US20220298668A1 - Method for suppressing increase in zinc concentration of plating solution and method for manufacturing zinc-based plating member - Google Patents
Method for suppressing increase in zinc concentration of plating solution and method for manufacturing zinc-based plating member Download PDFInfo
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- US20220298668A1 US20220298668A1 US17/297,470 US202017297470A US2022298668A1 US 20220298668 A1 US20220298668 A1 US 20220298668A1 US 202017297470 A US202017297470 A US 202017297470A US 2022298668 A1 US2022298668 A1 US 2022298668A1
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- 238000007747 plating Methods 0.000 title claims abstract description 185
- 239000011701 zinc Substances 0.000 title claims abstract description 109
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 104
- 238000000034 method Methods 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000000243 solution Substances 0.000 claims abstract description 83
- 239000008151 electrolyte solution Substances 0.000 claims abstract description 77
- 229910052751 metal Inorganic materials 0.000 claims abstract description 47
- 239000002184 metal Substances 0.000 claims abstract description 47
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 17
- 229910001297 Zn alloy Inorganic materials 0.000 claims abstract description 12
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 7
- 239000000956 alloy Substances 0.000 claims abstract description 7
- 239000012528 membrane Substances 0.000 claims description 30
- 238000005341 cation exchange Methods 0.000 claims description 21
- 230000002378 acidificating effect Effects 0.000 claims description 11
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 8
- 238000005275 alloying Methods 0.000 claims description 2
- 239000003014 ion exchange membrane Substances 0.000 description 22
- 238000002474 experimental method Methods 0.000 description 16
- 238000005868 electrolysis reaction Methods 0.000 description 10
- 238000003756 stirring Methods 0.000 description 9
- 239000003011 anion exchange membrane Substances 0.000 description 8
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 150000001450 anions Chemical class 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- -1 polypropylene Polymers 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- 239000011592 zinc chloride Substances 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229920001155 polypropylene Polymers 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000005192 partition Methods 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
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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
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- 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
-
- 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
- C25D17/002—Cell separation, e.g. membranes, diaphragms
-
- 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
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- 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
- C25D21/06—Filtering particles other than ions
-
- 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
-
- 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
- C25D21/16—Regeneration of process solutions
- C25D21/18—Regeneration of process solutions of electrolytes
-
- 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
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
-
- 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
- C25D17/06—Suspending or supporting devices for articles to be coated
Abstract
Provided is a method for suppressing an increase in the zinc concentration of a plating solution when a zinc alloy plating member using nickel as an alloy element is manufactured using a zinc alloy plating apparatus. The plating apparatus includes: a plating tank; a first diaphragm tank having a first diaphragm; a cathode holding member; a first anode holding member; a soluble zinc-containing member held by the first anode holding member; a soluble metal-containing member containing the nickel which is the alloy element; and a second anode holding member for anode-electrolyzing the soluble metal-containing member. The first diaphragm tank is arranged in a manner that the first electrolytic solution is in contact with one surface of the first diaphragm and the plating solution is in contact with the other surface of the first diaphragm during use.
Description
- The present invention relates to a method for suppressing an increase in the zinc concentration of a plating solution, and a method for manufacturing a zinc-based plating member.
-
Patent literature 1 describes a zinc alloy electroplating method including energization in an alkali-zinc alloy electroplating bath equipped with a cathode and an anode, wherein a cathode region including the cathode and an anode region including the anode are separated from each other by a separator containing an electrolytic solution gel that can be energized. - Patent literature 2 describes a plating bath characterized in that an anode (2) is isolated from an alkaline electrolytic solution (plating bath) by an ion exchange membrane (6) in an alkaline plating bath (1) for zinc-nickel film electrodeposition which has the anode (2) and a cathode (3).
- Patent literature 1: Japanese Patent No. 58320202
- Patent literature 2: Japanese Patent No. 4716568
- The present invention provides a method for suppressing an increase in the zinc concentration of a plating solution when an anode is soluble, and a method for manufacturing a zinc-based plating member.
- The present invention includes the following aspects.
- (1) A zinc-based plating apparatus for manufacturing a zinc-based plating member, including: a plating tank capable of accommodating a plating solution; a first diaphragm tank which is capable of accommodating a first electrolytic solution and has a first diaphragm including a first ion exchange membrane; a cathode holding member for cathode-electrolyzing a member to be plated that is in contact with the plating solution inside the plating tank during use; and a first anode holding member for anode-electrolyzing a soluble zinc-containing member that is in contact with the first electrolytic solution inside the first diaphragm tank during use; wherein the first diaphragm tank is arranged in a manner that the first electrolytic solution is in contact with one surface of the first diaphragm and the plating solution is in contact with the other surface of the first diaphragm during use.
- (2) The zinc-based plating apparatus according to (1), wherein the plating solution is acidic.
- (3) The zinc-based plating apparatus according to (1) or (2), wherein the first ion exchange membrane includes a cation exchange membrane.
- (4) The zinc-based plating apparatus according to any one of (1) to (3), wherein the first ion exchange membrane includes an anion exchange membrane.
- (5) The zinc-based plating apparatus according to any one of (1) to (4), further including the soluble zinc-containing member held by the first anode holding member.
- (6) The zinc-based plating apparatus according to any one of (1) to (5), further including a second anode holding member for anode-electrolyzing a soluble metal-containing member that is electrically connected to the plating solution during use.
- (7) The zinc-based plating apparatus according to (6), further including the soluble metal-containing member held by the second anode holding member.
- (8) The zinc-based plating apparatus according to (6) or (7), wherein the soluble metal-containing member contains a metal nobler than zinc as a soluble metal.
- (9) The zinc-based plating apparatus according to any one of (6) to (8), wherein the second anode holding member is arranged in a manner that the soluble metal-containing member is in contact with the plating solution during use.
- (10) The zinc-based plating apparatus according to any one of (6) to (9), further including a second diaphragm tank which is capable of accommodating a second electrolytic solution and has a second diaphragm including a second ion exchange membrane, wherein the second diaphragm tank is arranged in a manner that the second electrolytic solution which is in contact with the soluble metal-containing member inside the second diaphragm tank is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm during use.
- (11) The zinc-based plating apparatus according to (10), wherein the second ion exchange membrane includes a cation exchange membrane.
- (12) The zinc-based plating apparatus according to (10) or (11), wherein the second ion exchange membrane includes an anion exchange membrane.
- (13) A method for manufacturing a zinc-based plating member, in which a first diaphragm tank which has a first diaphragm including a first ion exchange membrane and accommodates a first electrolytic solution is arranged in a manner that the first electrolytic solution is in contact with one surface of the first diaphragm and a plating solution accommodated inside the plating tank is in contact with the other surface of the first diaphragm, a member to be plated that is in contact with the plating solution in the plating tank is cathode-electrolyzed, and a soluble zinc-containing member that is in contact with the first electrolytic solution inside the first diaphragm tank is anode-electrolyzed.
- (14) The method for manufacturing a zinc-based plating member according to (13), wherein the plating solution is acidic.
- (15) The method for manufacturing a zinc-based plating member according to (13) or (14), wherein the first ion exchange membrane includes a cation exchange membrane.
- (16) The method for manufacturing a zinc-based plating member according to any one of (13) to (15), wherein the first ion exchange membrane includes an anion exchange membrane.
- (17) The method for manufacturing a zinc-based plating member according to any one of (13) to (16), wherein a soluble metal-containing member that is in contact with the plating solution in the plating tank is anode-electrolyzed.
- (18) The method for manufacturing a zinc-based plating member according to any one of (13) to (16), wherein a second diaphragm tank which has a second diaphragm including a second ion exchange membrane and accommodates a second electrolytic solution is arranged in a manner that the second electrolytic solution is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm, and a soluble metal-containing member that is in contact with the second electrolytic solution in the second diaphragm tank is anode-electrolyzed.
- (19) The method for manufacturing a zinc-based plating member according to (18), wherein the second ion exchange membrane includes a cation exchange membrane.
- (20) The method for manufacturing a zinc-based plating member according to (18) or (19), wherein the second ion exchange membrane includes an anion exchange membrane.
- (21) The method for manufacturing a zinc-based plating member according to any one of (17) to (20), wherein the soluble metal-containing member contains a metal nobler than zinc as a soluble metal.
- [1] A method for suppressing an increase in the zinc concentration of a plating solution when a zinc alloy plating member using nickel as an alloy element is manufactured using a zinc alloy plating apparatus, wherein the plating apparatus includes: a plating tank capable of accommodating the plating solution which is acidic; a first diaphragm tank which is capable of accommodating the first electrolytic solution and has a first diaphragm composed of a cation exchange membrane; a cathode holding member for cathode-electrolyzing a member to be plated that is in contact with the plating solution inside the plating tank during use; a first anode holding member for anode-electrolyzing a soluble zinc-containing member that is in contact with the first electrolytic solution inside the first diaphragm tank during use; the soluble zinc-containing member held by the first anode holding member; a soluble metal-containing member containing the nickel which is the alloying element; and a second anode holding member for anode-electrolyzing the soluble metal-containing member; and the first diaphragm tank is arranged in a manner that the first electrolytic solution is in contact with one surface of the first diaphragm and the plating solution is in contact with the other surface of the first diaphragm during use.
- [2] The method for suppressing an increase in the zinc concentration of a plating solution according to [1], wherein the second anode holding member is arranged in a manner that the soluble metal-containing member is in contact with the plating solution during use.
- [3] The method for suppressing an increase in the zinc concentration of a plating solution according to [2], further including a second diaphragm tank which is capable of accommodating a second electrolytic solution and has a second diaphragm composed of a cation exchange membrane, wherein the second diaphragm tank is arranged in a manner that the second electrolytic solution which is in contact with the soluble metal-containing member inside the second diaphragm tank is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm during use.
- [4] A method for manufacturing a zinc-based plating member, in which a first diaphragm tank which has a first diaphragm composed of a cation exchange membrane and accommodates a first electrolytic solution is arranged in a manner that the first electrolytic solution is in contact with one surface of the first diaphragm and an acidic plating solution accommodated inside a plating tank is in contact with the other surface of the first diaphragm, a member to be plated that is in contact with the plating solution in the plating tank is cathode-electrolyzed, a soluble zinc-containing member that is in contact with the first electrolytic solution inside the first diaphragm tank is anode-electrolyzed, and a soluble metal-containing member containing nickel which is an alloy element is anode-electrolyzed, and thereby zinc-nickel plating is formed on the member to be plated while an increase in the zinc concentration of the plating solution is suppressed.
- [5] The method for manufacturing a zinc-based plating member according to [4], wherein the soluble metal-containing member is in contact with the plating solution in the plating tank.
- [6] The method for manufacturing a zinc-based plating member according to [4] or [5], wherein a second diaphragm tank which has a second diaphragm composed of a cation exchange membrane and accommodates a second electrolytic solution is arranged in a manner that the second electrolytic solution is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm, and the soluble metal-containing member that is in contact with the second electrolytic solution in the second diaphragm tank is anode-electrolyzed.
- According to the present invention, a method for suppressing an increase in the zinc concentration of a plating solution when an anode is soluble, and a method for manufacturing a zinc-based plating member are provided.
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FIG. 1 is an illustrative diagram of a zinc-based plating apparatus according to a first embodiment of the present invention. -
FIG. 2 is an illustrative diagram of a zinc-based plating apparatus according to a second embodiment of the present invention. - Hereinafter, embodiments of the present invention are described.
-
FIG. 1 is an illustrative diagram of a zinc-based plating apparatus according to a first embodiment of the present invention. A zinc-basedplating apparatus 100 according to the first embodiment is used for manufacturing a zinc-based plating member. Zinc-based plating is a general term for zinc plating and zinc alloy plating. A specific example of the zinc alloy plating may be zinc-nickel plating. - The zinc-based
plating apparatus 100 includes aplating tank 10, afirst diaphragm tank 20, acathode holding member 30, and a firstanode holding member 40. - The
plating tank 10 is capable of accommodating a plating solution PE, and inFIG. 1 , the plating solution PE is inside theplating tank 10. A specific example of the material constituting theplating tank 10 may be polypropylene. Theplating tank 10 may be equipped with a stirring apparatus for stirring the plating solution PE, or may be equipped with a filter for removing insoluble substances generated in the plating solution PE. Theplating tank 10 may be equipped with a circulation pump for stirring the plating solution PE and removing the insoluble substances. - The composition of the plating solution PE is appropriately set according to the type of the zinc-based plating. As a specific example, the plating solution PE is acidic. That is, in the embodiment, the plating solution PE is an acidic zinc-based plating solution. In the specification, the zinc-based plating solution is an electrolytic solution containing ions including zinc elements and is a liquid capable of forming a zinc-containing plating film on a member to be plated 31 that has been cathode-electrolyzed.
- Moreover, the zinc-based plating solution may contain insoluble components and may be in the form of a dispersion.
- The
first diaphragm tank 20 is capable of accommodating a first electrolytic solution E1, and inFIG. 1 , the first electrolytic solution E1 is inside thefirst diaphragm tank 20. Thefirst diaphragm tank 20 has afirst diaphragm 21 including a first ion exchange membrane. The first ion exchange membrane may include a cation exchange membrane or an anion exchange membrane. As described later, the first ion exchange membrane may preferably include a cation exchange membrane. - In the zinc-based
plating apparatus 100 according to the first embodiment, thefirst diaphragm tank 20 is located inside theplating tank 10, and thefirst diaphragm tank 20 is arranged in a manner that the first electrolytic solution E1 is in contact with one surface of the first diaphragm 21 (on the inner side of the first diaphragm tank 20) and the plating solution PE is in contact with the other surface of the first diaphragm 21 (on the outer side of the first diaphragm tank 20). - A specific example of the material constituting the
first diaphragm tank 20 may be polypropylene. Thefirst diaphragm tank 20 may be equipped with a stirring apparatus for stirring the first electrolytic solution E1 inside thefirst diaphragm tank 20, or may be equipped with a filter for removing insoluble substances generated in the first electrolytic solution E1. Thefirst diaphragm tank 20 may be equipped with a circulation pump for stirring the first electrolytic solution E1 and removing the insoluble substances. - In the embodiment, the
first diaphragm tank 20 is arranged inside theplating tank 10, but a part of the inside of theplating tank 10 may be partitioned and thefirst diaphragm 21 may be arranged in the partition. In this case, the inner side of the partitioned part becomes thefirst diaphragm tank 20, the first electrolytic solution E1 may be located inside thefirst diaphragm tank 20, and the plating solution PE may be located on the outer side of the partitioned part inside theplating tank 10. - The
cathode holding member 30 is used for cathode-electrolyzing the member to be plated 31 that is in contact with the plating solution PE inside theplating tank 10 during use. That is, thecathode holding member 30 has a function of holding the member to be plated 31 and a function of passing a cathode electrolytic current through the member to be plated 31. A shape of thecathode holding member 30 is appropriately set according to a shape of the member to be plated 31 to be held. InFIG. 1 , thecathode holding member 30 has the shape of a clip that clamps the member to be plated 31 having a plate shape. Thecathode holding member 30 is connected to acathode terminal 62 of apower supply apparatus 60 via wiring in order that the member to be plated 31 can be cathode-electrolyzed. - Moreover, in the specification, cathodic electrolysis means that electrolysis is performed at a negative potential relative to the potential of anodic electrolysis, and in relation to the ground potential, the potential of cathodic electrolysis may be a positive potential or a negative potential. Similarly, anodic electrolysis means that electrolysis is performed at a positive potential relative to the potential of cathodic electrolysis, and in relation to the ground potential, the potential of anodic electrolysis may be a positive potential or a negative potential.
- The first
anode holding member 40 is used for anode-electrolyzing a soluble zinc-containing member 41 that is in contact with the first electrolytic solution E1 inside the first diaphragm tank during use. That is, the firstanode holding member 40 has a function of holding the soluble zinc-containing member 41 and a function of passing an anode electrolytic current through the soluble zinc-containing member 41. A shape of the firstanode holding member 40 is appropriately set according to a shape of the soluble zinc-containing member 41 to be held. InFIG. 1 , the firstanode holding member 40 has the shape of a cage that holds the soluble zinc-containing member 41 composed of a plurality of zinc ingots (lumps). The firstanode holding member 40 is connected to ananode terminal 61 of thepower supply apparatus 60 via wiring in order that the soluble zinc-containing member 41 can be anode-electrolyzed. - The first electrolytic solution E1 is an electrolytic solution containing ions including zinc elements, and when the soluble zinc-containing member 41 is anode-electrolyzed, the zinc contained in the soluble zinc-containing member 41 can be dissolved as an ion. Moreover, the first electrolytic solution E1 may contain insoluble components and may be in the form of a dispersion.
- The zinc-based
plating apparatus 100 further includes a secondanode holding member 50 for anode-electrolyzing a soluble metal-containingmember 51 that is electrically connected to the plating solution PE during use. That is, the secondanode holding member 50 has a function of holding the soluble metal-containingmember 51 and a function of passing an anode electrolytic current through the soluble metal-containingmember 51. A shape of the secondanode holding member 50 is appropriately set according to a shape of the soluble metal-containingmember 51 to be held. InFIG. 1 , the firstanode holding member 40 has the shape of a cage that holds the soluble metal-containingmember 51 composed of a plurality of nickel ingots (lumps). The secondanode holding member 50 is connected to theanode terminal 61 of thepower supply apparatus 60 via wiring in order that the soluble metal-containingmember 51 can be anode-electrolyzed. - The soluble metal-containing
member 51 is held by the secondanode holding member 50 and located inside theplating tank 10, and is electrically connected to the plating solution PE in a manner of being in direct contact with the plating solution PE. The soluble metal-containingmember 51 can be a source of alloy elements in the zinc alloy plating. As described above, when the soluble metal-containingmember 51 is composed of the plurality of nickel ingots (lumps), the zinc alloy plating can be zinc-nickel plating. The soluble metal-containingmember 51 may contain a metal nobler than zinc as a soluble metal, such as the nickel described above. - Moreover, in
FIG. 1 , the firstanode holding member 40 and the secondanode holding member 50 are connected to thesame anode terminal 61, but the present invention is not limited hereto. The anodic electrolysis potential of the firstanode holding member 40 and the anodic electrolysis potential of the secondanode holding member 50 may be different from each other. -
FIG. 2 is an illustrative diagram of a zinc-based plating apparatus according to a second embodiment of the present invention. A zinc-basedplating apparatus 101 according to the second embodiment has the same basic configuration as the zinc-basedplating apparatus 100 according to the first embodiment. The difference of the zinc-basedplating apparatus 101 according to the second embodiment when compared with the zinc-basedplating apparatus 100 according to the first embodiment is that the secondanode holding member 50 is located inside asecond diaphragm tank 70 which accommodates a second electrolytic solution E2. - That is, the zinc-based
plating apparatus 101 includes thesecond diaphragm tank 70 having asecond diaphragm 71 including a second ion exchange membrane. Thesecond diaphragm tank 70 is arranged in a manner that the second electrolytic solution E2 is in contact with one surface of the second diaphragm 71 (on the inner side of the second diaphragm tank 70) and the plating solution PE is in contact with the other surface of the second diaphragm 71 (on the outer side of the second diaphragm tank 70). The second electrolytic solution E2 is in contact with the soluble metal-containingmember 51 held by the secondanode holding member 50 inside thesecond diaphragm tank 70. - A specific example of the material constituting the
second diaphragm tank 70 may be polypropylene. Thesecond diaphragm tank 70 may be equipped with a stirring apparatus for stirring the second electrolytic solution E2 inside thesecond diaphragm tank 70, or may be equipped with a filter for removing insoluble substances generated in the second electrolytic solution E2. Thesecond diaphragm tank 70 may be equipped with a circulation pump for stirring the second electrolytic solution E2 and removing the insoluble substances. - In the embodiment, the
second diaphragm tank 70 is arranged inside theplating tank 10, but a part of the inside of theplating tank 10 may be partitioned and thesecond diaphragm 71 may be arranged in the partition. In this case, the inner side of the partitioned part becomes thesecond diaphragm tank 70, the second electrolytic solution E2 may be located inside thesecond diaphragm tank 70, and the plating solution PE may be located on the outer side of the partitioned part inside theplating tank 10. - The second electrolytic solution E2 is an electrolytic solution, and when the soluble metal-containing
member 51 is anode-electrolyzed, the metal contained in the soluble metal-containingmember 51 can be dissolved as an ion. Moreover, the second electrolytic solution E2 may contain insoluble components and may be in the form of a dispersion. - The second ion exchange membrane may include a cation exchange membrane or an anion exchange membrane. The second ion exchange membrane may have the same configuration as the first ion exchange membrane, or may have a different configuration.
- The above embodiments have been described for facilitating the understanding of the present invention, but not for limiting the present invention. Therefore, each element disclosed in the above embodiments is intended to include all design changes and equivalents belonging to the technical scope of the present invention. For example, the
first diaphragm tank 20 may have a plurality offirst diaphragms 21 having different configurations, and thesecond diaphragm tank 70 may have a plurality ofsecond diaphragms 71 having different configurations. - Hereinafter, the effects of the present invention are described based on examples, but the present invention is not limited hereto.
- An acidic zinc-nickel plating solution having the composition shown in Table 1 was prepared.
-
TABLE 1 Acidic zinc-nickel plating solution Metas ANK-10 manufactured by Yuken Kogyo Co., Ltd. Zinc chloride 73 g/L Nickel chloride 81 g/L Potassium chloride 206 g/L Metas ANK-10K 125 ml/L Metas ANK-10D 12 ml/L Metas ANK- 10M 30 ml/L Metas ANK-10G 2 ml/ L Bath temperature 40° C. pH 5.4 (Zn: 35 g/L) (Ni: 20 g/L) - By using the zinc-based
plating apparatus 100 shown inFIG. 1 , the above acidic zinc-nickel plating solution was put into theplating tank 10 as the plating solution PE, and any one of the following electrolytic solutions was put into thefirst diaphragm tank 20 as the first electrolytic solution E1 (internal solution). - (Electrolytic solution A) zinc chloride concentration 50 g/L
- (Electrolytic solution B) zinc chloride concentration 500 g/L
- (Electrolytic solution C) zinc chloride concentration 0 g/L
- As the
first diaphragm 21 of thefirst diaphragm tank 20, any one of the ion exchange membranes shown in Table 2 was used. -
TABLE 2 Type of ion exchange membrane Product name Maker Type Selemion CMVN AGC Engineering Co., Ltd. Cation Neosepta CMB Astom Co., Ltd. Cation Neosepta AHA Astom Co., Ltd. Anion - Plating was performed under the conditions shown in Table 3. Moreover, the unit of energization time in Table 3 is hour.
-
TABLE 3 Internal solution Plating solution Ion Energization Zn before Zn after Zn before Zn after exchange Membrane time energization energization energization energization No. membrane type (hr) (g/L) (g/L) (g/L) (g/L) {circle around (1)} None — 25 — — 35.0 40.2 ↑ {circle around (2)} Neocepta AHA Anion 25 0 43.1 ↑ 35.0 20.5 ↓ {circle around (3)} Neosepta CMB Cation 25 25.0 39.5 ↑ 35.0 30.1 ↓ {circle around (4)} Neosepta CMB Cation 25 250.0 257.0 ↑ 35.0 32.5 ↓ {circle around (5)} Selemion CMVN Cation 25 25.0 28.5 ↑ 35.0 34.0 ↓ {circle around (6)} Selemion CMVN Cation 25 250.0 251.3 ↑ 35.0 34.5 ↓ - As shown in Table 3, when the
first diaphragm tank 20 was not arranged (Experiment No. 1), the zinc concentration in the plating solution PE was increased by energization (40.2 g/L). - On the other hand, when the
first diaphragm tank 20 having an anion membrane (anion exchange membrane) as thefirst diaphragm 21 was arranged and the zinc concentration of the first electrolytic solution E1 (internal solution) was 0 g/L (electrolytic solution C) (Experiment No. 2), an increase in the zinc concentration of the plating solution PE due to energization was suppressed (20.5 g/L). - When the
first diaphragm tank 20 having a cation membrane (cation exchange membrane) as thefirst diaphragm 21 was arranged and the zinc concentration of the first electrolytic solution E1 (internal solution) was 25 g/L (electrolytic solution A) (Experiment No. 3), an increase in the zinc concentration of the plating solution PE due to energization was suppressed (30.1 g/L). - When the
first diaphragm tank 20 having a cation membrane (cation exchange membrane) as thefirst diaphragm 21 was arranged and the zinc concentration of the first electrolytic solution E1 (internal solution) was 500 g/L (electrolytic solution A) (Experiment No. 4), an increase in the zinc concentration of the plating solution PE due to energization was suppressed (32.5 g/L). - When only the type of the cation exchange membrane was different from that in Experiment No. 3 and Experiment No. 4 (Experiment No. 5 and Experiment No. 6), similarly to Experiment No. 3 and Experiment No. 4, an increase in the zinc concentration of the plating solution PE due to energization was suppressed (Experiment No. 5: 34.0 g/L, Experiment No. 6: 34.5 g/L).
- Under the condition of Experiment No. 4, the effect of the
second diaphragm tank 70 was confirmed. When the nickel concentration after energization was measured under the condition of Experiment No. 4, the nickel concentration after energization was increased from 20.0 g/L before energization to 21.3 g/L. Table 4 shows the results obtained by using thesecond diaphragm tank 70 containing the second electrolytic solution E2 having an internal nickel concentration of 20 g/L. The nickel concentration when thesecond diaphragm 71 is an anion membrane (anion exchange membrane) (Experiment No. 7) was 16.7 g/L, and the nickel concentration when thesecond diaphragm 71 is a cation membrane (cation exchange membrane) (Experiment No. 8) was 18.5 g/L. In each case, an increase in the nickel concentration could be suppressed compared with the case where thesecond diaphragm tank 70 was not used. -
TABLE 4 Internal solution Plating solution Ion Energization Ni before Ni after Ni before Ni after exchange Membrane time energization energization energization energization No. membrane type (hr) (g/L) (g/L) (g/L) (g/L) {circle around (4)}′ None — 25 — — 20.0 21.3 ↑ {circle around (7)} Neosepta AHA Anion 25 20 29.9 ↑ 20.0 16.7 ↓ {circle around (8)} Neosepta CMB Cation 25 20 24.4 ↑ 20.0 18.5 ↓ - 100, 101 zinc-based plating apparatus
- 10 plating tank
- 20 first diaphragm tank
- 21 first diaphragm
- 30 cathode holding member
- 31 member to be plated
- 40 first anode holding member
- 41 soluble zinc-containing member
- 50 second anode holding member
- 51 soluble metal-containing member
- 60 power supply apparatus
- 61 anode terminal
- 62 cathode terminal
- 70 second diaphragm tank
- 71 second diaphragm
- E1 first electrolytic solution
- E2 second electrolytic solution
- PE plating solution
Claims (8)
1. A method for suppressing an increase in the zinc concentration of a plating solution when a zinc alloy plating member using nickel as an alloy element is manufactured using a zinc alloy plating apparatus, wherein
the plating apparatus comprises:
a plating tank capable of accommodating the plating solution which is acidic;
a first diaphragm tank which is capable of accommodating the first electrolytic solution and has a first diaphragm composed of a cation exchange membrane;
a cathode holding member for cathode-electrolyzing a member to be plated that is in contact with the plating solution inside the plating tank during use;
a first anode holding member for anode-electrolyzing a soluble zinc-containing member that is in contact with the first electrolytic solution inside the first diaphragm tank during use;
the soluble zinc-containing member held by the first anode holding member;
a soluble metal-containing member containing the nickel which is the alloying element; and
a second anode holding member for anode-electrolyzing the soluble metal-containing member,
wherein the first diaphragm tank is arranged in a manner that the first electrolytic solution is in contact with one surface of the first diaphragm and the plating solution is in contact with the other surface of the first diaphragm during use.
2. The method for suppressing an increase in the zinc concentration of a plating solution according to claim 1 , wherein the second anode holding member is arranged in a manner that the soluble metal-containing member is in contact with the plating solution during use.
3. The method for suppressing an increase in the zinc concentration of a plating solution according to claim 1 , further comprising a second diaphragm tank which is capable of accommodating a second electrolytic solution and has a second diaphragm composed of a cation exchange membrane, wherein the second diaphragm tank is arranged in a manner that the second electrolytic solution which is in contact with the soluble metal-containing member inside the second diaphragm tank is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm during use.
4. A method for manufacturing a zinc-based plating member, in which
a first diaphragm tank which has a first diaphragm composed of a cation exchange membrane and accommodates a first electrolytic solution is arranged in a manner that the first electrolytic solution is in contact with one surface of the first diaphragm and an acidic plating solution accommodated inside a plating tank is in contact with the other surface of the first diaphragm,
a member to be plated that is in contact with the plating solution in the plating tank is cathode-electrolyzed,
a soluble zinc-containing member that is in contact with the first electrolytic solution inside the first diaphragm tank is anode-electrolyzed, and a soluble metal-containing member containing nickel which is an alloy element is anode-electrolyzed,
and thereby zinc-nickel plating is formed on the member to be plated while an increase in the zinc concentration of the plating solution is suppressed.
5. The method for manufacturing a zinc-based plating member according to claim 4 , wherein the soluble metal-containing member is in contact with the plating solution in the plating tank.
6. The method for manufacturing a zinc-based plating member according to claim 4 , wherein a second diaphragm tank which has a second diaphragm composed of a cation exchange membrane and accommodates a second electrolytic solution is arranged in a manner that the second electrolytic solution is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm, and
the soluble metal-containing member is in contact with the second electrolytic solution in the second diaphragm tank is anode-electrolyzed.
7. The method for suppressing an increase in the zinc concentration of a plating solution according to claim 2 , further comprising a second diaphragm tank which is capable of accommodating a second electrolytic solution and has a second diaphragm composed of a cation exchange membrane, wherein the second diaphragm tank is arranged in a manner that the second electrolytic solution which is in contact with the soluble metal-containing member inside the second diaphragm tank is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm during use.
8. The method for manufacturing a zinc-based plating member according to claim 5 , wherein a second diaphragm tank which has a second diaphragm composed of a cation exchange membrane and accommodates a second electrolytic solution is arranged in a manner that the second electrolytic solution is in contact with one surface of the second diaphragm and the plating solution is in contact with the other surface of the second diaphragm, and
the soluble metal-containing member is in contact with the second electrolytic solution in the second diaphragm tank is anode-electrolyzed.
Applications Claiming Priority (3)
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JP2019214897A JP6750186B1 (en) | 2019-11-28 | 2019-11-28 | Method for suppressing increase in zinc concentration of plating solution and method for producing zinc-based plated member |
JP2019-214897 | 2019-11-28 | ||
PCT/JP2020/031629 WO2021106291A1 (en) | 2019-11-28 | 2020-08-21 | Method for suppressing increase in zinc concentration in plating solution, and method for producing zinc-based plating member |
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US20220298668A1 true US20220298668A1 (en) | 2022-09-22 |
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US17/297,470 Abandoned US20220298668A1 (en) | 2019-11-28 | 2020-08-21 | Method for suppressing increase in zinc concentration of plating solution and method for manufacturing zinc-based plating member |
Country Status (6)
Country | Link |
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US (1) | US20220298668A1 (en) |
EP (1) | EP3868924A4 (en) |
JP (1) | JP6750186B1 (en) |
CN (1) | CN113195798A (en) |
MX (1) | MX2021007195A (en) |
WO (1) | WO2021106291A1 (en) |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0048579A1 (en) * | 1980-09-23 | 1982-03-31 | Gkn Vandervell Limited | Method for the electro-deposition of lead alloys |
US20050082171A1 (en) * | 2003-10-20 | 2005-04-21 | Tetsuya Osaka | Preparation of soft magnetic thin film |
US20100116677A1 (en) * | 2008-11-11 | 2010-05-13 | Enthone Inc. | Galvanic bath and process for depositing zinc-based layers |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19834353C2 (en) | 1998-07-30 | 2000-08-17 | Hillebrand Walter Gmbh & Co Kg | Alkaline zinc-nickel bath |
US8377283B2 (en) * | 2002-11-25 | 2013-02-19 | Coventya, Inc. | Zinc and zinc-alloy electroplating |
JP4822268B2 (en) * | 2005-04-19 | 2011-11-24 | ユケン工業株式会社 | Recovery type electrogalvanizing method and apparatus |
JP4738910B2 (en) * | 2005-06-21 | 2011-08-03 | 日本表面化学株式会社 | Zinc-nickel alloy plating method |
EP1870495A1 (en) * | 2006-06-21 | 2007-12-26 | Atotech Deutschland Gmbh | Aqueous alkaline, cyanide-free, bath for the galvanic deposition of Zinc and Zinc alloy layers |
US20160024683A1 (en) * | 2013-03-21 | 2016-01-28 | Atotech Deutschland Gmbh | Apparatus and method for electrolytic deposition of metal layers on workpieces |
-
2019
- 2019-11-28 JP JP2019214897A patent/JP6750186B1/en active Active
-
2020
- 2020-08-21 US US17/297,470 patent/US20220298668A1/en not_active Abandoned
- 2020-08-21 CN CN202080006376.7A patent/CN113195798A/en active Pending
- 2020-08-21 WO PCT/JP2020/031629 patent/WO2021106291A1/en unknown
- 2020-08-21 EP EP20886179.9A patent/EP3868924A4/en not_active Withdrawn
- 2020-08-21 MX MX2021007195A patent/MX2021007195A/en unknown
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0048579A1 (en) * | 1980-09-23 | 1982-03-31 | Gkn Vandervell Limited | Method for the electro-deposition of lead alloys |
US20050082171A1 (en) * | 2003-10-20 | 2005-04-21 | Tetsuya Osaka | Preparation of soft magnetic thin film |
US20100116677A1 (en) * | 2008-11-11 | 2010-05-13 | Enthone Inc. | Galvanic bath and process for depositing zinc-based layers |
Also Published As
Publication number | Publication date |
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EP3868924A4 (en) | 2022-03-09 |
MX2021007195A (en) | 2022-03-18 |
CN113195798A (en) | 2021-07-30 |
WO2021106291A1 (en) | 2021-06-03 |
EP3868924A1 (en) | 2021-08-25 |
JP2021085068A (en) | 2021-06-03 |
JP6750186B1 (en) | 2020-09-02 |
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