of the roughened nickel layer 50 with the base material 20 is improved and shear durability can be obtained more stably.
• the total of the nickel deposition amount in the nickel layer is preferably 1.3 to 13.8 g/m 2 from the viewpoints of the adhesion with the base material and improvement in shear durability to loads from multiple directions. More preferred is 1.5 to 12 g/m 2 . Still more preferred is 1.7 to 8.8 g/m 2 from the viewpoint of shear durability.
• the deposition amount of nickel in the nickel layer can be measured by X-ray fluorescence (XRF) analysis or the like.
• the total deposition amount of nickel per side of the nickel-plated metal material in the case that the intermediate metal layer 40 is formed from the nickel layer alone is preferably 4.8 to 32.8 g/m 2 , more preferably 6.0 to 26.5 g/m 2 , and still more preferably 7.2 to 23.3 g/m 2 from the viewpoints of the adhesion with another member and improvement in shear durability.
• the above-described total deposition amount is the total of deposition amounts of nickel contained in the nickel layer and the roughened nickel layer, respectively.
• the thickness of the nickel layer is preferably 0.1 to 1.0 ⁇ m, more preferably 0.1 to 0.8 ⁇ m, from the viewpoints of making small the thickness of the entirety of the nickel-plated metal material 200 while ensuring shear durability or the like to loads from multiple directions. Furthermore, from the view point of shear durability, 0.12 ⁇ m or greater is preferred, with 0.15 ⁇ m or greater being particularly preferred.
• a thickness measurement based on an analysis by SEM-energy dispersive X-ray spectroscopy (EDX) can be applied.
• the intermediate metal layer 40 is a stacked layer of a nickel layer and an iron-nickel layer
• the iron-nickel alloy layer, the nickel layer, and the roughened nickel layer 50 may be stacked in this order from the base material 20.
• a metal layer of a kind different from nickel and iron may be formed between the base material 20 and the roughened nickel layer 50. From the viewpoint of improvement in the plating adhesion of the roughened nickel layer 50 with the base material, it is preferred to stack in the order of the iron-nickel alloy layer, the nickel layer, and the roughened nickel layer 50.
• the iron-nickel alloy layer is an alloy layer with iron (Fe) and nickel (Ni) contained therein, and is a metal layer in which an alloy formed of iron and nickel (also called an "iron-nickel alloy” or an "Fe-Ni alloy”) is contained.
• an alloy formed of iron and nickel also called an "iron-nickel alloy” or an "Fe-Ni alloy”
• the phase of this alloy formed of iron and nickel it may be any one of a solid solution, an eutectoid/eutectic, and a compound (intermetallic compound), or two or more of these phases may coexist.
• the iron-nickel alloy layer may contain one or more other metal elements and inevitable impurities insofar as the problem intended to be solved in the present invention can be solved.
• metal elements such as cobalt (Co) and molybdenum (Mo) and an additive element such as boron (B) may be contained in the iron-nickel alloy layer.
• the proportion of metal elements other than iron (Fe) and nickel (Ni) in the iron-nickel alloy layer is preferably 5 wt% or lower, more preferably 3 wt% or lower, and still more preferably 1 wt% or lower.
• the iron-nickel alloy layer may be a binary alloy formed substantially from only iron and nickel, the lower limit of the content proportion of one or more other metal element or elements except for inevitable impurities is 0%.
• the kinds and amounts of one or more other metal elements contained can be determined by known means such as X-ray fluorescence (XRF) spectrometer or glow discharge optical emission spectroscopy (GDS).
• XRF X-ray fluorescence
• GDS glow discharge optical emission spectroscopy
• the thickness of the iron-nickel alloy layer included in the nickel-plated metal material 200 of the present embodiment 0.4 ⁇ m or greater is preferred, 0.6 ⁇ m or greater is preferred, and 0.7 ⁇ m or greater is more preferred. No upper limit is imposed in particular, but as the resistance increases if excessively thick, the thickness is preferably 7.5 ⁇ m or smaller, more preferably 6 ⁇ m or smaller, per side.
• the thickness is preferably 6 ⁇ m or smaller, more preferably 3.5 ⁇ m or smaller from the viewpoint of avoidance of unevenness in metal deposition amount control and heat treatment.
• a thickness measurement based on an analysis by SEM-EDX on a cross-section of the nickel-plated metal material can be applied.
• a method that reads a thickness from a graph obtained by SEM-EDX can be applied as in PCT Patent Publication No. WO2022/231009 .
• the deposition amount of nickel in the iron-nickel alloy layer is preferably 0.89 to 26.7 g/m 2 . 1.3 to 17.8 g/m 2 is more preferred. It is to be noted that the deposition amount of nickel in the iron-nickel alloy layer can be measured by X-ray fluorescence (XRF) analysis or the like.
• the total of the deposition amount of nickel in the iron-nickel alloy layer and the deposition amount of nickel in the nickel layer is preferably 1.0 to 36.1 g/m 2 from the viewpoint of stable deposition of the roughened plating.
• the nickel deposition amount in the nickel layer is preferably 0.08 to 8.8 g/m 2 , more preferably 0.13 to 7.6 g/m 2 , and still more preferably 1.1 to 7.1 g/m 2 from the viewpoint of stable deposition of the roughened plating.
• the nickel-plated metal material 200 can be obtained by steps including, for example, nickel plating treatment, heat treatment for obtaining the iron-nickel alloy layer, strike nickel-plating treatment, undercoat nickel-plating treatment, and roughened nickel-plating treatment.
• the deposition amount of nickel in the nickel layer at this time can be controlled on the basis of the deposition amounts upon the strike nickel-plating treatment and the undercoat nickel-plating treatment.
• the nickel layer may be formed without allowing iron to diffuse to the surface in the above-described heat treatment step, and the strike nickel treatment and the undercoat nickel-plating treatment may be further applied to the nickel layer.
• the deposition amount of nickel in the nickel layer of the nickel-plated metal material 200 in the foregoing case is preferably determined through conversion to the deposition amount from the thickness by a cross-sectional observation.
• the total deposition amount of nickel per side of the nickel-plated metal material in the case that the iron-nickel alloy layer is included is preferably 4.5 to 55.1 g/m 2 , more preferably 5.9 to 39.9 g/m 2 , and still more preferably 8.1 to 36.5 g/m 2 from the viewpoints of adhesion with another member, improvement in shear durability, and improvement in corrosion resistance.
• the above-described total deposition amount is the total of deposition amounts of nickel contained in the iron-nickel alloy layer, the nickel layer, and the roughened nickel layer, respectively.
• the method described in PCT Patent Publication No. WO2020/017655 or PCT Patent Publication No. WO2021/020338 , or the like can be appropriately adopted, for example.
• the nickel deposition amount can be determined by measuring the total nickel amount with respect to the nickel-plated metal material 200 using X-ray fluorescence (XRF) analysis or the like.
• XRF X-ray fluorescence
• the intermediate metal layer 40 is formed on one side of the base material 20 in FIG. 2 , but without being limited to this configuration, such intermediate metal layers may be formed on both sides, respectively, of the base material 20 although not depicted in any of the figures. Further, in the case that the intermediate metal layers 40 are formed on both sides, the thickness of one of the intermediate metal layers 40 may be the same as or different from that of the other intermediate metal layer 40.
• a method by plating or plating and heat treatment is preferred.
• the plating include methods such as electrolytic plating, electroless plating, melt plating, dry plating, and the like. Of these, the method by electrolytic plating is particularly preferred from the viewpoints of cost, film thickness control, and the like.
• Examples of a manufacturing method in the case that the intermediate metal layer 40 is an iron-nickel alloy layer include a method that forms the nickel plating layer on at least one side of the base material 20 by a method such as electrolytic plating, and iron (Fe) in the base material 20 and nickel (Ni) in the nickel plating layer are then caused to diffuse into an alloy by thermal diffusion treatment or the like, and a method that forms an alloy layer by iron-nickel alloy plating.
• the nickel layer is obtained by a method that forms the nickel layer by leaving a region of nickel alone without allowing iron (Fe) to diffuse to the surface in the above-described thermal fusion treatment, a method that applies nickel plating after the above-described thermal fusion treatment to form the nickel layer, a method that forms the nickel layer by a combination of both of these methods, or a like method, or a roughened nickel layer may be formed after subjecting the surface-treated steel sheet, which has been provided with the iron-nickel alloy layer by the above-described thermal fusion treatment, to rolling or rolling and heat treatment. It is to be noted that details regarding these manufacturing methods will be mentioned later.
• the nickel-plated metal material 300 in the third embodiment is different from the above-mentioned first embodiment in that, as depicted in FIG. 3 , a coating metal layer 70 is included on the roughened nickel layer 50. Accordingly, this different point will be primarily described, the other points will be identified by the same reference signs, and their description is omitted.
• the roughened nickel layer 50 and the coating metal layer 70 may also be collectively called a "roughened layer.”
• individual surface texture parameters as measured from the side of the roughened layer should fall within the specified ranges in the first embodiment.
• the nickel-plated metal material 300 of the present embodiment is also used for collectors of positive electrodes or negative electrodes in secondary batteries and the like, electronic related devices, and so on. Without being limited to such collectors and electronic related devices, the nickel-plated metal material 300 can be suitably used also for members required to have high adhesion with other members (active materials, resins, and the like) such as battery members, members constituting electric/electronic related devices, interior members for automobiles and constructions, automobile members such as gaskets, and sliding members.
• other members active materials, resins, and the like
• the coating metal layer 70 is formed on the roughened nickel layer 50.
• Example of a metal material forming the coating metal layer 70 include zinc (Zn), tin (Sn), and chromium (Cr), and alloys thereof.
• the inclusion of the coating metal layer 70 is advantageous in that, as a whole, the nickel-plated metal material 300 is provided with improvement in sacrificial corrosion protection property or corrosion resistance.
• the coating metal layer 70 also contributes to improvement in adhesion between the roughened nickel layer 50 and the base material 20.
• the zinc deposition amount is preferably 0.5 to 22.0 g/m 2 .
• the chromium deposition amount is preferably 0.05 to 10.0 g/m 2 .
• the coating metal layer 70 is tin, the tin deposition amount is preferably 0.2 to 20.0 g/m 2 .
• Measurements of respective deposition amounts of zinc, chromium, and tin can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or inductively coupled plasma (ICP) emission spectroscopy.
• XRF X-ray fluorescence
• ICP inductively coupled plasma
• the coating metal layer 70 in the present embodiment can be formed by applying electroplating with the corresponding metal on the roughened nickel layer 50. It is to be noted that, in the third embodiment, the intermediate metal layer 40 in the second embodiment may more preferably be included between the roughened nickel layer 50 and the base material 20.
• each nickel-plated metal material includes a step (roughened nickel-plating step) that applies roughened nickel-plating to at least one side of the base material 20 to form the roughened nickel layer.
• the roughened nickel-plating step includes at least a first roughened nickel-plating step, and, after the first roughened nickel-plating step, may also include a second roughened nickel-plating step for improvement in the adhesion of the roughened nickel layer with the base material.
• nickel sulfate hexahydrate or/and nickel chloride hexahydrate are used such that their total amount is 10 g/L (inclusive) to less than 48 g/L, the chloride ion concentration is preferably 5 to 90 g/L, more preferably 5 to 75 g/L, and still more preferably 10 to 50 g/L, the ratio of nickel ions to ammonium ions is preferably 0.05 to 0.75, more preferably 0.05 to 0.60, still more preferably 0.05 to 0.50, and even still more preferably 0.05 to 0.30, in terms of the weight ratio of "nickel ions/ammonium ions," and the bath electrical conductivity at 50°C is preferably 5.00 to 30.00 S/m, more preferably 5.00 to 20.00 S/m, and still more preferably 7.00 to 20.00 S/m.
• chloride ion concentration 10 g/L or higher, a good roughened plating state is easily obtained even if the deposition amount in roughened nickel-plating is somewhat small.
• a method that adjusts the chloride ion concentration of the plating bath, the ratio of nickel ions to ammonium ions, and the bath electrical conductivity to the above-described ranges include, but are not particularly limited to, a method that uses, as the plating bath, one containing nickel sulfate hexahydrate, nickel chloride hexahydrate, and ammonium sulfate, and appropriately adjusts their blending amounts.
• ammonia to the nickel-plating bath may be conducted by using ammonia solution, ammonium chloride, or the like in place of ammonium sulfate.
• the ammonia concentration in the plating bath is preferably 6 to 35 g/L, more preferably 10 to 35 g/L, still more preferably 16 to 35 g/L, and even still more preferably 20 to 35 g/L.
• a basic nickel carbonate compound, hydrochloric acid, sodium chloride, potassium chloride, or the like may be used to control the chlorine ion concentration.
• a nickel-plated metal material which is excellent in shear durability and has adhesion with another member, is obtained by using, as a circulating bath, a plating bath of a formula, in which the chloride ion concentration, the ratio of nickel ions to ammonium ions, and the ammonia concentration have been controlled to the above-described ranges, and intermittently conducting plating treatment a plurality of times at a current density of 15.0 A/dm 2 or higher in the first roughened nickel-plating step.
• the expression "using as a circulating bath” means that electroplating is conducted while maintaining solution circulation by a pump through a plating solution in a plating tank. It is preferred for the solution circulation to control the pump-assisted circulation rate of the solution at a flow rate of 25 L/min or higher per 1000 L of the plating filled in the plating solution tank. Especially, if a tank of over 1000 L is used, the solution circulation is preferably a circulation that flows in from a lower part of the tank and flows out of the tank from an upper part of the tank.
• the expression "intermittently conducting plating treatment a plurality of times" means to define, as one cycle, three steps, that is, a step of inserting a base material or a pretreated base material into a plating bath, an energizing and electrolytically precipitating step, and a step of pulling up from the plating bath, and to repeat this cycle at least twice or more.
• the conventional roughened nickel-plating step has used, for example, a drum-type plating bath, or a single plating bath in a laboratory, and has conducted the above-described cycle in one cycle.
• a drum-type plating bath or a single plating bath in a laboratory
• the formation of preferentially growing protrusions is facilitated among protrusions that make up a roughened shape, thereby facilitating improvement of the adhesion with another member such as resin or the like.
• the protrusions other than the preferentially growing protrusions are excessively short, and the resin adhesion is significantly lowered. It has been therefore difficult to improve the shear durability.
• the present inventors have conducted diligent deliberation for a roughened shape, which can suppress preferential growth of protrusions and can obtain adhesion with another member, in order to obtain shear durability to loads in multiple directions upon continuous rolling or the like, and its manufacturing method, and have found that a roughened shape having shear durability can be obtained by combining control of the current density to 15.0 A/dm 2 or higher, circulation of a plating solution, and a plurality of times of plating treatment. Giving as a reason that a good roughened shape is obtained by such a combination, the following consideration can be made.
• the plating solution is constantly supplied with sufficient ion concentrations and without stagnation to a surface of a target (base material) that is under roughened nickel-plating treatment. Therefore, the ion concentrations in the plating solution in a neighborhood of the base material can be made even, thereby creating a state that irregularity is hard to occur on precipitation starting points, and hence making it possible to obtain still more precipitation points. Further, the adoption of a plurality of timings to dip into the plating solution can suppress some protrusions from preferentially growing, thereby allowing many protrusions to grow uniform.
• the chloride ion concentration and the ratio of nickel ions to ammonium ions to the above-described ranges, and the current density to 15.0 A/dm 2 or higher, precipitation in the height direction for the formation of protrusions and granule growth for the thickening of the protrusions can be promoted while suppressing such precipitation and growth that precipitated nickel-plating granules excessively grow in a horizontal direction into a layer.
• the current density is preferably 15.0 A/m 2 or higher, more preferably 18.0 A/m 2 or higher.
• the current density is preferably 40 A/dm 2 or lower, more preferably 35 A/dm 2 or lower.
• the current density during energization in each cycle is 15 to 40 A/dm 2
• the average current density in all the cycles is 15 to 40 A/dm 2 .
• the current density during energization in each cycle is 18 to 35 A/dm 2
• the average current density in all the cycles is 18 to 35 A/dm 2 . It is preferred to conduct the plating treatment with an electricity quantity of 100 to 1500 C/dm 2 in such a current density range.
• precipitation points increase in number or granule growth is prone to occur excessively if the total amount of nickel sulfate hexahydrate and nickel chlorate hexahydrate in the plating bath is 48 g/L or more. Even if a granular precipitate is formed and the surface is coarse compared with a general nickel plating, the intended roughened shape is thus difficult to be obtained in a case where, for example, tall protrusions are not formed, clearances are too small to obtain adhesion with another member, or aggregates cannot grow into the shape of a protrusion due to too many precipitation points. In a case of less than 10 g/L, on the other hand, nickel ions for the precipitation of nickel run out, and hence, there is a possibility that nickel may not precipitate and a roughened nickel layer may not be obtained.
• a roughened nickel layer excellent in shear durability and also excellent in adhesion with another member can be obtained.
• Examples of plating conditions are as follows.
• a plurality of plating treatment can be conducted in the circulating bath by adjusting the average current density and electrolysis time such that the total electricity quantity is controlled as described above.
• the plating time is preferably 7 to 60 seconds, because if the plating time is short, some protrusions are prone to preferentially grow, and if too long, protrusions grow uniform and tall protrusions are prone to grow.
• the roughened nickel layer may be obtained by only the above-described first roughened nickel-plating step, or the roughened nickel layer may be obtained by conducting the second roughened nickel-plating step under the below-described conditions after the first roughened nickel-plating step.
• Effects by the second roughened nickel-plating are as follows. Firstly, by promoting the growth of the individual plating granules in the aggregates of the protruding granular precipitate formed by the first roughened nickel-plating, minute clearances between the granules themselves inside the aggregates are filled up with a highly compatible crystalline structure, whereby the protrusions can be made more difficult to break. Secondly, on the roots of protrusions, nickel crystals precipitate, similarly filling up clearances between the base material and the particles of the roots of the protrusions, or covering both, whereby the adhesion between the base material and the protrusions is improved to make the protrusions more difficult to break.
• the side wall of the protrusion also undergoes granule growth, and the protrusion can be made thicker and more difficult to break.
• the granules on the tips of protrusions to grow, better adhesion with another member can be obtained, and the tip particles are made hard to fall off when they come into contact with rolls or the like, whereby the shear durability can be also improved.
• the roughened shape obtained in the first roughened nickel-plating step is provided with sufficient shear durability and sufficient adhesion with another member, it is not absolutely necessary to go through the second roughened nickel-plating step, but in the first embodiment and the second embodiment, it is preferred to conduct the second roughened nickel-plating step.
• a step of forming the coating metal layer 70 may be conducted after the second roughened nickel-plating step, or the step of forming the coating metal layer 70 may be conducted instead of the second roughened nickel-plating step.
• the deposition amount of the roughened nickel layer is preferably 3.5 to 19.0 g/m 2 , more preferably 4.5 to 14.5 g/m 2 , and still more preferably 5.5 to 13.9 g/m 2 .
• the nickel deposition amount in the first roughened nickel-plating (hereinafter also called the "first deposition amount”) is preferably controlled to 3.5 to 12.0 g/m 2 from the viewpoints of assurance of adhesion with another member and improvement in shear durability. From the viewpoint of the improvement in the adhesion with another member, the first deposition amount is controlled more preferably to g/m 2 or more. In addition, from the viewpoints of suppressing the preferential growth of some protrusions and improving the shear durability, the first deposition amount is controlled more preferably to 9.3 g/m 2 or less, and still more preferably to 8.9 g/m 2 or less.
• the lower limit of the nickel deposition amount in the second roughened nickel-plating step (hereinafter also called the "second deposition amount") is 0.0 g/m 2 .
• the second adhesion amount is preferably 1.0 g/m 2 or more, more preferably 1.5 g/m 2 or more.
• the second adhesion amount is preferably 7.0 g/m 2 or less, more preferably 5.2 g/m 2 or less, and still more preferably 5.0 g/m 2 or less.
• the intermediate metal layer is a nickel layer in the manufacturing method of the nickel-plated metal material depicted in FIG. 2
• a step of forming a nickel layer by applying nickel plating onto the base material 20 (hereinafter also referred to as the "nickel-plating step” or the “undercoat nickel-plating step”) may be included. Examples of nickel-plating conditions for the nickel-plating step will hereinafter be described.
• a known nickel sulfamate bath or citrate bath may also be used beside the above-described Watts bath.
• an additive such as a known gloss agent may be added to the plating bath to form gloss nickel-plating or semi-gloss nickel-plating.
• the base material is a metal sheet made of Al or an Al-based alloy
• strike nickel-plating treatment may be applied under the below-described conditions before the roughened nickel-plating step or undercoat nickel-plating step.
• the base material is a metal sheet made of an alloy based on one type selected from a pure metal selected from Ni, Fe other than a carbon steel sheet, and Ni, or if an iron-nickel alloy layer is formed, it is preferred to go through a step of strike nickel-plating treatment.
• an iron-nickel alloy layer forming step may be included to form the iron-nickel alloy layer on the base material 20.
• the above-mentioned roughened nickel-plating step may be conducted after the above-mentioned iron-nickel alloy layer forming step.
• the iron-nickel alloy layer forming step can form the iron-nickel alloy layer through thermal diffusion by applying thermal diffusion after forming the nickel-plating layer on at least one side of a steel sheet as the base material 20 by electrolytic plating. It is to be noted that, in this case, the above-mentioned nickel-plating conditions can be applied as the step which forms the nickel-plating layer.
• the heat treatment after the formation of the nickel-plating layer continuous annealing or batch annealing (box annealing) can be conducted.
• the continuous annealing treatment can be conducted at 650°C to 950°C for a soaking time in a range of 15 to 150 seconds.
• the batch annealing (box annealing) treatment can be conducted at 450°C to 690°C, for a soaking time in a range of 1.5 to 20 hours, and for a total time of heatup, soaking, and cooling time in a range of 4 to 80 hours. Rolling may be applied after the above-described heat treatment. Further, heat treatment may be conducted again after the rolling.
• the iron-nickel alloy layer as the intermediate metal layer may also be formed by applying alloy electrolytic plating to at least one side of the base material 20 using an iron-nickel alloy plating bath containing iron ions and nickel ions. Examples of plating conditions will hereinafter be described.
• the deposition amount of nickel in the intermediate metal layer to be formed on the base material 20 is preferably 1.3 to 36.1 g/m 2 per side. If the deposition amount exceeds 36.1 g/m 2 , the operability of electrolytic plating is lowered, so that the cost increases significantly. If the deposition amount is less than 1.3 g/m 2 , there is a possibility that irregular shapes are prone to occur in the subsequent roughened nickel-plating step, and such a deposition amount is not preferred accordingly.
• the present embodiment can suppress the formation of protrusions having a prominent height. As a result, not only shear durability but also plating adhesion can be heightened, whereby the deposition amount of nickel in the intermediate metal layer can be reduced.
• the deposition amount of nickel in the nickel layer to be formed by nickel plating or strike nickel-plating is preferably 1.3 to 13.8 g/m 2 , more preferably 1.5 to 12 g/m 2 , and still more preferably 1.7 to 8.8 g/m 2 per side from the viewpoint of improvement in shear durability.
• the nickel deposition amount of the nickel layer to be formed by nickel plating and strike nickel-plating after the formation of the iron-nickel alloy layer is preferably 0.08 to 8.8 g/m 2 , more preferably 0.13 to 7.6 g/m 2 , and still more preferably 1.1 to 7.1 g/m 2 from the viewpoints of improvement in shear durability and improvement in corrosion resistance.
• the above-mentioned step of forming the nickel layer and the above-mentioned step of forming the iron-nickel alloy layer may be both included.
• the nickel layer can be formed in a known nickel bath such as the above-mentioned Watts bath, nickel sulfamate bath, or citrate bath.
• the above-described manufacturing method of the nickel-plated metal material may include, shortly before forming the nickel layer, a step of applying known strike nickel-plating treatment.
• the nickel layer and the iron-nickel alloy layer may be stacked together by allowing a nickel portion to remain when conducting diffusion by heat treatment in the step of forming the iron-nickel alloy layer.
• the manufacturing method of the nickel-plated metal material depicted in FIG. 3 may include a step (coating metal plating step) of forming a coating metal layer by applying coating metal plating onto the roughened nickel layer formed by the above-mentioned roughened nickel-plating step.
• bath composition for the electro-zinc plating and plating conditions are as follows.
• a bath that uses a sulfate salt as a supply source for zinc ions and is appropriately added with a conductive adjuvant such as ammonium sulfate or sulfuric acid to increase the electrical conductivity of the plating solution.
• a conductive adjuvant such as ammonium sulfate or sulfuric acid
• an additive such as a known gloss agent may be added to the plating bath to form gloss zinc plating or semi-gloss zinc plating.
• a chromium layer is formed as the coating metal layer 70, it can be formed by conducting chromium plating or chromate treatment. Examples of chromium plating conditions are as follows.
• bath composition for the electro-tin plating and plating conditions are as follows.
• measurements of the zinc deposition amount, the chromium deposition amount, and the tin deposition amount can be conducted by using a known method such as X-ray fluorescence (XRF) analysis or ICP emission spectroscopy.
• XRF X-ray fluorescence
• the root mean square height Rq which is a surface texture parameter on the surface of the roughened nickel layer 50, was measured by following JIS B0601-2013 as described below.
• a laser microscope manufactured by Olympus Corporation, 3D measuring laser microscope "LEXT OLS5000”
• an analysis image of 259 ⁇ m ⁇ 258 ⁇ m visual field was acquired under conditions of a 50 ⁇ objective lens (lens name: "MPLAPON50XLEXT").
• denoising and inclination correction as automated correction processing were then conducted on the acquired analysis image.
• the icon for surface roughness measurement was clicked to perform an analysis, whereby the surface texture parameter was obtained.
• a root mean square height Rq is a surface texture parameter by a contour curve method, which is obtained by following JIS B0601-2013.
• JIS B0601-2013 With a view to obtaining cross-sectional curves in the above 259 ⁇ m ⁇ 258 ⁇ m visual field, it was assumed that the cross-sectional curves were obtained in a direction perpendicular to the rolling direction (or the rolling direction in continuous rolling) of the base material, and 15 cross-sectional curves were obtained such that they are separated at equal intervals in the above-described vision field.
• a root mean square height was measured 15 times, and their average value was calculated as the root mean square height Rq. It is to be noted that the analysis was made under no conditions, without setting any of filter criteria (F operation, S filter, L filter) for analysis.
• a peel test by the self-adhesive tape so applied was conducted under the guidelines of the pull-off testing method described in JIS H 8504.
• the self-adhesive tape after the peel test was applied to a base paper sheet of the same kind as that of the above-described reference sample, and its lightness L* and chromaticities a* and b* were measured by using the spectrophotometer as in the above.
• the adhesion with resin was evaluated. Specifically, a peel test was conducted to evaluate the resin adhesion, and peel strength was obtained. A description will hereinafter be made regarding its measuring method. Firstly, a nickel-plated metal material (30 mm ⁇ 150 mm) was provided. A polypropylene film of 140 ⁇ m thickness (25 mm ⁇ 150 mm) was heat-sealed to the side of the roughened nickel layer by a heat sealer (manufactured by TESTER SANGYO CO., LTD., "TP-701-B”), whereby a specimen was obtained.
• a heat sealer manufactured by TESTER SANGYO CO., LTD., "TP-701-B
• the heat-sealing temperature was set to 156°C, the heating time was set to 5 seconds, and the heating pressure was set to 0.2 MPa.
• the resin film was then pulled relative to the base material in a 180° direction at a rate of 50 mm/min by a tension testing machine (manufactured by Shimadzu Corporation, "AGS-X 5kN"), whereby its peel strength was obtained. Owing to the use of the peel test that pulls in the 180° direction, loads from multiple directions after the bonding with the resin were also evaluated. On the basis of the following criteria, an evaluation of the resin adhesion was made.
• a filter paper P (cotton fibers) was placed on a surface of a nickel-plated metal material, the surface being on the side of a roughened nickel layer, a jig J was mounted on the filter paper P ( FIG. 4(a) ), and a load of 1 kg was applied from above ( FIG. 4(b) ).
• a load of 1 kg was applied from above ( FIG. 4(b) ).
• the filter paper P was taken out, and the amount of nickel stuck on the filter paper P was determined by X-ray fluorescence measurement.
• An evaluation of shear durability was made on the basis of whether or not the deposition amount (g/m 2 ) of nickel on a contact surface of the filter paper P satisfied the criteria to be described hereinafter.
• the determination was made on the basis of the deposition amount (g/m 2 ) of all pieces of metal on the filter paper P.
• the evaluation of shear durability was made on the basis of whether or not the total value of a deposition amount (g/m 2 ) of nickel and a deposition amount (g/m 2 ) of tin on the contact surface of the filter paper P satisfied the following criteria.
• a cold-rolled foil (thickness: 200 ⁇ m) of low-carbon aluminum-killed steel having a chemical composition presented below was first provided as the base material 20.
• nickel plating was conducted on both sides of the steel foil under the below-described conditions, whereby a nickel-plating layer was formed. It is to be noted that conditions for the nickel plating were set as follows.
• a surface-treated steel foil having an iron-nickel alloy layer on both sides was obtained.
• the thickness of the surface-treated steel foil was 60 ⁇ m.
• the thickness of the iron-nickel alloy layer was checked by GDS, it was found to be 3.1 ⁇ m.
• the nickel deposition amount on the surface of the surface-treated steel foil having the above-described iron-nickel alloy layer was measured by using an X-ray fluorescence spectrometer (instrument name: "ZSX100e” manufactured by Rigaku Corporation), it was found to be 13.5 g/m 2 .
• undercoat nickel layer On each surface of the above-described surface-treated steel foil, a nickel layer (hereinafter referred to as the "undercoat nickel layer") to be located between the iron-nickel alloy layer and a roughened nickel layer was formed under the undercoat nickel-plating conditions presented below, whereby the undercoat nickel layer was formed in a deposition amount of 3.9 g/m 2 . It is to be noted that strike nickel-plating was applied in a deposition amount of 0.1 g/m 2 shortly before the undercoat nickel-plating. The undercoat nickel layer was formed on both sides.
• the "roughened nickel layer” was next formed. It is to be noted that the roughened nickel layer was formed by applying the following first roughened nickel-plating and the second roughened nickel-plating.
• Values of Rq and Sz on an outermost surface formed on the roughened nickel layer of the nickel-plated metal material are presented in Table 1. Values of individual surface texture parameters are also presented in Table 1. Using the laser microscope (manufactured by Olympus Corporation, 3D measuring laser microscope "LEXT OLS5000”), the surface texture parameters were measured under the conditions of the 50 ⁇ objective lens of OLS5000. The adhesion between the base material and the roughened nickel layer, the resin adhesion, and the amount of nickel deposited on a filter paper in a scratch test were also measured. The individual measurement results or evaluation results based on the measurement results are presented in Table 1.
• Example 1 was followed except that, as presented in Table 2, the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the average current density and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the average current density and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating in the first roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amount of a roughened nickel layer obtained by the first roughened nickel-plating were different. It is to be noted that the second roughened nickel-plating was not conducted. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the average current density and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the average current density and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• Example 1 was followed except that, as presented in Table 2, the number of plating bath insertions, average current density, and electrolysis time in the first roughened nickel-plating, and the deposition amounts of roughened nickel layers obtained by the first roughened nickel-plating and second roughened nickel-plating were different. The results are presented in Table 1 and Table 2.
• a 60 ⁇ m-thick cold-rolled steel foil of low-carbon aluminum-killed steel was provided as a base material 20.
• the treatment before the undercoat nickel-plating was not conducted on the base material 20.
• an undercoat nickel layer with the deposition amount presented in Table 1 was formed by using the undercoat nickel-plating conditions in Example 1.
• a "roughened nickel layer" was formed on the undercoat nickel layer.
• the first roughened nickel-plating conditions were set as described below.
• the second roughened nickel-plating conditions were set to be the same as those in Example 1.
• the deposition amount was set as in Table 1. Otherwise, Example 1 was followed.
• the results are presented in Table 1 and Table 2.
• the first roughened nickel-plating conditions were set as described below. Further, the nickel deposition amounts by the first roughened nickel-plating and second roughened nickel-plating were set as presented in Table 1. Otherwise, Comparative Example 5 was followed. The results are presented in Table 1 and Table 2.
• a 60 ⁇ m-thick cold-rolled steel foil of low-carbon aluminum-killed steel was provided as a base material 20.
• the treatment before the undercoat nickel-plating was not conducted on the base material 20.
• an undercoat nickel layer with the deposition amount presented in Table 1 was formed by using the undercoat nickel-plating conditions in Example 1.
• the first roughened nickel-plating was conducted under the conditions presented in Table 4.
• Example 1 coating treatment was conducted under the coating metal layer forming conditions described hereinafter, whereby a roughened layer having a coating metal layer made of tin (hereinafter also called a "coating tin layer”) was formed on a roughened nickel layer on one side.
• the deposition amount was set as presented in Table 4. Otherwise, Example 1 was followed.
• the roughened layer in the present Example was formed by the first roughened nickel-plating step and the coating metal layer forming step, which formed the coating metal layer, under the conditions presented in Table 4.
• a coating treatment step was executed by using tin plating. The results are presented in Table 3 and Table 4.
• the coating tin layer was obtained under the above-described conditions.
• Example 13 was followed except that the tin deposition amount in the coating metal layer obtained by the coating treatment step was changed by adjusting the electrolysis time. The results are presented in Table 3 and Table 4.
• Example 13 was followed except that the nickel deposition amount in the roughened nickel layer obtained by the first roughened nickel-plating and the tin deposition amount in the coating metal layer obtained by the coating treatment step were changed by adjusting the electrolysis time.
• the results are presented in Table 3 and Table 4.
• Example 13 was followed except that the nickel deposition amount in the roughened nickel layer obtained by the first roughened nickel-plating and the tin deposition amount in the coating metal layer obtained by the coating treatment step were changed by adjusting the electrolysis time.
• the results are presented in Table 3 and Table 4.
• Examples 1 to 15 have been confirmed to be preferred in all characteristics including not only plating adhesion but also adhesion with another member and shear durability, as the resin adhesion (peel test) was 13N/25 mm or higher and the deposition amount in the evaluation of shear durability by the scratch test was less than 2.0 g/m 2 .
• the resin adhesion peel test
• Comparative Example 5 Comparative Example 7
• Rq fell outside the prescribed range, thereby failing to achieve the object from the viewpoint of shear durability.
• Comparative Example 4 and Comparative Example 6 either Rq or Sz fell outside the range, thereby failing to achieve the object from the viewpoint of adhesion with another member.
• the nickel-plated metal materials in this disclosure can be suitably used for members required to have high adhesion with other members (active materials, resins, and the like) in battery members, members constituting electric/electronic related devices, interior members for automobiles and constructions, automobile members such as gaskets, and sliding members.

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