WO2018189916A1 - 電気めっき方法及び装置 - Google Patents
電気めっき方法及び装置 Download PDFInfo
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- WO2018189916A1 WO2018189916A1 PCT/JP2017/017949 JP2017017949W WO2018189916A1 WO 2018189916 A1 WO2018189916 A1 WO 2018189916A1 JP 2017017949 W JP2017017949 W JP 2017017949W WO 2018189916 A1 WO2018189916 A1 WO 2018189916A1
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- plating layer
- electroplating
- metal element
- base material
- plating
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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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/02—Slide fasteners
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/16—Apparatus for electrolytic coating of small objects in bulk
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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
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/16—Apparatus for electrolytic coating of small objects in bulk
- C25D17/18—Apparatus for electrolytic coating of small objects in bulk having closed containers
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
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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
- C25D5/007—Electroplating using magnetic fields, e.g. magnets
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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
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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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline layers
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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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
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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
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
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- A—HUMAN NECESSITIES
- A44—HABERDASHERY; JEWELLERY
- A44B—BUTTONS, PINS, BUCKLES, SLIDE FASTENERS, OR THE LIKE
- A44B19/00—Slide fasteners
- A44B19/24—Details
- A44B19/26—Sliders
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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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/10—Agitating of electrolytes; Moving of racks
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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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/625—Discontinuous layers, e.g. microcracked layers
Definitions
- the present disclosure relates to an electroplating method and apparatus.
- Patent Document 1 stirs the object 6 to be plated on the elastic body 4 in accordance with the expansion and contraction of the elastic body 4 at the bottom of the processing container 1.
- electroplating by energization between the first electrode 7 and the second electrode 12 provided on the elastic body 4. This stirring and electroplating are performed simultaneously.
- the elastic body 4 is deformed by an air cylinder.
- FIG. 2 of the same document shows a state where the rod of the air cylinder is retracted
- FIG. 3 of the same document shows a state where the rod is advanced.
- the object 6 to be plated is agitated by repeating the states of FIGS.
- Patent Document 2 discloses that the pipe 1 in the barrel 2 is smoothed with a medium 7 during copper plating in paragraph 0052 of the same document.
- Patent Document 3 discloses a plating apparatus that uses a centrifugal force generated by rotating a plating chamber to perform plating on an object to be plated.
- the plating chamber 4 includes a rotating body 11 provided with a cathode 10, a tubular member 3, and an anode 13 loosely fitted to the tubular member 3 inside the rotating body 11.
- the rotating body 11 is driven by an electric motor 18.
- the rotating body 11 rotates, the workpiece 1 in the rotating body 11 is pressed against the cathode 10 according to the centrifugal force.
- a plating layer is formed on the external electrode of the workpiece 1 facing the anode 13.
- Patent Document 4 relates to a plating apparatus similar to Patent Document 3.
- Patent document 4 discloses introducing a stirring medium into a plating process chamber in order to suppress aggregation of a to-be-plated object and a conductive medium.
- An electroplating method includes: A stirring step of causing a group of base materials (51) settled in the electrolytic solution in the electroplating tank (10) to flow in the circumferential direction along the inner wall (19) of the electroplating tank (10); An electroplating step of electroplating the group of base materials (51) flowing along the circumferential direction in the electrolytic solution in the electroplating tank (10); The flow along the circumferential direction of the group of base materials (51) occurs with the flow along the circumferential direction of the magnetic media (30) in the electrolytic solution in the electroplating tank (10), or Occurs with the rotation of the stirring section (46) provided on the bottom side of the electroplating tank (10), A lower cathode in which at least a part of the group of base materials (51) flowing along the circumferential direction in the electrolytic solution in the electroplating tank (10) is provided on the bottom side of the electroplating tank (10).
- the base material (51) which is in contact with (21) and located above the base material (51) in contact with the lower catho
- the lower cathode (21) extends along the circumferential direction in the vicinity of the inner wall (19) on the bottom side of the cylindrical portion (11) of the electroplating tank (10).
- an upper anode (22) provided above the lower cathode (21) extends along the circumferential direction.
- the stirring section (46) is rotatably provided on the bottom side of the electroplating tank (10) and constitutes at least a part of the bottom of the electroplating tank (10).
- the electroplating tank (10) includes a cylindrical portion (11), and the cylindrical portion (11) is a stationary member.
- the magnetic media (30) is a rod or needle-like member.
- the maximum rpm of the substrate (51) in the electroplating tank (10) is less than 40 rpm.
- the substrate (51) comprises one or more substrate metal elements, A plating layer (52) comprising at least a first plating layer metal element and a second plating layer metal element different from the first plating layer metal element immediately above the substrate (51) by the electroplating step.
- the second plating layer metal element is the same metal element as at least one of the one or more base metal elements;
- the ratio of the second plating layer metal element in the plating layer (52) continuously decreases in accordance with the distance from the base material (51) in the thickness direction of the plating layer (52), and / or There is no clear interface between the substrate (51) and the plating layer (52).
- the ratio of the first plating layer metal element on the surface of the plating layer (52) is less than 100% or less than 90%.
- the plating layer (52) has a thickness of 150 nm or less, or 100 nm or less.
- the plating layer (52) has an opposite surface (52s) opposite the substrate (51); The decrease in the ratio of the second plating layer metal element in the plating layer (52) reaches the opposite surface (52s) or in the vicinity of the opposite surface (52s) in the thickness direction of the plating layer (52). Continue until.
- the substrate (51) includes a plurality of the substrate metal elements
- the plating layer (52) includes a plurality of the second plating layer metal elements, The proportion of each second plating layer metal element in the plating layer (52) decreases as the plating layer (52) moves away from the substrate (51) in the thickness direction.
- the proportion of the first plating layer metal element in the plating layer (52) decreases as the thickness of the plating layer (52) approaches the substrate (51). .
- the substrate (51) is a metal or alloy containing at least copper as the substrate metal element.
- the plating layer (52) is a metal or alloy containing at least tin as the first plating layer metal element.
- the plating layer (52) has an opposite surface (52s) opposite the substrate (51);
- the opposite surface (52s) is formed with two-dimensionally dense particle-like portions and / or small lump-like portions.
- the plating material (5) including the base material (51) and the plating layer (52) is at least a part of the clothing component (7).
- An electroplating apparatus includes: An electroplating tank (10) for storing an electrolytic solution is used, and a lower cathode (21) provided on the bottom side of the electroplating tank (10) and an upper anode (22) provided above the lower cathode (21).
- An electroplating tank (10) comprising: A stirring mechanism (40) for causing a group of substrates (51) settled in the electrolytic solution in the electroplating tank (10) to flow in the circumferential direction along the inner wall (19) of the electroplating tank (10);
- the flow along the circumferential direction of the group of base materials (51) occurs with the flow along the circumferential direction of the magnetic media (30) in the electrolytic solution in the electroplating tank (10), or Occurs with the rotation of the stirring section (46) provided on the bottom side of the electroplating tank (10),
- At least a part of the group of base materials (51) flowing along the circumferential direction in the electrolytic solution in the electroplating tank (10) is in contact with the lower cathode (21), and the lower cathode (21).
- the base material (51) positioned above the base material (51) in contact with the lower electrode (21) is electrically connected to the lower cathode (21) through at least the base material (51) in contact with the lower cathode (21). Connected.
- the stirring mechanism (40) acts magnetically on the group of magnetic media (30) in the electrolyte in the electroplating tank (10) to cause the group of magnetism.
- the media (30) is caused to flow along the circumferential direction, and accordingly, the group of base materials (51) are caused to flow along the circumferential direction.
- the stirring mechanism (40) is A stirring portion (46) rotatably provided on the bottom side of the electroplating tank (10); A rotational force supply mechanism (47) is provided for supplying rotational force to the stirring section (46).
- the stirring portion (46) includes a radial array of wings (463) protruding upward.
- the electroplating tank (10) includes a cylindrical portion (11) having an opening (18) in the upper portion that allows charging or collection of the base material (51),
- the lower cathode (21) extends along the circumferential direction in the vicinity of the inner wall (19) on the bottom side of the cylindrical portion (11).
- the cylindrical portion (11) is a stationary member.
- the maximum rpm of the substrate (51) in the electroplating tank (10) is less than 40 rpm.
- An electroplating apparatus is the electroplating apparatus according to any one of the above, wherein the base material (51) includes one or more base metal elements.
- a plating layer (52) including at least a first plating layer metal element and a second plating layer metal element different from the first plating layer metal element is formed directly on the base material (51), The second plating layer metal element is the same metal element as at least one of the one or more base metal elements;
- the ratio of the second plating layer metal element in the plating layer (52) continuously decreases in accordance with the distance from the base material (51) in the thickness direction of the plating layer (52), and / or There is no clear interface between the substrate (51) and the plating layer (52).
- the proportion of the first plating layer metal element (Sn) decreases as it approaches the substrate in the thickness direction of the plating layer. It is a figure which shows element distribution in the cross section of the plating material which concerns on 1 aspect of this indication, the 1st plating layer metal element (Sn) exists in a plating layer, and a base metal element (Cu) is a base material and a plating layer. It indicates that the base metal element (Zn) exists in the base material and the plating layer. It is shown that Cu exists near the surface of the plating layer rather than Zn. It is a SEM photograph which shows the section of the plating material concerning one mode of this indication, and shows that a clear interface does not exist between a substrate and a plating layer.
- the base metal element (Zn) is not present in the plating layer. It is a SEM photograph which shows the state of the surface of the plating layer of the conventional plating material, and it is shown that the crack and the pinhole are formed. It is a schematic graph which shows the change of the ratio of each metal element of the plating material in the thickness direction of the plating layer which concerns on 1 aspect of this indication.
- the proportion of the second plating layer metal element (Zn) in the plating layer continuously decreases as the plating layer moves away from the substrate in the thickness direction.
- the proportion of the first plating layer metal element (Cu) decreases as it approaches the substrate in the thickness direction of the plating layer.
- the proportion of the second plating layer metal element (Cu) in the plating layer continuously decreases as the plating layer is separated from the substrate in the thickness direction.
- the proportion of the first plating layer metal element (Zn) decreases as it approaches the substrate in the thickness direction of the plating layer.
- the proportion of the second plating layer metal element (Cu, Zn) in the plating layer decreases steeply and continuously as the distance from the substrate in the thickness direction of the plating layer.
- the proportion of the first plating layer metal element (Sn) decreases as it approaches the substrate in the thickness direction of the plating layer.
- the thickness of the plating layer is further thinner than in the case of FIG.
- It is a schematic graph at the time of forming a plating layer thinner than FIG. It is a mimetic diagram showing roughly the layer structure of the plating material concerning one mode of this indication, and the plating layer formed just above the substrate contains the ground plating layer and the surface plating layer. It is a schematic graph which shows the change of the ratio of each metal element of the plating material in the thickness direction of the plating layer which concerns on 1 aspect of this indication.
- the base plating layer is made of a certain first plating layer metal element (Sn).
- the surface plating layer is made of another first plating layer metal element (Cu). It is a schematic graph which shows the change of the ratio of each metal element of the plating material in the thickness direction of the plating layer which concerns on 1 aspect of this indication.
- the proportion of the second plating layer metal element (Zn) in the plating layer continuously decreases as the plating layer moves away from the substrate in the thickness direction.
- the proportion of the first plating layer metal element (Cu) decreases as it approaches the substrate in the thickness direction of the plating layer.
- the proportion of the second plating layer metal element (Fe) in the plating layer continuously decreases as the plating layer moves away from the substrate in the thickness direction.
- the proportion of the first plating layer metal element (Cu) decreases as it approaches the substrate in the thickness direction of the plating layer.
- FIG. 22 is a schematic partial cross-sectional view of the electroplating apparatus along X22-X22 in FIG. 21. It is a schematic graph which shows that the maximum rpm of a base material increases according to the time passage of a stirring and electroplating process. It is a mimetic diagram showing a schematic structure of an electroplating device of an example which is not limited and can be used for manufacture of a plating material concerning one mode of this indication.
- FIG. 22 is a schematic partial cross-sectional view of the electroplating apparatus along X22-X22 in FIG. 21. It is a schematic graph which shows that the maximum rpm of a base material increases according to the time passage of a stirring and electroplating process. It is a mimetic diagram showing a schematic structure of an electroplating device of an example which is not limited and can be used for manufacture of a plating material concerning one mode of this indication.
- FIG. 22 is a schematic partial cross-sectional view of the electroplating apparatus along X22-X22 in FIG
- FIG. 25 is a schematic top schematic view of the stirring unit of the electroplating apparatus shown in FIG. 24, showing that the stirring unit includes a radial array of wings protruding upward.
- Each feature included in one or more disclosed embodiments and example embodiments is not individually independent.
- Those skilled in the art can combine each example embodiment and / or each feature without undue explanation.
- Those skilled in the art can also understand the synergistic effect of this combination. In principle, duplicate description between the embodiments is omitted.
- the reference drawings are mainly for description of the invention, and may be simplified for convenience of drawing.
- a plurality of characteristics described with respect to a certain plating material and / or manufacturing method of a plating material and a certain electroplating method and / or electroplating apparatus are understood as a combination of these characteristics, and others. It is understood as an individual feature that is independent of the feature. An individual feature is understood as an independent individual feature without requiring a combination with other features, but is also understood as a combination with one or more other individual features. The description of all individual feature combinations is redundant to those skilled in the art and is omitted. Individual features are manifested by expressions such as “some embodiments”, “some cases”, “some examples”.
- the individual characteristics are not effective only for the plating material and / or the manufacturing method of the plating material and the electroplating method and / or the electroplating apparatus disclosed in the drawings, for example. It is understood as a universal feature that can also be applied to a method for producing a plating material and various other electroplating methods and / or electroplating apparatuses.
- first”, “second”, and “third” are used to logically distinguish the nouns to which these are attached.
- first is not used to indicate that there is only one noun to which it is attached (except where it is explicitly indicated).
- a plurality of second plating layer metal elements the presence of a plurality of metal elements as the second plating layer metal elements is indicated.
- first, second, and third are not used to indicate that the nouns to which they are attached are different (except when explicitly indicated as such).
- the third metal element is the same metal element as at least one of the one or more first metal elements”
- the third metal element can be the same as the first metal element. .
- FIG. 1 is a schematic perspective view of the cap of the plating material 5.
- FIG. 2 is a schematic perspective view of a clothing component 7 in which a cap of the plating material 5 is attached to the core material 6.
- FIG. 3 is a schematic diagram schematically showing the layer structure of the plating material 5, and shows a base 51 and a plating layer 52 formed immediately above the base 51.
- the interface 53 of the base material 51 and the plating layer 52 is illustrated by a solid line, there is actually no clear interface.
- the base material 51 contains one or more base metal elements.
- the plating layer 52 includes one or more first plating layer metal elements.
- the plating layer 52 includes a base metal element in addition to the first plating layer metal element.
- FIG. 1 is a schematic perspective view of the cap of the plating material 5.
- FIG. 2 is a schematic perspective view of a clothing component 7 in which a cap of the plating material 5 is attached to the core material 6.
- FIG. 3 is a schematic diagram schematically showing the layer structure of
- FIG. 4 is a schematic graph showing changes in the ratio of each metal element of the plating material 5 in the thickness direction of the plating layer 52.
- the proportion of the second plating layer metal element (Cu, Zn) in the plating layer 52 continuously decreases as the plating layer 52 moves away from the base material 51 in the thickness direction.
- the proportion of the first plating layer metal element (Sn) decreases as the thickness of the plating layer 52 approaches the substrate 51.
- FIG. 5 is a diagram showing an element distribution in a cross section of the plating material 5, wherein the first plating layer metal element (Sn) is present in the plating layer 52, and the base metal element (Cu) is the base material 51 and the plating layer. 52 indicates that the base metal element (Zn) is present in the base 51 and the plating layer 52.
- FIG. 6 is an SEM photograph showing a cross section of the plating material 5 according to one embodiment of the present disclosure, and shows that there is no clear interface between the base material 51 and the plating layer 52.
- FIG. 7 is an SEM photograph showing the state of the surface of the plating layer 52, and it is shown that the particulate portions and / or small block portions are densely formed in two dimensions.
- the plating material 5 includes a base material 51 and a plating layer 52 formed immediately above the base material 51.
- the plating material 5 may be a component in which the base 51 is covered with at least a plating layer 52.
- the plating material 5 may be at least a part of the clothing component 7.
- the plating material 5 is a part of the clothing component 7 and is combined with another part to produce the clothing component 7.
- the plating material 5 is a cap-shaped base 51 that is a cap, and plating that is formed on the surface of the base 51 or covers the entire surface of the base 51. It has a layer 52.
- the plating material 5 of FIG. 1 is attached to the core material 6, and the clothing component 7 is constructed. In the field of clothing parts, it is strongly required to ensure variations in the metal color and metallic luster of the clothing parts while suppressing materials and / or manufacturing costs.
- the base material 51 includes one or more base metal elements.
- the plating layer 52 includes at least a first plating layer metal element and a second plating layer metal element different from the first plating layer metal element.
- the base material 51 consists of a pure metal
- the base material 51 contains one base metal element.
- the base material 51 consists of an alloy
- the base material 51 contains two or more base metal elements.
- a trace amount of inevitable impurities or inevitable metals may be included in the process of manufacturing or refining a metal material such as pure metal or alloy.
- the substrate 51 is made of brass (CuZn)
- the substrate 51 can contain other trace amounts of metals or alloys.
- the Sn electrode material for electroplating may contain a trace amount of metal other than Sn.
- the base metal element can be any arbitrary metal element.
- the first and second plating layer metal elements, or other plating layer metal elements, can be any arbitrary metal element.
- the second plating layer metal element contained in the plating layer 52 is the same metal element as at least one of the one or more base metal elements.
- the first plating layer metal element is Sn
- the second plating layer metal element is Cu and / or Zn.
- the first plating layer metal element (Sn in the example of FIG. 4) is different from at least one base metal element (both Cu and Zn in the example of FIG. 4).
- the first plating layer metal element included in the plating layer 52 is different from at least one of the plurality of base metal elements (this is better understood from reference to FIG. 11 and the like). .
- the second plating layer metal element in the plating layer 52 (in accordance with the separation from the substrate 51 in the thickness direction of the plating layer 52).
- the ratio of Cu and Zn) decreases continuously.
- there is no clear interface between the plated layer 52 and the substrate 51 as can be seen from the non-limiting example demonstration of FIG.
- the adhesion between the substrate 51 and the plating layer 52 is enhanced.
- the occurrence of peeling at the interface between the substrate 51 and the plating layer 52 can be reduced and / or the thickness of the plating layer 52 can be reduced.
- the first plating layer metal element is derived from metal ions present in the electrolyte during electroplating.
- the second plating layer metal element is derived from the base metal element of the base 51.
- the plating layer can be defined as a layer including a metal deposited on the substrate by electroplating in the thickness direction. Therefore, in this specification, a plating layer may contain metals other than the metal deposited on the base material by electroplating.
- the plating layer metal element described above is a metal element constituting the plating layer, in other words, a metal element contained in the plating layer.
- the second plating layer metal element can be derived from the composition of the substrate.
- the first plating layer metal element need not be derived from the composition of the substrate. More specifically, without limitation, the first plating layer metal element may be a metal element deposited on the substrate as at least a part of the plating layer.
- the first plating layer metal element is supplied into the plating solution separately from the base material, and coincides with the metal element of the deposit of metal ions that migrates toward the base material.
- the second plating layer metal element is not limited to precipitates on the substrate.
- the second plating layer metal element is a base metal element that was present in or included in the base material to be plated and / or a base metal element that has been eluted and deposited from the base material to be plated. obtain.
- the base metal element is a metal element constituting the base, in other words, a metal element contained in the base.
- the ratio of the metal element on the surface of the plating layer can be easily changed by changing the thickness of the plating layer.
- the ratio of the metal element differs between the surface of the plating layer having a thickness T1 in FIG. 4 and the surface of the plating layer having a thickness T2 in FIG.
- the configuration of the plating layer can be changed by changing the thickness of the plating layer, and variations of the plating layer can be easily obtained.
- Variations in the plating layer can be variations in chemical properties, electrical properties, and / or physical properties depending on the proportion of elements.
- the variation of the plating layer can be a variation of the color of the plating layer.
- the boundary L1 of a plating layer and a base material is drawn.
- the first plating layer metal element (Sn) is not completely zero in the base material region deeper than the boundary L1. However, this is due to errors in the measurement and data output process.
- the first plating layer metal element (Sn) does not exist in the region of the substrate 51.
- a curve showing the change in the proportion of the first plating layer metal element in the thickness direction of the plating layer 52 and the base in the thickness direction of the plating layer 52 are shown. Curves showing changes in the ratio of the metal elements intersect.
- the opposite surface 52 s of the plating layer 52 is also referred to as the surface of the plating layer 52.
- the decrease in the proportion of the second plating layer metal element in the plating layer 52 extends to the opposite surface 52s in the thickness direction of the plating layer 52 or It continues until it reaches the vicinity of the opposite surface 52s.
- the plating layer 52 is not formed so thick that there is no change in the proportion of the base metal element. The thinning of the plating layer 52 contributes to a reduction in the amount of metal material used for forming the plating layer.
- the substrate 51 includes a plurality of substrate metal elements
- the plating layer 52 includes a plurality of substrate metal elements
- the plating layer 52 The ratio of each second plating layer metal element in the plating layer 52 decreases as the distance from the substrate 51 increases in the thickness direction.
- the base material 51 includes three or more base metal elements is also assumed. It is also assumed that the plating layer 52 includes two or more plating layer metal elements.
- the element ratio depends on atomic percent (at%). That is, when the proportion of an element is large, the atomic percentage value of that element is large.
- the atomic percentage is determined using a JAMP9500F Auger electron spectroscopic analyzer manufactured by JEOL Ltd.
- the base metal element and the first plating layer metal element may be various arbitrary metal elements.
- the base metal 51 is made of brass (CuZn), and the base metal element is copper (Cu). And zinc (Zn).
- the substrate 51 is a metal or alloy containing at least copper as a substrate metal element.
- the plating layer 52 is a metal or alloy containing at least tin (Sn) as the first plating layer metal element.
- the base 51 includes a plurality of base metal elements (for example, Cu, Sn), and the plating layer 52 includes a plurality of second plating layer metal elements (for example, Cu, Sn, etc.). Sn).
- the proportion of each second plating layer metal element (for example, Cu, Sn) in the plating layer 52 decreases as the plating layer 52 moves away from the substrate 51 in the thickness direction.
- the opposite surface 52s of the plating layer 52 is formed with two-dimensionally dense particle portions and / or small block portions.
- the plated layer 52 may have increased alkali, acid, and chemical resistance due to its dense surface state. Even if the plating layer 52 is made thin, sufficient chemical resistance of the plating layer 52 is ensured.
- the thickness of the plating layer 52 is 150 nm or less, or 100 nm or less. In the plating materials according to some embodiments, there is no particular problem in terms of plating adhesion even when the thickness of the plating layer 52 is 150 nm or less or 100 nm or less.
- the minimum thickness may be set in consideration of the productivity of the plating material. From such a viewpoint, 150 nm or less or 100 nm or less is preferable. However, the thickness is not limited to this, and the film thickness may be further increased by continuing the plating time.
- the boundary between the substrate 51 and the plating layer 52 is determined based on the measurement method shown in FIG. 4 and / or FIG. In the measurement method of FIG. 4, the boundary between the base material 51 and the plating layer 52 is determined by the depth from the surface of the plating layer 52 that reaches the ratio of the predetermined base metal element in the base material 51. In the measurement method of FIG.
- the boundary between the base material 51 and the plating layer 52 for the product of the present invention should be determined as follows.
- a position where the ratio of the base metal element reaches 98% with respect to the maximum ratio of the main base metal element in the base 51 is determined as a boundary between the base 51 and the plating layer 52.
- the main base metal element in the base material 51 is the single base metal element.
- the main base metal element in the base material 51 is the base metal element having the largest proportion, that is, atomic percent, when the base material 51 includes a plurality of base metal elements.
- the atomic percentage of Cu which is the metal component with the largest proportion (metal component with the largest atomic percent), is 80 at.
- a position where 98% of% is reached is defined as a boundary.
- the conventional barrel plating and stationary plating are not in the interface-free state as in the embodiment of the present invention, but have a clear interface, and the position is defined as the boundary between the substrate 51 and the plating layer 52.
- the position of the average height (Rc) of the irregularities on the surface is defined as the boundary between the substrate 51 and the plating layer 52 for convenience.
- FIG. 8 is an SEM photograph showing a cross section of a conventional plating material, and shows that an interface exists between the substrate and the plating layer.
- FIG. 9 is a diagram showing an element distribution in a cross section of a conventional plating material, in which a plating layer metal element (Sn) is present in the plating layer, and a plating layer metal element and a base metal element (Cu) are base material and plating.
- the film thickness may be increased to more than 200 nm in order to improve the color tone and surface state of the plating surface, and the plating layer is simple on the base material. Therefore, the boundary between the substrate 51 and the plating layer 52 can be clearly identified visually. However, since the surface of the base material actually has fine irregularities, the interface is the irregular surface itself.
- FIG. 10 is an SEM photograph showing the state of the surface of the plating layer of the conventional plating material, and shows that cracks and pinholes are formed.
- the base material is made of brass (CuZn), and the plating layer is made of a CuSn alloy.
- the elemental percentage of Cu and the elemental percentage of Sn are substantially constant.
- FIG. 8 there is a clear interface between the plating layer and the substrate, which is understood from the difference in the metal structure between the plating layer and the substrate.
- the plating layer does not contain Zn as a base metal element.
- the reason why the plating layer contains Cu is that Cu is a plating layer metal element.
- cracks D1 and pinholes D2 exist on the surface of the plating layer.
- Corrosion and collapse of the plating layer can proceed due to the entry of alkali, acid, and chemical into the crack D1 and the pinhole D2.
- a plating thickness of about 10,000 nm or more is required.
- a thickness of 100 nm such as 250 nm is used.
- a compromise is made where a plating layer having a thickness of up to 200 nm is formed, and it can withstand a certain practical level with respect to problems such as plating peeling, oxidation and discoloration.
- the plating layer of the conventional plating material in FIGS. 8 to 10 is formed by barrel plating.
- Barrel plating is a method in which a material to be plated, a base material referred to in the present specification, is placed in a barrel (rotary basket) immersed in a plating bath, and electroplating is performed while rotating the barrel.
- a large amount of material to be plated can be electroplated at a time.
- the plating layer of the plating material according to the embodiment of FIGS. 1 to 7 is formed by a non-limiting example method described later with reference to FIGS. 19 to 28, it should not necessarily be limited to this method. is not.
- One of ordinary skill in the art can improve on existing barrel plating or devise other methods that are quite different to achieve a plating layer according to the present disclosure.
- the plating material according to the embodiment illustrated in FIGS. 1 to 7 can contribute to solving the conventional problem of low adhesion due to the interface between the base material and the plating layer. Even if the plating layer is formed thick, if there is an interface between the plating layer and the substrate, peeling of the plating layer can be induced. Additionally or alternatively, the plating material according to the embodiment illustrated in FIGS. 1 to 7 can contribute to solving the conventional problem that the plating layer is thick. Additionally or alternatively, the plating material according to the embodiment illustrated in FIGS. 1 to 7 can contribute to solving the conventional problem that there are a large number of cracks and / or pinholes on the surface of the plating layer.
- FIG. 11 is a schematic graph showing a change in the ratio of each metal element of the plating material in the thickness direction of the plating layer.
- the substrate 51 is made of brass (CuZn)
- the first plating layer metal element is copper (Cu).
- the proportion of the second plating layer metal element (Zn) in the plating layer continuously decreases as the plating layer moves away from the substrate in the thickness direction.
- the first plating layer metal element is copper (Cu)
- a change in the ratio of the metal element (Cu) derived from the substrate 51 in the plating layer cannot be observed.
- the ratio of the metal element (Cu) decreases as the thickness of the plating layer approaches the substrate.
- the change in the ratio of the metal element (Cu) in the plating layer in FIG. 11 indicates the change in the total ratio of Cu as the base metal element and Cu as the first plating layer metal element.
- the change in the ratio of the metal element (Cu) in the plating layer in FIG. It is confirmed that the ratio of the first plating layer metal element (Cu) decreases as it approaches the substrate.
- FIG. 12 is a schematic graph showing a change in the ratio of each metal element of the plating material in the thickness direction of the plating layer.
- the base material 51 is made of brass (CuZn), and the first plating layer metal element is zinc (Zn).
- the proportion of the second plating layer metal element (Cu) in the plating layer continuously decreases as the distance from the substrate in the thickness direction of the plating layer.
- the first plating layer metal element is zinc (Zn)
- the proportion of the metal element (Zn) decreases in accordance with the approach to the substrate in the thickness direction of the plating layer.
- the first plating layer metal element (Zn) in accordance with the approach to the substrate in the thickness direction of the plating layer. ) To reduce the percentage.
- FIG. 13 is a schematic graph showing a change in the ratio of each metal element of the plating material in the thickness direction of the plating layer.
- the base material 51 is made of brass (CuZn)
- the first plating layer metal element is tin (Sn).
- the proportion of the second plating layer metal element (Cu or Zn) in the plating layer decreases steeply and continuously as the distance from the substrate in the thickness direction of the plating layer.
- the proportion of the first plating layer metal element (Sn) decreases as it approaches the substrate in the thickness direction of the plating layer.
- the plating layer is formed by an apparatus different from that of FIG. 4, and the remarkable effect that the thickness of the plating layer is thinner than the plating layer of FIG. 4 is obtained.
- the thickness of the plating layer should not necessarily be limited to the thicknesses of the above examples.
- the thickness of the plating is larger than 20 nm, a plating material having a color closer to the silver color that is the color of the Sn material can be obtained.
- the thickness of the plating is smaller than 20 nm, a plating material having a color closer to yellow, which is the color of the brass of the base material 51, can be obtained.
- the plating thickness in FIG. 13 is 10 nm is shown in FIG.
- the plating material of the embodiment of FIG. 13 has a light gold color, while yellow has a slightly stronger color.
- a plating material having an advantage in adhesion over conventional barrel plating can be obtained.
- FIG. 15 is a schematic diagram schematically showing the layer structure of the plating material, and the plating layer formed immediately above the substrate includes a base plating layer and a surface plating layer.
- FIG. 16 is a schematic graph showing a change in the ratio of each metal element of the plating material in the thickness direction of the plating layer.
- the plating layer is composed of a base plating layer and a surface plating layer.
- the substrate 51 is made of brass (CuZn)
- the first plating layer metal element of the base plating layer is made of tin (Sn)
- the first plating layer metal element of the surface plating layer is copper (Cu ).
- the proportion of the second plating layer metal element (Cu or Zn) in the base plating layer continuously decreases as the plating layer is separated from the substrate in the thickness direction.
- the proportion of the first plating layer metal element (Sn) in the base plating layer continuously decreases as the thickness approaches the substrate in the thickness direction of the plating layer.
- the proportion of the second plating layer metal element (Zn) in the surface plating layer continuously decreases in accordance with the separation from the base plating layer in the thickness direction of the plating layer, and the first plating layer metal element ( The ratio of Sn) decreases continuously as well.
- the first plating layer metal element of the surface plating layer is copper (Cu)
- a change in the ratio of the metal element (Cu) derived from the substrate 51 in the surface plating layer cannot be observed.
- the proportion of the metal element (Cu) in the surface plating layer decreases in the thickness direction of the surface plating layer in accordance with the approach to the base plating layer in the thickness direction of the surface plating layer. It supports that the ratio of the metal element (Cu) derived from the base material 51 of the plating layer decreases.
- FIG. 17 is a schematic graph showing a change in the ratio of each metal element of the plating material in the thickness direction of the plating layer.
- the substrate 51 is made of zinc (Zn)
- the first plating layer metal element of the plating layer is copper (Cu).
- the proportion of the second plating layer metal element (Zn) in the plating layer continuously decreases as the plating layer moves away from the substrate in the thickness direction.
- the proportion of the first plating layer metal element (Cu) decreases as it approaches the substrate in the thickness direction of the plating layer.
- FIG. 18 is a schematic graph showing changes in the ratio of each metal element of the plating material in the thickness direction of the plating layer.
- the base material 51 is made of stainless steel and contains a base metal element (Fe).
- the first plating layer metal element of the plating layer is copper (Cu).
- the proportion of the second plating layer metal element (Fe) in the plating layer continuously decreases as the plating layer moves away from the substrate in the thickness direction.
- the proportion of the first plating layer metal element (Cu) decreases as it approaches the substrate in the thickness direction of the plating layer.
- the thickness of the portion in which the ratio of the second plating layer metal element continuously decreases in accordance with the separation from the base material 51 in the thickness direction of the plating layer 52 is 10 nm or more. Or 20 nm or more, or 60 nm or more.
- FIG. 17 shows that the ratio of the second plating layer metal element (Zn) continuously decreases in the thickness range of 60 nm and / or 400 nm or more.
- FIG. 18 shows that the ratio of the second plating layer metal element (Fe) decreases in the thickness range of 60 nm and / or 100 nm or more.
- FIG. 4 shows that the ratio of the second plating layer metal element (Cu) continuously decreases in the thickness range of 60 nm or more.
- FIG. 4 shows that the ratio of the second plating layer metal element (Zn) continuously decreases in the thickness range of 40 nm or more.
- 11 and 12 are the same as FIG.
- FIG. 13 shows that the ratio of the second plating layer metal element (Cu, Zn) continuously and steeply decreases in the thickness range of 10 nm and / or 20 nm or more.
- the thickness of the portion where the proportion of the second plating layer metal element continuously decreases as the distance from the substrate 51 in the thickness direction of the plating layer 52 is 80 nm or less. Or 60 nm or less, or 30 nm or less, or 20 nm or less.
- FIG. 4 shows that the ratio of the second plating layer metal element (Cu, Zn) continuously decreases in the thickness range of 80 nm or less or 60 nm or less.
- FIG. 13 shows that the ratio of the second plating layer metal element (Cu, Zn) continuously and steeply decreases in the thickness range of 30 nm or less and / or 20 nm or less.
- the proportion of the first plating layer metal element on the surface of the plating layer 52 is less than 100% or less than 90%. Because of the second plating metal element in the plating layer, the ratio of the first plating layer metal element on the outermost surface of the plating layer 52 does not become 100%. The ratio of the first plating layer metal element on the surface of the plating layer 52 is theoretically less than 100%, or less than 90% even when foreign matter and measurement error are taken into consideration. For example, in the embodiment of FIG. 13, the plating is finished when Sn which is the first plating layer metal element reaches 35%.
- the ratio of the metal element of the plating layer is theoretically 100% on the surface of the plated material after the completion of plating, or 90% or more in consideration of foreign matter and measurement error. Yes.
- FIG. 19 is a schematic flowchart showing a non-limiting example manufacturing method of a plating material.
- FIG. 20 is a schematic diagram illustrating a schematic configuration of an electroplating apparatus of a non-limiting example that can be used for manufacturing a plating material.
- FIG. 21 is a schematic top view of the plating tank of the electroplating apparatus, showing an arrangement example of the cathode and the anode in the plating tank, and showing the low friction material provided at the bottom of the plating tank.
- FIG. 22 is a schematic partial cross-sectional view of the electroplating apparatus along X22-X22 in FIG.
- FIG. 23 is a schematic graph showing that the maximum rpm of the substrate increases with time of the stirring and electroplating steps.
- FIG. 24 is a schematic diagram showing a schematic configuration of an electroplating apparatus of a non-limiting example that can be used for manufacturing a plating material.
- FIG. 25 is a schematic top view of the stirring unit of the electroplating apparatus shown in FIG.
- FIG. 26 is a schematic diagram showing a schematic configuration of the electroplating apparatus, and shows an example in which a hollow or non-hollow cylindrical part is provided in the central part of the plating tank.
- FIG. 27 is a schematic diagram showing a schematic configuration of the electroplating apparatus, and shows an example in which the arrangement of the cathode and the anode is different.
- FIG. 28 is a schematic diagram showing a schematic configuration of the electroplating apparatus, and shows a plate-like stirring unit.
- the method for producing a plating material includes a step of introducing a base material containing a base metal element into an electroplating tank, and a step of electroplating while causing the base material to flow in the circumferential direction in the electroplating tank. May be included.
- a plating layer containing a first plating layer metal element different from the base metal element is formed immediately above the base material.
- the formed plating layer further includes a base metal element.
- the ratio of the second plating layer metal element in the plating layer decreases as the distance from the substrate in the thickness direction of the plating layer decreases, and / or a clear interface between the plating layer and the substrate. Does not exist.
- step of electroplating while allowing the base material to flow in the circumferential direction in the electroplating tank is based on the disclosure described later, and a group of base materials that have settled in the electrolytic solution in the electroplating tank It can be understood to include an agitation step for flowing in the circumferential direction along the electroplating process and an electroplating step for electroplating a group of substrates flowing in the circumferential direction in the electrolytic solution in the electroplating tank.
- An electroplating apparatus 1 includes an electroplating tank 10 that stores an electrolytic solution, and a group of substrates that have settled in the electrolytic solution stored in the electroplating tank 10.
- the stirring mechanism 40 which makes 51 flow is provided.
- the electrolytic solution is, for example, a cyan electrolytic solution.
- the base material 51 may be referred to as a material to be plated.
- the stirring mechanism 40 causes the group of base materials 51 that have settled in the electrolyte stored in the electroplating tank 10 to move around the inner wall 19 of the electroplating tank 10 while maintaining a substantially settled state. Flow in the direction.
- the stirring mechanism 40 magnetically acts on the group of magnetic media 30 in the electrolytic solution of the electroplating tank 10 to cause the group of magnetic media 30 to flow.
- the magnetic media 30 flows, the magnetic media 30 collides with the base material 51.
- the kinetic force of the magnetic medium 30 is transmitted to the base material 51, and the base material 51 starts to flow.
- the flow of the base material 51 is maintained or promoted by continuous or intermittent collision of the magnetic media 30 with respect to the base material 51.
- the substrate 51 and the plating layer 52 are polished by the contact and collision between the substrates 51 and the contact and collision between the substrate 51 and the magnetic medium 30.
- the stirring mechanism 40 causes the group of base materials 51 to flow in the circumferential direction by the rotation of the stirring unit 46 provided on the bottom side of the electroplating tank 10.
- the stirring mechanism 40 includes a stirring unit 46 that is rotatably provided on the bottom side of the electroplating tank 10, and a rotational force supply mechanism 47 that supplies a rotational force to the stirring unit 46.
- Each base material 51 flows in the circumferential direction in accordance with the rotation of the stirring unit 46.
- the base material 51 and the plating layer 52 are polished by contact and collision between the base materials 51 before the plating layer 52 is formed, and contact and collision between the base materials 51 in the growth process of the plating layer 52.
- the stirring unit 46 is rotatably provided on the bottom side of the electroplating tank 10 and constitutes at least a part of the bottom of the electroplating tank 10. Due to the rotation of the stirring unit 46, at least a part of the bottom of the electroplating tank 10 rotates relative to the cylindrical part 11 of the electroplating tank 10.
- the electroplating tank 10 includes a cylindrical portion 11 and a bottom portion 12 in some cases.
- the cylinder part 11 is a cylindrical member having an opening 18 in the upper part that allows the base material 51 to be charged or collected.
- a bottom portion 12 is provided at the lower end of the cylindrical portion 11.
- the electroplating tank 10 and the cylinder part 11 are stationary members.
- the cylinder part 11 is arranged so that the central axis of the cylinder part 11 coincides with a rotation axis AX5 described later. In some cases, the central axis of the cylindrical portion 11 and the rotation axis AX5 coincide with the vertical direction. Therefore, the group of base materials 51 put into the electroplating tank 10 is sedimented in the electrolytic solution downward in the vertical direction and is deposited on the bottom 12.
- the electroplating apparatus 1 includes a lower cathode 21 provided on the bottom side of the electroplating tank 10 and an upper anode 22 provided above the lower cathode 21.
- the bottom side is equal to the direction in which the base material 51 of the base material 51 put into the electrolytic solution of the electroplating tank 10 sinks.
- the lower cathode 21 is connected to the negative electrode of the power source 90, and the upper anode 22 is connected to the positive electrode of the power source 90.
- the metal ions released or eluted from the upper anode 22 into the electrolyte solution or the metal ions previously placed in the electrolyte solution receive electrons from the substrate 51 in direct contact with the lower cathode 21, and other substrates. Electrons are received from the substrate 51 electrically connected to the lower cathode 21 via 51. After receiving the electrons, the metal ions are deposited on the substrate 51 to form a plating layer.
- the substrate 51 in direct contact with the lower cathode 21 can supply the electrons transferred from the lower cathode 21 to the substrate 51 to the metal ions.
- the base material 51 that is not in direct contact with the lower cathode 21 and is electrically connected to the lower cathode 21 via one or more other base materials 51 is transmitted via the other one or more base materials 51.
- the electrons derived from the lower cathode 21 can be supplied to the metal ions.
- the group of substrates 51 flows along the circumferential direction while maintaining a substantially settled state in the electrolytic solution stored in the electroplating tank 10, and at least one of the group of substrates 51.
- the substrate 51 is in contact with the lower cathode 21, and the substrate 51 positioned above the substrate 51 in contact with the lower cathode 21 is electrically connected to the lower cathode 21 through at least the substrate 51 in contact with the lower cathode 21. Is done.
- the group of base materials 51 are in contact with the lower cathode 21 and are electrically connected to the lower cathode 21, and are not in contact with the lower cathode 21 and at least the first base material 51.
- a plurality of base materials 51 belonging to the second group electrically connected to the lower cathode 21 through at least one base material 51 belonging to the group may be included.
- the group of base materials 51 includes a plurality of members belonging to a third group electrically connected to the lower cathode 21 via at least one base material 51 belonging to the first group and at least one base material 51 belonging to the second group.
- a substrate 51 may be included.
- Flowing along the circumferential direction while maintaining a substantially settled state means a state in which most of the base material 51 does not float in the electrolytic solution. Flowing along the circumferential direction while maintaining a substantially settled state does not eliminate the presence of the substrate 51 that temporarily floats due to accidental disturbance of the flow of the electrolyte or collision between the substrates 51.
- a group of base materials 51 are plated while rotating at a low speed of 3 to 8 rpm, and the plating is performed until uniform and non-uniform plating is obtained. It takes a long time.
- the method of the present disclosure it is possible to promote shortening of the time required until uniform and non-uniform color plating is obtained. In some cases, the time required for the plating process is halved compared to barrel plating.
- the lower cathode 21 extends along the circumferential direction in the vicinity of the inner wall 19 on the bottom side of the cylindrical portion 11 (see, for example, FIG. 21).
- the lower cathode 21 may be an annular electrode located on the bottom side of the electroplating tank 10. Since the group of base materials 51 flows in the circumferential direction, when the lower cathode 21 includes an annular electrode, good contact between the base material 51 and the lower cathode 21 is ensured.
- the circumferential direction is a direction that travels along the inner wall 19 of the electroplating tank 10, and is not limited to a direction conforming to a perfect circular shape, but includes a direction conforming to an elliptical shape or other shapes.
- the lower cathode is preferably annular, other shapes such as a rod shape, a plate shape, and a spherical shape may be used, or the entire bottom portion 12 of the electroplating tank 10 may be used as the cathode.
- the upper anode 22 extends along the circumferential direction. Thereby, it is avoided or suppressed that a difference occurs in the growth rate of the plating layer in the circumferential direction. More specifically, the upper anode 22 extends along the circumferential direction on the opening 18 side of the cylindrical portion 11.
- the upper anode 22 is an annular electrode located at the upper part of the electroplating tank 10.
- the upper anode 22 is a metal wire, although not necessarily limited thereto, and is provided so as to be easily replaceable with a new metal wire.
- the upper anode 22 may be spherical, plate-shaped, or chip-shaped. As the upper anode 22, various kinds of metals and materials can be adopted.
- one or more metals selected from the group consisting of carbon, stainless steel, copper, tin, zinc, brass, titanium, gold, silver, nickel, chromium, lead, palladium, cobalt, platinum, ruthenium, and rhodium.
- the upper anode 22 elutes into the electrolytic solution, and the volume and weight are reduced with the passage of time. Note that the fact that the anode and the cathode extend along the circumferential direction does not mean a complete circle, but includes a state where the electrodes are arranged intermittently along the circumferential direction.
- the desired finish color can be secured by appropriately adjusting the metal species of the upper anode 22 and the composition of the electrolytic solution.
- the base material 51 is covered with a gold, black, silver, light copper, dark copper, or brown plating layer.
- various kinds of metals can be adopted.
- a plating layer also grows on the lower cathode 21. Therefore, in some cases, the plating layer is removed or the lower cathode 21 is replaced at an appropriate timing.
- the electroplating apparatus 1 further includes a lid 15 in some cases.
- the lid 15 is provided with a hole for passing a wiring connected to the upper anode 22.
- the height of the upper anode 22 in the depth direction of the electroplating tank 10 is determined by determining the distance between the upper anode 22 and the lid 15. In other words, the upper anode 22 is positioned at an appropriate height in the electroplating tank 10 by covering the electroplating tank 10 with the lid 15.
- a group of magnetic media 30 is introduced into the electroplating tank 10.
- the stirring mechanism 40 in FIG. 20 does not directly act on the base material 51 to cause the base material 51 to flow, but acts on the base material 51 via the group of magnetic media 30.
- one magnetic medium 30 is sufficiently smaller than one substrate 51.
- the specific type of magnetic media 30 can vary.
- the magnetic medium 30 may be a rod or a needle-like member.
- the magnetic media 30 may be a sphere, a rectangular parallelepiped, a cube, or a pyramid.
- the magnetic medium 30 is typically made of stainless steel, but is not necessarily limited thereto.
- the outermost plating layer of the base material 51 can be effectively polished when it collides with the base material 51.
- the upper anode 22 may be suspended by a rod without using the lid 15.
- the flow of the group of base materials 51 along the circumferential direction causes the stirring mechanism 40 to magnetically act on the group of magnetic media 30 in the electrolytic solution of the electroplating tank 10. This is ensured by causing the group of magnetic media 30 to flow along the circumferential direction.
- the flow of the group of base materials 51 along the circumferential direction occurs with the flow of the magnetic media 30 in the electrolytic solution in the electroplating tank 10 along the circumferential direction.
- the magnetic medium 30 flows along the circumferential direction, the magnetic medium 30 has a larger kinetic force than the base material 51. Effective polishing of the plating layer during growth is promoted.
- the stirring mechanism 40 includes an electric motor 41, a rotating shaft 42, a rotating plate 43, and one or more permanent magnets 44 in some cases.
- the rotational force generated by the electric motor 41 is transmitted directly or indirectly to the rotating shaft 42, the rotating plate 43 fixed to the rotating shaft 42 rotates, and the permanent magnet 44 on the rotating plate 43 rotates in the circumferential direction.
- a rotational force transmission system such as a non-supporting belt is provided between the electric motor 41 and the rotating shaft 42.
- a specific configuration of the stirring mechanism 40 is appropriately determined by those skilled in the art.
- the agitation mechanism 40 can include a magnetic circuit.
- the magnetic medium 30 can flow along the circumferential direction without rotation of a physical member.
- the permanent magnet 44 is fixed to the upper surface of the rotating plate 43 such that, for example, the N pole is directed vertically upward.
- the magnetic medium 30 is attracted to the permanent magnet 44. Accordingly, the magnetic medium 30 is taken to the permanent magnet 44 according to the circumferential movement of the permanent magnet 44. In this manner, the circumferential flow of the magnetic medium 30 is achieved, and thereby the circumferential flow of the substrate 51 is achieved.
- the stirring unit 46 includes a disk portion 461 that forms at least a part of the bottom of the electroplating tank 10, and a rotating shaft 462 that is connected to the disk portion 461.
- the upper surface of the disk portion 461 coincides with the bottom surface of the bottom portion 12 of the electroplating tank 10.
- a protrusion 464 that protrudes upward in the vertical direction is provided at the center of the upper surface of the disk portion 461.
- a radial array of wing parts 463 projecting upward, that is, vertically upward is provided on the upper surface of the disk part 461.
- the wing parts 463 are provided radially with respect to the center of the disk part 461.
- the flow along the circumferential direction of the group of base materials 51 is generated along with the rotation of the stirring unit 46 provided on the bottom side of the electroplating tank 10.
- the stirring unit 46 rotates around the rotation axis AX5
- the wing portion 463 also rotates around the rotation axis AX5. Focusing on one wing portion 463, the wing portion 463 travels along the circumferential direction, and in this process, a flow is generated in the electrolyte solution, and a flow along the circumferential direction of the base material 51 is generated.
- the wing portion 463 can directly contact and collide with the base material 51. In some cases, the wing 463 has a low height with respect to the upper surface of the disk portion 461. Smooth rotation of the stirring unit 46 is promoted. In this way, uniform stirring of the base material 51 in the electroplating tank 10 is promoted.
- the cylinder part 11 of the electroplating tank 10 is a stationary member.
- the inclined portion provided in the radially outer region of the disk portion 461 is disposed on the flange portion 119 extending toward the radially inner side provided at the lower end of the cylindrical portion 11 of the electroplating tank 10.
- a drain pipe (not shown) is connected to the gap between the inclined portion of the disk portion 461 and the flange portion 119.
- the electrolytic solution in the electroplating tank 10 can be discharged by opening and closing the drain pipe.
- Rotational force supply mechanism 47 includes an electric motor 471 and a power transmission belt 472.
- the rotational force of the electric motor 471 is transmitted to the rotating shaft 462 of the stirring unit 46 via the power transmission belt 472.
- the rotation shaft 462 rotates, the disk portion 461 connected to the rotation shaft 462 rotates, and the wing portion 463 on the upper surface of the disk portion 461 moves along the circumferential direction.
- the group of base materials 51 that have settled on the disk portion 461 of the stirring portion 46 in the electrolytic solution of the electroplating tank 10 move along the circumferential direction.
- the low friction material 13 is provided on the bottom surface of the bottom portion 12 radially inward of the lower cathode 21. Thereby, the flow of the base material 51 on the bottom portion 12 is promoted.
- a low friction material is provided on the inner wall 19 of the electroplating bath 10.
- the low friction material is, for example, a resin sheet, and is made of, for example, polyethylene, polypropylene, polyvinyl chloride, or polyurethane.
- stirring and electroplating are performed simultaneously.
- the surface of the substrate 51 is polished, and the surface of the plating layer 52 on the substrate 51 is polished.
- the magnetic medium 30 collides with the base material 51 and also the base materials 51 collide with each other, so that the plating can be advanced while affecting the surface state. It is assumed that a continuous change in the ratio of the metal elements of the plating layer 2 occurs. Also in the apparatus of FIG. 24, by adjusting the number of rotations and causing the base materials 51 to collide with each other at a rate of a certain frequency or more, the plating can be advanced while affecting the surface state.
- the plating layers shown in FIGS. 4, 11, 12, and 16 to 18 are formed by the electroplating apparatus 1 shown in FIG.
- the plating layers in FIGS. 13 and 14 are formed by the electroplating apparatus 1 in FIG.
- polishing the plating layer during the plating layer growth process seems to be contrary to the initial purpose of growing the plating layer.
- the flatness of the plating layer increases from the thin stage, and as a result, the desired finish with the thin plating layer, in other words, the desired flatness and glossiness are achieved.
- the reduction in the thickness of the plating layer results in a reduction in time and electric power required for electroplating, and can significantly contribute to a reduction in the product unit price of the plating material 5 and / or the clothing part 7.
- the flatness of the surface of the substrate 51 is remarkably low in the initial stage of the stirring and electroplating process. Therefore, the group of base materials 51 settled in the solution of the electroplating tank 10 does not flow due to contact resistance with other surrounding base materials 51 despite the collision of the magnetic media 30. Even in such a case, the flatness of the outermost surface of the substrate 51 increases with the increase in the number of collisions with the magnetic medium 30 with the passage of time, the increase in the number of collisions between the substrates 51, and the growth of the plating layer. The flow of the group of base materials 51 is promoted.
- the switch of the power supply 90 is turned on, and a voltage is applied between the lower cathode 21 and the upper anode 22.
- the electric motor 41 is turned on, the rotating shaft 42 rotates, and the permanent magnet 44 rotates along the circumferential direction. Entrained by the permanent magnet 44, the magnetic medium 30 flows along the circumferential direction.
- the base material 51 is pressed by the magnetic medium 30 and receives a force flowing along the circumferential direction.
- the contact resistance between the base materials 51 is large between the time t1 and the time t2, and the flow along the circumferential direction of the base material 51 does not occur. That is, the maximum rpm (revolutions per minute) of the base material 51 is substantially zero.
- FIG. 23 some variations of the maximum rpm change are shown by a solid line, a one-dot broken line, and a two-dot broken line.
- the change in the maximum rpm is the geometric shape of the electroplating tank 10, the volume of the electroplating tank 10, the number and / or weight of the base material 51 put into the electroplating tank 10, the number and / or weight of the magnetic media 30, and the electric motor.
- the number of rotations 41 and the number and arrangement of the permanent magnets 44 may depend.
- the end time of the stirring and electroplating process is appropriately determined by those skilled in the art through testing.
- the calculation method of rpm is as follows, for example. First, the circumferential movement distance of the specific base material 51 per unit time is measured. Next, the distance per minute is converted. In this way, rpm is obtained.
- the maximum rpm is based on the assumption that, for example, any 10 base materials 51 that flow relatively quickly visually are used as samples. That is, it is not realistic to obtain rpm for all of the group of base materials 51. Therefore, the maximum rpm means the maximum value of rpm calculated for the specific ten substrates 51.
- the identification and interpretation of the maximum rpm specified in the claims shall also be in accordance with the method described in this paragraph.
- the flow direction of the substrate 51 is reversed during the stirring process.
- production of the aggregation of the base material 51 on the bottom part 12 of the electroplating tank 10 can be accelerated
- the stirring process the rotation of the electric motor 41 is stopped and the rotation direction of the electric motor 41 is reversed.
- production of the aggregation of the base material 51 on the bottom part 12 of the electroplating tank 10 can be accelerated
- the stirring mechanism 40 it may be difficult to obtain the stirring force of the base material 51, and it may be difficult to uniformly stir the base material 51. Such a problem can be avoided or suppressed by causing the stirring mechanism 40 to stop stirring and / or reverse stirring during the stirring process.
- the maximum rpm of the substrate 51 When the maximum rpm of the substrate 51 is large, it is assumed that the probability that the substrate 51 moves radially outward in accordance with the centrifugal force and contacts the lower cathode 21 of the electroplating tank 10 is increased. However, when the maximum rpm of the substrate 51 is large, there is a concern that the probability of occurrence of the non-powered substrate 51 is increased. When the probability of occurrence of the base material 51 in the non-powered state is increased, this results in variations in the plating thickness of the individual base materials 51 in the group of base materials 51. In view of this point, in the present embodiment, the maximum rpm of the base material 51 in the electroplating tank 10 is maintained below the optimum value. Thereby, plating thickness variation can be reduced effectively.
- the non-powered base material 51 means a base material 51 that is not in direct contact with the lower cathode 21 and is not electrically connected to the lower cathode 21 via another base material 51. To do. As will be apparent to those skilled in the art, the non-powered base material 51 suffers from a bipolar phenomenon.
- the rotation speed of stirring is adjusted so that the lower the weight of the base material charged at one time is, the lower the rotation speed of the base material or the inner diameter of the electroplating tank 10 is set.
- the maximum rotation speed (rpm) of the base material 51 in the electroplating tank 10 may be a rotational speed that allows the base material 51 to maintain a substantially settled state.
- the rotation speed of the base material 51 varies depending on the input amount of the base material 51, it is preferable that the input amount and the rotation speed be such that the subsidence state can be substantially maintained.
- the input amount of the base material 51 is 10 to 8000 grams with respect to 20 to 30 liters of plating solution, and the magnetic media is placed in an electroplating tank of about 50 cc to 400 cc.
- the maximum rpm of the base material 51 in the electroplating tank 10 is maintained below 40 rpm. Thereby, plating thickness variation can be reduced effectively.
- the maximum rpm of the substrate 51 in the electroplating tank 10 is less than 30 rpm, or less than 25 rpm, or less than 20 rpm, or less than 15 rpm, or Maintained below 10 rpm.
- the maximum rpm of the base material 51 in the electroplating tank 10 is maintained below 120 rpm. Thereby, plating thickness variation can be reduced effectively.
- the maximum rpm of the substrate 51 in the electroplating tank 10 is less than 100 rpm, less than 80 rpm, less than 70 rpm, less than 60 rpm, or Maintained below 50 rpm.
- the collision frequency between the base materials 51 may be adjusted by setting the number of rotations as described above. You may make it produce the collision of the base material 51.
- a hollow or non-hollow cylindrical portion is provided in the center of the electroplating tank 10.
- the flow path of the substrate 51 is limited to the outside in the radial direction, that is, on the lower cathode 21. Thereby, the generation
- the cylindrical portion is electrically conductive and is a nonmagnetic material. Even in such a case, the same description as described above applies.
- FIG. 27 shows an example in which the arrangement of the lower cathode 21 and the upper anode 22 is different.
- the lower cathode 21 is an annular wire.
- the upper anode 22 is an annular wire.
- the lower cathode 21 is fixed near the inner wall 19 on the bottom side of the electroplating tank 10.
- the upper anode 22 is fixed near the inner wall 19 on the opening 18 side of the electroplating tank 10. Even in such a case, the same description as described above applies.
- the stirring unit 46 and / or the disk unit 461 has a flat plate shape.
- the lower cathode 21 is disposed on the flange portion 119 described above. Even in such a case, the same description as described above applies.
- FIG. 29 is a schematic front view of a slide fastener, which is referred to in order to show variations of plating materials.
- the plating material 5 may be a metal material part included in the slide fastener 8, for example, a stopper 81, a slider 82, and a handle 83.
- Example 1 relates to an example using magnetic media as described with reference to FIG.
- a plating tank having a radius of 300 mm and a depth of 150 mm, that is, a volume of 40 liters was used.
- the plating tank is made of metal.
- a rubber sheet was affixed to the inner peripheral surface of the cylindrical portion of the plating tank, and a polyethylene low friction material was affixed to the bottom of the plating tank.
- the exposed part between the rubber sheet and the low friction material was used as the cathode.
- the cathode is provided by a part of the plating tank.
- the cathode is formed in an annular shape continuously in the circumferential direction.
- the anode was immersed in the solution in a suspended manner.
- a copper wire was used as the anode.
- Stainless steel pins were used as magnetic media.
- One stainless steel pin has a length of 5 mm and a diameter of 0.5 mm.
- Stainless steel pins were added to the plating tank for 100 cc.
- a button shell was used as the substrate.
- the shell has been subjected to a degreasing and cleaning process.
- the input amount of the shell is 1 kg.
- the rotation speed of the electric motor was 1800 rpm.
- the rotational speed of the solution is 30 rpm.
- the rotational speed of the solution can be determined based on observations of floating indicators.
- the rotational speed of the shell is less than 40 rpm.
- Most of the shells were in a power supply state, and a plating layer having a uniform thickness could be formed.
- Example 2 The same as Example 1 except that 2 kg of shells and 200 cc of stainless steel pins were added. Most of the shells were in a power supply state, and a plating layer having a uniform thickness could be formed.
- Example 3 is the same as Example 1 except that 3 kg of shells, 250 cc of stainless steel pins are added, and the rotation direction of the electric motor 41 is intermittently reversed at intervals of 30 seconds. Most of the shells were in a power supply state, and a plating layer having a uniform thickness could be formed. However, some shells do not flow well, and it is expected that the thickness of the plating layer is uneven while not being confirmed.
- a plating material specified as follows is disclosed.
- -Appendix 1 A substrate (51) comprising one or more substrate metal elements;
- the plating layer (52) includes at least a first plating layer metal element and a second plating layer metal element different from the first plating layer metal element;
- the second plating layer metal element is the same metal element as at least one of the one or more base metal elements;
- the ratio of the second plating layer metal element in the plating layer (52) continuously decreases in accordance with the distance from the base material (51) in the thickness direction of the plating layer (52), and / or A plating material having no clear interface between the substrate (51) and the plating layer (52).
- the base material includes one or more base metal elements
- the plating layer includes at least first and second plating layer metal elements.
- the base metal element, the first plating layer metal element, and the second plating layer metal element are the first metal element, the second metal element, and the third metal. May alternatively be referred to as an element.
- the invention described in the claims is specified as shown in the following supplementary notes.
- a substrate (51) comprising one or more first metal elements;
- the plating layer (52) includes at least a second metal element and a third metal element different from the second metal element;
- the third metal element is the same metal element as at least one of the one or more first metal elements;
- the proportion of the third metal element in the plating layer (52) decreases continuously as the distance from the substrate (51) increases in the thickness direction of the plating layer (52), and / or the substrate.
- the plating material in which a clear interface does not exist between the said plating layer (52).
- the substrate (51) comprises one or more substrate metal elements;
- the plating layer (52) includes at least a first plating layer metal element and a second plating layer metal element different from the first plating layer metal element;
- the second plating layer metal element is the same metal element as at least one of the one or more base metal elements;
- the ratio of the second plating layer metal element in the plating layer (52) continuously decreases in accordance with the distance from the base material (51) in the thickness direction of the plating layer (52), and / or
- the plating material according to appendix 3 or 4 wherein there is no clear interface between the substrate (51) and the plating layer (52).
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Abstract
Description
電気めっき槽(10)内の電解液に沈降した一群の基材(51)を前記電気めっき槽(10)の内壁(19)沿いの周方向に流動させる撹拌工程と、
前記電気めっき槽(10)内の前記電解液において前記周方向沿いに流動する前記一群の基材(51)を電気めっきする電気めっき工程を含み、
前記一群の基材(51)の前記周方向沿いの流動が、前記電気めっき槽(10)内の前記電解液中の磁性メディア(30)の前記周方向沿いの流動に伴って生じ、若しくは、前記電気めっき槽(10)の底側に設けられた撹拌部(46)の回転に伴って生じ、
前記電気めっき槽(10)内の前記電解液において前記周方向沿いに流動する前記一群の基材(51)の少なくとも一部が、前記電気めっき槽(10)の底側に設けられた下部カソード(21)に接触し、前記下部カソード(21)に接触した基材(51)よりも上方に位置する基材(51)が、少なくとも前記下部カソード(21)に接触した前記基材(51)を介して前記下部カソード(21)に電気的に接続される。
前記電気めっき工程により前記基材(51)の直上に、少なくとも第1のめっき層金属元素と、前記第1のめっき層金属元素とは異なる第2のめっき層金属元素を含むめっき層(52)が形成され、
前記第2のめっき層金属元素が、前記1以上の基材金属元素の少なくとも一つと同一の金属元素であり、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における前記第2のめっき層金属元素の割合が連続的に減少する、及び/又は、前記基材(51)と前記めっき層(52)の間に明確な界面が存在しない。
前記めっき層(52)における前記第2のめっき層金属元素の割合の減少は、前記めっき層(52)の厚み方向において前記反対面(52s)に至るまで又は前記反対面(52s)の近傍に至るまで継続する。
前記めっき層(52)が、複数の前記第2のめっき層金属元素を含み、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における各第2のめっき層金属元素の割合が減少する。
前記反対面(52s)には粒子状部分及び/又は小塊状部分が2次元状に密集して形成されている。
電解液を蓄える電気めっき槽(10)にして、前記電気めっき槽(10)の底側に設けられた下部カソード(21)及び前記下部カソード(21)よりも上方に設けられる上部アノード(22)を備える電気めっき槽(10)と、
前記電気めっき槽(10)内の前記電解液に沈降した一群の基材(51)を前記電気めっき槽(10)の内壁(19)沿いの周方向に流動させる撹拌機構(40)を備え、
前記一群の基材(51)の前記周方向沿いの流動が、前記電気めっき槽(10)内の前記電解液中の磁性メディア(30)の前記周方向沿いの流動に伴って生じ、若しくは、前記電気めっき槽(10)の底側に設けられた撹拌部(46)の回転に伴って生じ、
前記電気めっき槽(10)内の前記電解液において前記周方向沿いに流動する前記一群の基材(51)の少なくとも一部が、前記下部カソード(21)に接触し、前記下部カソード(21)に接触した基材(51)よりも上方に位置する基材(51)が、少なくとも前記下部カソード(21)に接触した前記基材(51)を介して前記下部カソード(21)に電気的に接続される。
前記電気めっき槽(10)の底側において回転可能に設けられた撹拌部(46)と、
前記撹拌部(46)に回転力を供給する回転力供給機構(47)を備える。
前記下部カソード(21)が、前記筒部(11)の底側の内壁(19)近傍で前記周方向沿いに延びる。
前記基材(51)の直上に、少なくとも第1のめっき層金属元素と、前記第1のめっき層金属元素とは異なる第2のめっき層金属元素を含むめっき層(52)が形成され、
前記第2のめっき層金属元素が、前記1以上の基材金属元素の少なくとも一つと同一の金属元素であり、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における前記第2のめっき層金属元素の割合が連続的に減少する、及び/又は、前記基材(51)と前記めっき層(52)の間に明確な界面が存在しない。
実施例1は、図20を参照して説明したように磁性メディアを用いる例に関する。半径300mm、深さ150mm、つまり容積40リットルのめっき槽を用いた。めっき槽は金属製である。めっき槽の筒部の内周面にゴムシートを貼り付け、めっき槽の底部にポリエチレン製の低摩擦材を貼り付けた。ゴムシートと低摩擦材の間の露出部をカソードとして用いた。つまり、カソードは、めっき槽の一部が提供する。カソードは、周方向に連続して環状に構成される。アノードは、吊り下げ式にて溶液中に浸漬した。アノードとしては銅ワイヤを用いた。磁性メディアとしてステンレスピンを用いた。一つのステンレスピンの大きさは、長さ5mm、直径0.5mmである。ステンレスピンを100cc分だけめっき槽に加えた。基材としてはボタン用のシェルを用いた。シェルは、真鍮(Cu:Zn=65:35)製である。シェルは、脱脂及び洗浄工程を経たものである。シェルの投入量は、1kgである。電動モーターの回転速度は、1800rpmとした。溶液の回転速度は、30rpmである。溶液の回転速度は、浮遊する指標の観測に基づいて決定できる。シェルの回転速度は、40rpm未満である。ほとんどのシェルが給電状態にあり、均一な厚みのめっき層を形成することができた。
シェルを2kg投入し、ステンレスピンを200cc投入した点を除いて実施例1と同様である。ほとんどのシェルが給電状態にあり、均一な厚みのめっき層を形成することができた。
シェルを3kg投入し、ステンレスピンを250cc投入し、電動モーター41の回転方向を30秒間隔で間欠的に反転させた点を除いて実施例1と同様である。大半のシェルが給電状態にあり、均一な厚みのめっき層を形成することができた。しかし、一部のシェルが上手く流動せず、未確認ながら、めっき層の厚みにむらが生じていることが予想される。
-付記1-
1以上の基材金属元素を含む基材(51)と、
前記基材(51)の直上に形成されためっき層(52)を備え、
前記めっき層(52)が、少なくとも、第1のめっき層金属元素と、前記第1のめっき層金属元素とは異なる第2のめっき層金属元素を含み、
前記第2のめっき層金属元素が、前記1以上の基材金属元素の少なくとも一つと同一の金属元素であり、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における前記第2のめっき層金属元素の割合が連続的に減少する、及び/又は、前記基材(51)と前記めっき層(52)の間に明確な界面が存在しない、めっき材。
-付記2-
1以上の第1金属元素を含む基材(51)と、
前記基材(51)の直上に形成されためっき層(52)を備え、
前記めっき層(52)が、少なくとも、第2金属元素と、前記第2金属元素とは異なる第3金属元素を含み、
前記第3金属元素が、前記1以上の第1金属元素の少なくとも一つと同一の金属元素であり、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における前記第3金属元素の割合が連続的に減少する、及び/又は、前記基材(51)と前記めっき層(52)の間に明確な界面が存在しない、めっき材。
-付記3-
基材(51)と、
前記基材(51)の直上に形成されためっき層(52)を備え、
前記めっき層(52)が、前記基材(51)とは反対側の反対面(52s)を有し、
前記反対面(52s)には粒子状部分及び/又は小塊状部分が2次元状に密集して形成されている、めっき材。
-付記4-
前記反対面(52s)にはクラック又はピンホールが実質的に存在しない、付記3に記載のめっき材。
-付記5-
前記基材(51)が、1以上の基材金属元素を含み、
前記めっき層(52)が、少なくとも、第1のめっき層金属元素と、前記第1のめっき層金属元素とは異なる第2のめっき層金属元素を含み、
前記第2のめっき層金属元素が、前記1以上の基材金属元素の少なくとも一つと同一の金属元素であり、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における前記第2のめっき層金属元素の割合が連続的に減少する、及び/又は、前記基材(51)と前記めっき層(52)の間に明確な界面が存在しない、付記3又は4に記載のめっき材。
51 基材
52 めっき層
Claims (27)
- 電気めっき槽(10)内の電解液に沈降した一群の基材(51)を前記電気めっき槽(10)の内壁(19)沿いの周方向に流動させる撹拌工程と、
前記電気めっき槽(10)内の前記電解液において前記周方向沿いに流動する前記一群の基材(51)を電気めっきする電気めっき工程を含み、
前記一群の基材(51)の前記周方向沿いの流動が、前記電気めっき槽(10)内の前記電解液中の磁性メディア(30)の前記周方向沿いの流動に伴って生じ、若しくは、前記電気めっき槽(10)の底側に設けられた撹拌部(46)の回転に伴って生じ、
前記電気めっき槽(10)内の前記電解液において前記周方向沿いに流動する前記一群の基材(51)の少なくとも一部が、前記電気めっき槽(10)の底側に設けられた下部カソード(21)に接触し、前記下部カソード(21)に接触した基材(51)よりも上方に位置する基材(51)が、少なくとも前記下部カソード(21)に接触した前記基材(51)を介して前記下部カソード(21)に電気的に接続される、電気めっき方法。 - 前記下部カソード(21)が、前記電気めっき槽(10)の筒部(11)の底側の内壁(19)近傍で前記周方向沿いに延びる、請求項1に記載の電気めっき方法。
- 前記下部カソード(21)よりも上方に設けられる上部アノード(22)が、前記周方向沿いに延びる、請求項1又は2に記載の電気めっき方法。
- 前記撹拌部(46)は、前記電気めっき槽(10)の底側に回転可能に設けられ、前記電気めっき槽(10)の底部の少なくとも一部を構成する、請求項1乃至3のいずれか一項に記載の電気めっき方法。
- 前記電気めっき槽(10)が筒部(11)を含み、前記筒部(11)が静止部材である、請求項1乃至4のいずれか一項に記載の電気めっき方法。
- 前記磁性メディア(30)が棒又は針状の部材である、請求項1乃至5のいずれか一項に記載の電気めっき方法。
- 前記電気めっき槽(10)内における前記基材(51)の最大rpmが40rpm未満である、請求項1乃至6のいずれか一項に記載の電気めっき方法。
- 前記基材(51)が、1以上の基材金属元素を含み、
前記電気めっき工程により前記基材(51)の直上に、少なくとも第1のめっき層金属元素と、前記第1のめっき層金属元素とは異なる第2のめっき層金属元素を含むめっき層(52)が形成され、
前記第2のめっき層金属元素が、前記1以上の基材金属元素の少なくとも一つと同一の金属元素であり、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における前記第2のめっき層金属元素の割合が連続的に減少する、及び/又は、前記基材(51)と前記めっき層(52)の間に明確な界面が存在しない、請求項1乃至7のいずれか一項に記載の電気めっき方法。 - 前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記第2のめっき層金属元素の割合が連続的に減少する部分の厚みが10nm以上、又は20nm以上、又は、60nm以上である、請求項8に記載の電気めっき方法。
- 前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記第2のめっき層金属元素の割合が連続的に減少する部分の厚みが、80nm以下、又は60nm以下、又は、30nm以下、又は、20nm以下である、請求項8又は9に記載の電気めっき方法。
- 前記めっき層(52)の表面において前記第1のめっき層金属元素の割合は100%未満、又は、90%未満である、請求項8乃至10のいずれか一項に記載の電気めっき方法。
- 前記めっき層(52)の厚みが、150nm以下、又は100nm以下である、請求項8乃至11のいずれか一項に記載の電気めっき方法。
- 前記めっき層(52)が、前記基材(51)とは反対側の反対面(52s)を有し、
前記めっき層(52)における前記第2のめっき層金属元素の割合の減少は、前記めっき層(52)の厚み方向において前記反対面(52s)に至るまで又は前記反対面(52s)の近傍に至るまで継続する、請求項8乃至12のいずれか一項に記載の電気めっき方法。 - 前記基材(51)が、複数の前記基材金属元素を含み、
前記めっき層(52)が、複数の前記第2のめっき層金属元素を含み、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における各第2のめっき層金属元素の割合が減少する、請求項8乃至13のいずれか一項に記載の電気めっき方法。 - 前記めっき層(52)の厚み方向において前記基材(51)に接近するに応じて前記めっき層(52)における前記第1のめっき層金属元素の割合が減少する、請求項8乃至14のいずれか一項に記載の電気めっき方法。
- 前記基材(51)が前記基材金属元素として少なくとも銅を含む金属又は合金である、請求項8乃至15のいずれか一項に記載の電気めっき方法。
- 前記めっき層(52)が、前記第1のめっき層金属元素として少なくとも錫を含む金属又は合金である、請求項8乃至16のいずれか一項に記載の電気めっき方法。
- 前記めっき層(52)が、前記基材(51)とは反対側の反対面(52s)を有し、
前記反対面(52s)には粒子状部分及び/又は小塊状部分が2次元状に密集して形成されている、請求項8乃至17のいずれか一項に記載の電気めっき方法。 - 前記基材(51)と前記めっき層(52)を含むめっき材(5)が、服飾部品(7)の少なくとも一部である、請求項8乃至18のいずれか一項に記載の電気めっき方法。
- 電解液を蓄える電気めっき槽(10)にして、前記電気めっき槽(10)の底側に設けられた下部カソード(21)及び前記下部カソード(21)よりも上方に設けられる上部アノード(22)を備える電気めっき槽(10)と、
前記電気めっき槽(10)内の前記電解液に沈降した一群の基材(51)を前記電気めっき槽(10)の内壁(19)沿いの周方向に流動させる撹拌機構(40)を備え、
前記一群の基材(51)の前記周方向沿いの流動が、前記電気めっき槽(10)内の前記電解液中の磁性メディア(30)の前記周方向沿いの流動に伴って生じ、若しくは、前記電気めっき槽(10)の底側に設けられた撹拌部(46)の回転に伴って生じ、
前記電気めっき槽(10)内の前記電解液において前記周方向沿いに流動する前記一群の基材(51)の少なくとも一部が、前記下部カソード(21)に接触し、前記下部カソード(21)に接触した基材(51)よりも上方に位置する基材(51)が、少なくとも前記下部カソード(21)に接触した前記基材(51)を介して前記下部カソード(21)に電気的に接続される、電気めっき装置。 - 前記撹拌機構(40)は、前記電気めっき槽(10)内の前記電解液中の一群の磁性メディア(30)に対して磁気的に作用して前記一群の磁性メディア(30)を前記周方向沿いに流動させ、これに伴って、前記周方向沿いの前記一群の基材(51)の流動が生じる、請求項20に記載の電気めっき装置。
- 前記撹拌機構(40)は、
前記電気めっき槽(10)の底側において回転可能に設けられた撹拌部(46)と、
前記撹拌部(46)に回転力を供給する回転力供給機構(47)を備える、請求項20に記載の電気めっき装置。 - 前記撹拌部(46)は、上方に突出する翼部(463)の放射状配列を含む、請求項22に記載の電気めっき装置。
- 前記電気めっき槽(10)が、基材(51)の投入又は回収を許容する開口(18)を上部に有する筒部(11)を含み、
前記下部カソード(21)が、前記筒部(11)の底側の内壁(19)近傍で前記周方向沿いに延びる、請求項20乃至23のいずれか一項に記載の電気めっき装置。 - 前記筒部(11)が静止部材である、請求項24に記載の電気めっき装置。
- 前記電気めっき槽(10)内における前記基材(51)の最大rpmが40rpm未満である、請求項20乃至25のいずれか一項に記載の電気めっき装置。
- 前記基材(51)が1以上の基材金属元素を含む請求項20乃至26のいずれか一項に記載の電気めっき装置であって、
前記基材(51)の直上に、少なくとも第1のめっき層金属元素と、前記第1のめっき層金属元素とは異なる第2のめっき層金属元素を含むめっき層(52)が形成され、
前記第2のめっき層金属元素が、前記1以上の基材金属元素の少なくとも一つと同一の金属元素であり、
前記めっき層(52)の厚み方向において前記基材(51)から離間するに応じて前記めっき層(52)における前記第2のめっき層金属元素の割合が連続的に減少する、及び/又は、前記基材(51)と前記めっき層(52)の間に明確な界面が存在しない、電気めっき装置。
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021130874A1 (ja) | 2019-12-24 | 2021-07-01 | Ykk株式会社 | 電気めっき装置及びめっき物の製造方法 |
WO2023013054A1 (ja) * | 2021-08-06 | 2023-02-09 | Ykk株式会社 | ファスナーストリンガー、ファスナーチェーン及びスライドファスナーの製造方法、並びに電気めっき装置 |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP3733934A4 (en) * | 2017-12-26 | 2021-07-14 | Hallmark Technology Co., Ltd. | ELECTRODEPOSITION ASSEMBLY MECHANISM |
CN114746585A (zh) * | 2019-12-24 | 2022-07-12 | Ykk株式会社 | 电镀系统 |
JP2021160117A (ja) * | 2020-03-31 | 2021-10-11 | 株式会社日立製作所 | 積層体、金属めっき液、および積層体の製造方法 |
JP7466069B1 (ja) | 2023-03-13 | 2024-04-11 | 三井金属鉱業株式会社 | 亜鉛箔及びその製造方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5741944B2 (ja) | 1978-06-29 | 1982-09-06 | ||
JPH01139799A (ja) | 1987-11-25 | 1989-06-01 | Kanehiro Metaraijingu:Kk | バレルメッキ装置 |
JP4725051B2 (ja) | 2004-08-04 | 2011-07-13 | 株式会社村田製作所 | めっき方法およびめっき装置 |
JP2012062566A (ja) * | 2010-08-16 | 2012-03-29 | Hitachi Metals Ltd | メッキ装置 |
JP2013119650A (ja) | 2011-12-07 | 2013-06-17 | Mitsubishi Electric Corp | 部分めっき工法 |
WO2013141166A1 (ja) * | 2012-03-23 | 2013-09-26 | 株式会社Neomaxマテリアル | はんだ被覆ボールおよびその製造方法 |
JP2015063711A (ja) | 2013-09-24 | 2015-04-09 | 吉昭 濱田 | 表面処理装置およびめっき方法 |
WO2016075828A1 (ja) * | 2014-11-14 | 2016-05-19 | 合同会社ナポレ企画 | 服飾付属部品の表面電解処理方法、服飾付属品及びその製造方法 |
Family Cites Families (39)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4725051Y1 (ja) | 1968-11-09 | 1972-08-05 | ||
JP2628184B2 (ja) * | 1988-04-25 | 1997-07-09 | 日新製鋼株式会社 | 微粉末に金属を電気めっきする方法 |
JPH0544083A (ja) * | 1991-08-13 | 1993-02-23 | Nisshin Steel Co Ltd | 粉末の電気めつき法 |
JPH0711479A (ja) | 1993-06-28 | 1995-01-13 | Nkk Corp | 亜鉛系合金めっき鋼板及びその製造方法 |
JP3087554B2 (ja) * | 1993-12-16 | 2000-09-11 | 株式会社村田製作所 | メッキ方法 |
US6010610A (en) * | 1996-04-09 | 2000-01-04 | Yih; Pay | Method for electroplating metal coating(s) particulates at high coating speed with high current density |
US5911865A (en) * | 1997-02-07 | 1999-06-15 | Yih; Pay | Method for electroplating of micron particulates with metal coatings |
KR100589449B1 (ko) * | 1997-04-17 | 2006-06-14 | 세키스이가가쿠 고교가부시키가이샤 | 전자회로부품 |
JP3282585B2 (ja) * | 1998-06-02 | 2002-05-13 | 株式会社村田製作所 | メッキ装置及びメッキ方法 |
JP2002042556A (ja) * | 2000-07-28 | 2002-02-08 | Hitachi Cable Ltd | フラットケーブル用導体及びその製造方法並びにフラットケーブル |
JP2002069667A (ja) | 2000-08-28 | 2002-03-08 | Sony Corp | 多元素錫合金めっき被膜とその形成方法 |
JP3746221B2 (ja) | 2001-10-11 | 2006-02-15 | 日本エレクトロプレイテイング・エンジニヤース株式会社 | カップ式めっき装置 |
JP3930832B2 (ja) * | 2003-06-06 | 2007-06-13 | 株式会社山本鍍金試験器 | 水槽 |
JP4367149B2 (ja) | 2004-01-30 | 2009-11-18 | 日立電線株式会社 | フラットケーブル用導体及びその製造方法並びにフラットケーブル |
JP2006032851A (ja) | 2004-07-21 | 2006-02-02 | Mitsui Mining & Smelting Co Ltd | 被覆銅、ホイスカの発生抑制方法、プリント配線基板および半導体装置 |
JP2009065005A (ja) * | 2007-09-07 | 2009-03-26 | Panasonic Corp | チップ状電子部品の製造方法 |
US8231773B2 (en) * | 2007-12-11 | 2012-07-31 | GM Global Technology Operations LLC | Method of treating nanoparticles using an intermittently processing electrochemical cell |
JP4959592B2 (ja) | 2008-01-18 | 2012-06-27 | 株式会社日立製作所 | ネットワーク映像モニタリングシステム及びモニタ装置 |
US8698002B2 (en) * | 2009-01-20 | 2014-04-15 | Mitsubishi Shindoh Co., Ltd. | Conductive member and method for producing the same |
JP4987028B2 (ja) | 2009-03-31 | 2012-07-25 | Jx日鉱日石金属株式会社 | プリント基板端子用銅合金すずめっき材 |
WO2010144509A2 (en) | 2009-06-08 | 2010-12-16 | Modumetal Llc | Electrodeposited, nanolaminate coatings and claddings for corrosion protection |
CN101954618A (zh) * | 2009-07-13 | 2011-01-26 | 豪昱电子有限公司 | 磁力研磨机 |
JP5435355B2 (ja) | 2009-09-04 | 2014-03-05 | 日立金属株式会社 | メッキ装置 |
JP5650899B2 (ja) * | 2009-09-08 | 2015-01-07 | 上村工業株式会社 | 電気めっき装置 |
JP5598754B2 (ja) * | 2010-06-08 | 2014-10-01 | 日立金属株式会社 | めっき装置 |
JP2012025975A (ja) * | 2010-07-20 | 2012-02-09 | Hitachi Metals Ltd | メッキ装置 |
JP2012087388A (ja) * | 2010-10-21 | 2012-05-10 | Furukawa Electric Co Ltd:The | 表面処理銅箔及び銅張積層板 |
US20120245019A1 (en) * | 2011-03-23 | 2012-09-27 | Brookhaven Science Associates, Llc | Method and Electrochemical Cell for Synthesis of Electrocatalysts by Growing Metal Monolayers, or Bilayers and Treatment of Metal, Carbon, Oxide and Core-Shell Nanoparticles |
RU2464361C1 (ru) * | 2011-04-11 | 2012-10-20 | Федеральное государственное образовательное учреждение высшего профессионального образования "РОССИЙСКИЙ ГОСУДАРСТВЕННЫЙ АГРАРНЫЙ ЗАОЧНЫЙ УНИВЕРСИТЕТ" | Устройство для нанесения гальванических покрытий |
JP5741944B2 (ja) | 2011-09-02 | 2015-07-01 | 株式会社村田製作所 | めっき装置、及びめっき方法 |
EP2842338A1 (en) | 2012-04-24 | 2015-03-04 | VID SCALE, Inc. | Method and apparatus for smooth stream switching in mpeg/3gpp-dash |
US9388502B2 (en) * | 2012-07-12 | 2016-07-12 | Ykk Corporation | Button or fastener member of copper-plated aluminum or aluminum alloy and method of production thereof |
CN102925937B (zh) * | 2012-09-07 | 2015-07-01 | 上海大学 | 磁场下连续制备高硅钢薄带的方法及装置 |
JP5667152B2 (ja) * | 2012-09-19 | 2015-02-12 | Jx日鉱日石金属株式会社 | 表面処理めっき材およびその製造方法、並びに電子部品 |
JP2014070265A (ja) * | 2012-10-01 | 2014-04-21 | Panasonic Corp | バレルめっき装置およびこのバレルめっき装置を用いた電子部品の製造方法 |
RU153631U1 (ru) * | 2014-01-09 | 2015-07-27 | Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Волгоградский государственный аграрный университет | Гальваническая ванна для покрытия деталей цилиндрической формы |
JP6197778B2 (ja) | 2014-10-24 | 2017-09-20 | Jfeスチール株式会社 | 容器用鋼板およびその製造方法 |
JP6463622B2 (ja) * | 2014-11-27 | 2019-02-06 | Ykk株式会社 | めっき装置、めっきユニット、及びめっきライン |
JP6328288B2 (ja) | 2017-03-23 | 2018-05-23 | Ykk株式会社 | 服飾付属部品の表面電解処理装置 |
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Patent Citations (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5741944B2 (ja) | 1978-06-29 | 1982-09-06 | ||
JPH01139799A (ja) | 1987-11-25 | 1989-06-01 | Kanehiro Metaraijingu:Kk | バレルメッキ装置 |
JP4725051B2 (ja) | 2004-08-04 | 2011-07-13 | 株式会社村田製作所 | めっき方法およびめっき装置 |
JP2012062566A (ja) * | 2010-08-16 | 2012-03-29 | Hitachi Metals Ltd | メッキ装置 |
JP2013119650A (ja) | 2011-12-07 | 2013-06-17 | Mitsubishi Electric Corp | 部分めっき工法 |
WO2013141166A1 (ja) * | 2012-03-23 | 2013-09-26 | 株式会社Neomaxマテリアル | はんだ被覆ボールおよびその製造方法 |
KR20130133097A (ko) * | 2012-03-23 | 2013-12-05 | 가부시키가이샤 네오맥스 마테리아르 | 땜납 피복 볼 및 그 제조 방법 |
JP2015063711A (ja) | 2013-09-24 | 2015-04-09 | 吉昭 濱田 | 表面処理装置およびめっき方法 |
WO2016075828A1 (ja) * | 2014-11-14 | 2016-05-19 | 合同会社ナポレ企画 | 服飾付属部品の表面電解処理方法、服飾付属品及びその製造方法 |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2021130874A1 (ja) | 2019-12-24 | 2021-07-01 | Ykk株式会社 | 電気めっき装置及びめっき物の製造方法 |
EP4083273A4 (en) * | 2019-12-24 | 2022-11-30 | Ykk Corporation | ELECTROPLATING APPARATUS AND METHOD OF MAKING A PLATED PRODUCT |
WO2023013054A1 (ja) * | 2021-08-06 | 2023-02-09 | Ykk株式会社 | ファスナーストリンガー、ファスナーチェーン及びスライドファスナーの製造方法、並びに電気めっき装置 |
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