CN112458523B - Ceramic anode electroplating bath - Google Patents
Ceramic anode electroplating bath Download PDFInfo
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- CN112458523B CN112458523B CN202011259365.8A CN202011259365A CN112458523B CN 112458523 B CN112458523 B CN 112458523B CN 202011259365 A CN202011259365 A CN 202011259365A CN 112458523 B CN112458523 B CN 112458523B
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- ceramic anode
- tank
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- 239000000919 ceramic Substances 0.000 title claims abstract description 233
- 238000009713 electroplating Methods 0.000 title abstract description 53
- 238000007747 plating Methods 0.000 claims abstract description 132
- 229910052751 metal Inorganic materials 0.000 claims abstract description 25
- 239000002184 metal Substances 0.000 claims abstract description 25
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 38
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 34
- 239000010936 titanium Substances 0.000 claims description 31
- 238000000498 ball milling Methods 0.000 claims description 27
- 239000000843 powder Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 21
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 19
- 238000001816 cooling Methods 0.000 claims description 18
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 18
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 18
- 238000005245 sintering Methods 0.000 claims description 18
- 239000011230 binding agent Substances 0.000 claims description 17
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 15
- 239000005751 Copper oxide Substances 0.000 claims description 15
- 229910000431 copper oxide Inorganic materials 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 15
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 13
- 238000007873 sieving Methods 0.000 claims description 12
- 239000002002 slurry Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 8
- 239000011701 zinc Substances 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 239000006256 anode slurry Substances 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 238000007731 hot pressing Methods 0.000 claims description 6
- 235000021355 Stearic acid Nutrition 0.000 claims description 4
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 4
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001282 organosilanes Chemical class 0.000 claims description 4
- 239000008117 stearic acid Substances 0.000 claims description 4
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229920000609 methyl cellulose Polymers 0.000 claims description 3
- 239000001923 methylcellulose Substances 0.000 claims description 3
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 3
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- LNAZSHAWQACDHT-XIYTZBAFSA-N (2r,3r,4s,5r,6s)-4,5-dimethoxy-2-(methoxymethyl)-3-[(2s,3r,4s,5r,6r)-3,4,5-trimethoxy-6-(methoxymethyl)oxan-2-yl]oxy-6-[(2r,3r,4s,5r,6r)-4,5,6-trimethoxy-2-(methoxymethyl)oxan-3-yl]oxyoxane Chemical compound CO[C@@H]1[C@@H](OC)[C@H](OC)[C@@H](COC)O[C@H]1O[C@H]1[C@H](OC)[C@@H](OC)[C@H](O[C@H]2[C@@H]([C@@H](OC)[C@H](OC)O[C@@H]2COC)OC)O[C@@H]1COC LNAZSHAWQACDHT-XIYTZBAFSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims 3
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229910021645 metal ion Inorganic materials 0.000 abstract description 8
- 238000012423 maintenance Methods 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 21
- 230000000052 comparative effect Effects 0.000 description 14
- 230000007797 corrosion Effects 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 14
- 238000000034 method Methods 0.000 description 8
- 150000001768 cations Chemical class 0.000 description 7
- 239000011159 matrix material Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 5
- 238000005868 electrolysis reaction Methods 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005452 bending Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000010405 anode material Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 235000010981 methylcellulose Nutrition 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000003796 beauty Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000011195 cermet Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- 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
- C25D17/02—Tanks; Installations therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/10—Sintering only
- B22F3/1003—Use of special medium during sintering, e.g. sintering aid
- B22F3/1007—Atmosphere
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
- B22F3/12—Both compacting and sintering
- B22F3/14—Both compacting and sintering simultaneously
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/005—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides comprising a particular metallic binder
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/12—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on oxides
-
- 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
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- 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
- C25D7/00—Electroplating characterised by the article coated
Abstract
The application discloses a ceramic anode electroplating bath, and relates to the technical field of electroplating baths. The application discloses a ceramic anode electroplating bath, which comprises a plurality of common electroplating baths, a plating solution, plating metal and an electroplating auxiliary bath, wherein the plating metal and the plating solution are arranged in the common electroplating baths, the ceramic anode electroplating bath also comprises a ceramic anode plating bath, an anode pipeline and a ceramic anode auxiliary bath, the common electroplating baths and the ceramic anode plating bath are connected with the electroplating auxiliary bath through connecting pipes, a ceramic anode and the plating solution are arranged in the ceramic anode plating bath, the ceramic anode is fixed at the anode of the ceramic anode plating bath, the ceramic anode is provided with a plurality of ceramic barrels, the ceramic barrels are connected with the ceramic anode auxiliary bath through the anode pipeline, and the ceramic barrels are internally provided with anode solution and plating metal. The ceramic anode electroplating bath provided by the application can control the concentration of plating metal ions in the electroplating bath, improve the yield of products and reduce the production cost and the maintenance cost of the plating solution.
Description
Technical Field
The application belongs to the technical field of electroplating baths, and particularly relates to a ceramic anode electroplating bath.
Background
Electroplating is a process of plating a thin layer of other metals or alloys on the surface of some metals by utilizing the electrolysis principle, and is a process of adhering a metal film on the surface of the metal or other material parts by utilizing the electrolysis so as to play roles of preventing the metal from being oxidized (such as rust), improving the wear resistance, conductivity, reflectivity, corrosion resistance (such as copper sulfate and the like), improving the beauty and the like. During electroplating, plating metal or other insoluble materials are used as an anode, a workpiece to be plated is used as a cathode, and cations of the plating metal are reduced on the surface of the workpiece to be plated to form a plating layer. The electroplating bath is one electroplating apparatus for electroplating liquid, and when DC current passes through the electroplating bath, oxidation reaction occurs at the interface between anode and solution and reduction reaction occurs at the interface between cathode and solution to produce the required electroplated product. The plating tank can be used for plating zinc, copper, nickel, gold and other electroplating products.
In the electroplating process, cations generated by plating metal and cations in the bath solution are deposited on the product under the action of charges to form a compact plating layer. In the prior art, as the cation generated by the plating metal is far more than that required by the product, the concentration of the cation in the bath solution is gradually increased and exceeds the control range, so that the stability of the bath solution is maintained, the yield of the product is improved, the discharge of wastewater is greatly burdened, more polishing agent is needed to be added to maintain the bath solution, and the maintenance cost and the production cost are increased.
At present, oxide ceramic or cermet is used as an anode material, mainly because of good thermochemical stability, strong corrosion resistance, oxidation resistance, conductivity and shock resistance, and is mainly used for replacing a carbon anode to become one of inert anode materials for molten salt electrolysis. The ceramic anode is used in the electroplating bath, and the excellent mechanical property, corrosion resistance and conductivity of the ceramic anode are mainly utilized to control the concentration of metal ions of a plating layer in the electroplating bath, so that the production cost is reduced, and the service life of the electroplating bath is prolonged.
Disclosure of Invention
The application provides a ceramic anode electroplating bath, which mainly aims to control the concentration of anode metal ions in the electroplating bath, improve the yield of products and reduce the production cost and the maintenance cost of plating solution.
In order to solve the technical problems, the application provides a ceramic anode electroplating bath, which comprises a plurality of common electroplating tanks, a plating solution and an electroplating auxiliary tank, wherein the plating solution is arranged in the common electroplating tanks, and further comprises a ceramic anode electroplating tank, an anode pipeline and a ceramic anode auxiliary tank, the common electroplating tank and the ceramic anode electroplating tank are connected with the electroplating auxiliary tank through connecting pipes, a ceramic anode and the plating solution are arranged in the ceramic anode electroplating tank, the ceramic anode is fixed at the anode of the ceramic anode electroplating tank, the ceramic anode is provided with a plurality of ceramic barrels, the ceramic barrels are connected with the ceramic anode auxiliary tank through the anode pipeline, and anode solution and plating metal are arranged in the ceramic barrels.
Further, a circulating pump is arranged on the anode pipeline.
Further, the ceramic anode is fixed on two side groove walls of the ceramic anode plating groove anode.
Further, the ceramic barrel is Ti/TiO 2 -NiFe 2 O 4 And (3) ceramics.
Further, the Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared from the following raw materials in parts by weight: 15-30 parts of nickel oxide, 30-50 parts of ferric oxide, 10-30 parts of titanium oxide, 5-20 parts of titanium powder, 1-3 parts of organic binder, 3-6 parts of yttrium oxide and oxygen3-6 parts of copper.
Further, the Ti/TiO 2 -NiFe 2 O 4 The preparation method of the ceramic comprises the following specific steps:
(1) Weighing the raw materials according to the weight parts, and then vacuum drying the raw materials for 4 hours at 110 ℃;
(2) Uniformly mixing ferric oxide and nickel oxide, placing the mixture in a ball mill, adding 3wt% of absolute ethyl alcohol into the ball mill, performing ball milling for 1-2h, adding titanium oxide, performing ball milling for 2h, adding 200wt% of absolute ethyl alcohol, and performing ball milling for 10h to obtain ceramic slurry; wherein the ball milling speed is 320r/min, and the ball-material ratio is 3:1;
(3) Drying the slurry at 110 ℃ for 8-10h, cooling, and sieving with 120 meshes to obtain powder;
(4) Placing the dried and sieved powder into a high-temperature sintering furnace, performing normal-pressure high-temperature sintering under the air atmosphere, wherein the sintering temperature is 1200-1300 ℃, the heat preservation time is 2 hours, cooling to room temperature along with the furnace, grinding, and sieving with a 120-mesh sieve to obtain ceramic powder;
(5) Uniformly mixing the ceramic powder, titanium powder, yttrium oxide and copper oxide, adding an organic binder and 300wt% absolute ethyl alcohol, ball-milling for 12 hours to obtain ceramic anode slurry, drying the ceramic anode slurry at 120 ℃ for 3-4 hours, cooling, and sieving with a 120-mesh sieve to obtain ceramic anode powder;
(6) Putting ceramic anode powder into a hot-pressing mold with a required shape, sintering at 110-1200deg.C under 2-3MPa, holding for 4 hr, cooling to room temperature, taking out, coarse grinding, fine grinding, polishing, and cleaning to obtain Ti/TiO 2 -NiFe 2 O 4 And (3) ceramics.
Further, the organic binder is one or more of polyvinyl alcohol, polymethyl methacrylate, stearic acid, methyl cellulose and organosilane.
A ceramic anode plating tank can be used for products of zinc plating, zinc plating nickel plating, copper plating, tin plating, aluminum plating and gold plating.
The application has the following beneficial effects:
1. the plating bath is internally provided with the ceramic anode plating bath, the anode pipeline and the ceramic anode auxiliary tank, the ceramic anode is fixed in the ceramic anode plating bath, and cations dissolved by plating metal can be isolated in the ceramic anode by the ceramic anode, but free movement of charges is not limited, so that the plating process of a product is not influenced, and cations in bath solution can be deposited on the product.
2. The plating tank provided with the ceramic anode is connected with other common plating tanks through the electroplating auxiliary tank, so that redundant zinc ions in other plating tanks can be consumed, the concentration of zinc ions in the whole plating tank can be controlled, and the method has great advantages in reducing the maintenance cost of tank liquor, the production cost of products and the discharge cost of wastewater.
3. The ceramic barrel of the application is made of Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared, has excellent corrosion resistance and conductivity, prolongs the service life of the ceramic anode, and further reduces the production cost.
4. NiFe in the preparation process of the ceramic barrel 2 O 4 As a ceramic matrix material, the ceramic matrix material has excellent corrosion resistance in high-temperature plating solution, and after titanium oxide is added, the titanium oxide is easy to interact with nickel oxide and ferric oxide in the sintering process, so that the viscosity of a glass phase is reduced, and the wettability of the ceramic matrix material is improved; the addition of titanium oxide further improves the corrosion resistance and mechanical properties of the ceramic matrix material; the titanium oxide is converted into rutile type during sintering, so that the conductivity of the ceramic matrix material is enhanced.
5. The titanium powder is added in the preparation process of the ceramic barrel, has strong chemical activity, has great affinity with oxides, copper oxide and yttrium oxide in a ceramic matrix material, has good wettability to metal oxides and can permeate between the metal oxides, so that a compact ceramic material is formed, and the mechanical strength and corrosion resistance of the ceramic barrel are improved; the advantages of the metal material can be exerted due to the addition of the titanium powder, so that the conductivity of the ceramic barrel is enhanced, the normal movement of charges in the ceramic anode plating tank is ensured, and further, the consumption of metal ions in the tank liquor during the production of products is ensured, and the normal metal plating on the surface of the products is not influenced.
6. According to the application, the copper oxide and the yttrium oxide are doped into the ceramic matrix material in a composite manner, and the addition of the copper oxide greatly improves the corrosion resistance of the ceramic barrel; the yttrium oxide can form liquid phase with other oxides during high-temperature sintering, the density and mechanical property of the ceramic barrel can be improved, and the yttrium oxide can also remarkably improve Ti/TiO 2 -NiFe 2 O 4 The conductivity of the ceramic.
7. According to the application, the ceramic anode is arranged in the electroplating bath, so that metal ions dissolved from the plating metal are isolated in the ceramic barrel, but the free movement of charges in the ceramic anode plating bath is not influenced, and the metal ions in the plating solution can be deposited on a product, so that the concentration of the plating metal ions in the electroplating bath is controlled, the yield of the product is improved, and the production cost and the maintenance cost of the plating solution are reduced. The ceramic barrel is prepared by compounding copper oxide and yttrium oxide and doping Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared, has excellent mechanical property, corrosion resistance and conductivity, prolongs the service life of the electroplating bath, and reduces the electroplating cost.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application and do not constitute a limitation on the application. In the drawings:
FIG. 1 is a schematic view of a ceramic anode plating bath according to an embodiment of the application;
FIG. 2 is a schematic structural view of an embodiment of the inside of a ceramic anode of the present application.
The attached drawings are identified: 1. a ceramic anode plating tank; 2. a common plating tank; 3. electroplating the auxiliary groove; 4. a ceramic anode auxiliary groove; 5. a ceramic anode; 6. an anode pipe; 7. a connecting pipe; 8. a ceramic barrel.
Detailed Description
Certain terms are used throughout the description and claims to refer to particular components. Those of skill in the art will appreciate that a hardware manufacturer may refer to the same component by different names. The description and claims do not take the form of an element differentiated by name, but rather by functionality. The description hereinafter sets forth a preferred embodiment for practicing the application, but is not intended to limit the scope of the application, as the description is given for the purpose of illustrating the general principles of the application. The scope of the application is defined by the appended claims.
The present application will be described in further detail below with reference to the drawings, but is not limited thereto.
Example 1:
as shown in fig. 1, a ceramic anode plating tank according to an embodiment of the present application includes a plurality of general plating tanks 2, a plating solution (not shown), a plating metal (not shown), and a plating sub-tank 3, the plating metal and the plating solution being disposed in the general plating tanks 2. For example, a galvanization process (the plating metal is a zinc plate, and the plating solution is a zinc ion solution): the product is put into the electroplating bath and electrified, zinc ions are generated by the zinc plate and deposited on the product under the action of charges to form a compact zinc plating layer.
As shown in fig. 1, the ceramic anode plating tank according to the embodiment of the present application further includes a ceramic anode plating tank 1, an anode pipe 6, and a ceramic anode sub-tank 4. The common plating tank 2 and the ceramic anode plating tank 1 are connected with the electroplating auxiliary tank 3 through the connecting pipe 7, so that plating solution can circulate between the common plating tank 2 and the ceramic anode plating tank 1, and the ion concentration in the plating solution in each plating tank is the same.
As shown in fig. 2, a ceramic anode 5 and plating solution are disposed in a ceramic anode plating tank 1, the ceramic anode 5 is fixed at the anode of the ceramic anode plating tank 1, a plurality of ceramic barrels 8 are disposed in the ceramic anode, the ceramic barrels 8 are connected with a ceramic anode auxiliary tank 4 through an anode pipe 6, and a circulating pump (not shown in the figure) is mounted on the anode pipe 6. An anolyte and a plating metal are arranged in the ceramic barrel 8. The anolyte is mixed in the ceramic anode auxiliary tank 4 through the anode pipeline 6, and the anolyte and the plating solution are isolated from each other and are not contacted with each other. The ceramic barrel 8 in the application can isolate most of internal and external ion exchange (zinc ions, nickel ions and the like) but does not influence free movement of charges, so that ions dissolved out of the interior of the ceramic barrel 5 do not enter the plating solution, and only ions in the plating solution are consumed when a product is produced, thereby reducing the ion concentration in the plating solution. Then the plating solution in the ceramic anode plating tank 1 is mixed with the plating solution in the common plating tank 2, so that the concentration of the plating solution in the common plating tank 2 is reduced, and the concentration of ions in the whole plating tank is effectively controlled, thereby improving the yield of products and reducing the production cost and the maintenance cost of the plating solution.
In this embodiment 1, the ceramic bucket 8 is fixed on both side walls of the ceramic anode plating tank 1 at the anode.
The ceramic anode plating tank of the present application can be used for plating products such as copper plating, tin plating, aluminum plating, and gold plating, in addition to zinc plating, and is not limited to the plating products listed in the present application.
It is noted that the ceramic bucket 8 of the present application is not limited to be fixed to both side walls of the tank at the anode of the ceramic anode plating tank 1, and may be fixed to any position at the anode of the ceramic anode plating tank 1. In addition, the ceramic barrels 8 of the present application include at least 1 ceramic barrel.
The ceramic anode electroplating bath comprises the following mounting steps:
a. firstly, preparing a required ceramic anode 5, anolyte and a ceramic anode auxiliary tank 4;
b. fixing a plurality of ceramic barrels 8 in a ceramic anode 5 at the anode of a common plating tank (can be arranged on the tank walls at two sides of the anode of the common plating tank or in the middle or other positions of the anode of the common plating tank), forming a ceramic anode plating tank by combining the common plating tanks, and then connecting the ceramic barrels 8 with a ceramic anode auxiliary tank 4 by using an anode pipeline 6;
c. filling ceramic anode liquid into a ceramic barrel 8 of a ceramic anode 5, and starting a circulating pump to circulate with a ceramic anode auxiliary tank 4;
d. the flying targets filled with the plating metal are arranged in a ceramic barrel 8 of a ceramic anode 5, and the conduction condition of each place is checked to ensure good conduction;
e. and placing the product in the electroplating bath and electrifying to finish the electroplating process.
Example 2 ceramic barrels in ceramic anode plating baths
The ceramic barrel in the ceramic anode electroplating bath is Ti/TiO 2 -NiFe 2 O 4 Ceramic of Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared from the following raw materials in parts by weight: 15 parts of nickel oxide, 50 parts of ferric oxide, 20 parts of titanium oxide, 15 parts of titanium powder, 1 part of organic binder, 3 parts of yttrium oxide and 6 parts of copper oxide. The organic binder is polyvinyl alcohol.
Ti/TiO 2 -NiFe 2 O 4 The preparation method of the ceramic comprises the following specific steps:
(1) The raw materials are weighed according to the weight portions, and then the raw materials are dried in vacuum for 4 hours at 110 ℃.
(2) Mixing ferric oxide and nickel oxide uniformly, placing the mixture into a ball mill, adding 3wt% of absolute ethyl alcohol into the ball mill, performing ball milling for 1-2h, adding titanium oxide, performing ball milling for 2h, adding 200wt% of absolute ethyl alcohol, and performing ball milling for 10h to obtain ceramic slurry. Wherein the ball milling speed is 320r/min, and the ball-material ratio is 3:1; the 3wt% of absolute ethyl alcohol refers to that the mass of the absolute ethyl alcohol accounts for 3 percent of the sum of the mass of the ferric oxide and the nickel oxide; the absolute ethanol with the weight percent of 200 refers to that the absolute ethanol accounts for 200 percent of the total mass of the ferric oxide, the nickel oxide and the titanium oxide.
(3) And (3) drying the ceramic slurry at 110 ℃ for 8-10 hours, cooling, and sieving with a 120-mesh sieve to obtain powder.
(4) And (3) placing the dried and sieved powder into a high-temperature sintering furnace, performing normal-pressure high-temperature sintering under the air atmosphere, wherein the sintering temperature is 1200-1300 ℃, the heat preservation time is 2 hours, cooling to room temperature along with the furnace, grinding, and sieving with a 120-mesh sieve to obtain the ceramic powder.
(5) Uniformly mixing the ceramic powder, titanium powder, yttrium oxide and copper oxide, adding an organic binder and 300wt% absolute ethyl alcohol, and ball-milling for 12 hours to prepare ceramic anode slurry; and (3) placing the ceramic anode slurry at 120 ℃ for drying for 3-4 hours, cooling, and sieving with a 120-mesh sieve to obtain ceramic anode powder. By 300wt% absolute ethyl alcohol is meant that the mass of absolute ethyl alcohol is 300% of the sum of the mass of ceramic powder, yttria and copper oxide.
(6) Putting ceramic anode powder into a hot-pressing mold with a required shape, sintering at 110-1200deg.C under 2-3MPa, holding for 4 hr, cooling to room temperature, taking out, coarse grinding, fine grinding, polishing, and cleaning to obtain Ti/TiO 2 -NiFe 2 O 4 And (3) ceramics.
Example 3 ceramic barrels in ceramic anode plating baths
The ceramic barrel in the ceramic anode electroplating bath is Ti/TiO 2 -NiFe 2 O 4 Ceramic of Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared from the following raw materials in parts by weight: 30 parts of nickel oxide, 30 parts of ferric oxide, 10 parts of titanium oxide, 20 parts of titanium powder, 3 parts of organic binder, 6 parts of yttrium oxide and 3 parts of copper oxide. The organic binder is polymethyl methacrylate and stearic acid, and the mass ratio of the two binders is 3:1.
Ti/TiO 2 -NiFe 2 O 4 The preparation method of the ceramic is the same as in example 2, with specific reference to example 2.
Example 4 ceramic barrels in ceramic anode plating baths
The ceramic barrel in the ceramic anode electroplating bath is Ti/TiO 2 -NiFe 2 O 4 Ceramic of Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared from the following raw materials in parts by weight: 20 parts of nickel oxide, 40 parts of ferric oxide, 30 parts of titanium oxide, 5 parts of titanium powder, 2 parts of organic binder, 4 parts of yttrium oxide and 5 parts of copper oxide. The organic binder is stearic acid and methyl cellulose, and the mass ratio of the two binders is 1:1.
Ti/TiO 2 -NiFe 2 O 4 The preparation method of the ceramic is the same as in example 2, with specific reference to example 2.
Example 5 ceramic barrels in ceramic anode plating baths
The ceramic barrel in the ceramic anode electroplating bath is Ti/TiO 2 -NiFe 2 O 4 Ceramic of Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared from the following raw materials in parts by weight: 25 parts of nickel oxide and oxygen45 parts of ferric oxide, 20 parts of titanium oxide, 10 parts of titanium powder, 2 parts of organic binder, 5 parts of yttrium oxide and 5 parts of copper oxide. The organic binder is an organosilane.
Ti/TiO 2 -NiFe 2 O 4 The preparation method of the ceramic is the same as in example 2, with specific reference to example 2.
Comparative example 1 NiFe 2 O 4 Ceramic barrel
NiFe 2 O 4 The preparation method of the ceramic barrel comprises the following steps:
(1) The nickel oxide and iron oxide raw materials were weighed in parts by weight as in example 5, and then the raw materials were dried in vacuo at 110℃for 4 hours.
(2) Mixing ferric oxide and nickel oxide uniformly, placing into a ball mill, adding 3wt% absolute ethyl alcohol into the ball mill, performing ball milling for 1-2h, adding organosilane, performing ball milling for 2h, adding 200wt% absolute ethyl alcohol, and performing ball milling for 10h to obtain ceramic slurry. Wherein the ball milling speed is 320r/min, and the ball-material ratio is 3:1.
(3) And (3) drying the ceramic slurry at 110 ℃ for 8-10 hours, cooling, and sieving with a 120-mesh sieve to obtain powder.
(4) Loading the powder into hot-pressing mold with required shape, sintering at 110-1200deg.C under 2-3MPa, holding for 4 hr, cooling to room temperature, taking out, coarse grinding, fine grinding, polishing, and cleaning to obtain T-NiFe 2 O 4 And (3) ceramics.
Comparative example 2 TiO 2 -NiFe 2 O 4 Ceramic barrel
TiO 2 -NiFe 2 O 4 The preparation method of the ceramic barrel comprises the following steps:
(1) The raw materials were weighed according to the parts by weight in the above example 5: nickel oxide, iron oxide and titanium oxide, and then the raw materials were dried in vacuo at 110 ℃ for 4 hours.
(2) Mixing ferric oxide and nickel oxide uniformly, placing the mixture into a ball mill, adding 3wt% of absolute ethyl alcohol into the ball mill, performing ball milling for 1-2h, adding titanium oxide, performing ball milling for 2h, adding 200wt% of absolute ethyl alcohol, and performing ball milling for 10h to obtain ceramic slurry. Wherein the ball milling speed is 320r/min, and the ball-material ratio is 3:1.
(3) And (3) drying the ceramic slurry at 110 ℃ for 8-10 hours, cooling, and sieving with a 120-mesh sieve to obtain powder.
(4) Loading the powder into hot-pressing mold with required shape, sintering at 110-1200deg.C under 2-3MPa, holding for 4 hr, cooling to room temperature, taking out, coarse grinding, fine grinding, polishing, and cleaning to obtain TiO 2 -NiFe 2 O 4 And (3) ceramics.
Comparative example 3 Ti/TiO 2 -NiFe 2 O 4 Ceramic barrel
Ti/TiO 2 -NiFe 2 O 4 The preparation method of the ceramic barrel comprises the following specific steps:
(1) The raw materials were weighed according to the parts by weight in the above example 5: nickel oxide, iron oxide, titanium powder and titanium oxide, and then the raw materials were dried in vacuo at 110 ℃ for 4 hours.
(2) Mixing ferric oxide and nickel oxide uniformly, placing the mixture in a ball mill, adding 3wt% of absolute ethyl alcohol into the ball mill, performing ball milling for 1-2h, adding titanium oxide and titanium powder, performing ball milling for 2h, adding 200wt% of absolute ethyl alcohol, and performing ball milling for 10h to obtain ceramic slurry. Wherein the ball milling speed is 320r/min, and the ball-material ratio is 3:1.
(3) And (3) drying the ceramic slurry at 110 ℃ for 8-10 hours, cooling, and sieving with a 120-mesh sieve to obtain powder.
(4) Putting ceramic anode powder into a hot-pressing mold with a required shape, sintering at 110-1200deg.C under 2-3MPa, holding for 4 hr, cooling to room temperature, taking out, coarse grinding, fine grinding, polishing, and cleaning to obtain Ti/TiO 2 -NiFe 2 O 4 And (3) ceramics.
Comparative example 4 Ti/TiO 2 -NiFe 2 O 4 Ceramic barrel
Ti/TiO 2 -NiFe 2 O 4 The raw material composition and the preparation method of the ceramic barrel are the same as in example 5, except that the ceramic barrel is prepared in the following manner as in example 5In comparative example 4, copper oxide was not added, and the other components and the operation steps were unchanged.
Comparative example 5 Ti/TiO 2 -NiFe 2 O 4 Ceramic barrel
Ti/TiO 2 -NiFe 2 O 4 The raw material composition and the preparation method of the ceramic barrel were the same as in example 5, except that yttrium oxide was not added in this comparative example 4, and the other components and the operation steps were unchanged.
The ceramic barrels prepared according to examples 2-5 and comparative examples 1-5 above were tested for mechanical properties, conductivity and corrosion resistance (electrolyte composition: 90wt% Na 3 AlF 6 、5wt% CaF 2 And 5wt% Al 2 O 3 The electrolysis temperature was 960℃and the electrolysis time was 8 hours, and the test results are shown in Table 1 below.
TABLE 1 results of performance measurements for ceramic barrels
| Flexural Strength/MPa | Fracture toughness/MPa.m 1/2 | Conductivity/10 6 S·cm -1 | Corrosion rate/10 -3 g·cm -2 ·h -1 | Annual corrosion depth/cm.y -1 | |
| Example 2 | 164.5 | 9.6 | 78.4 | 0.824 | 1.225 |
| Example 3 | 157.2 | 10.2 | 65.8 | 0.719 | 1.072 |
| Example 4 | 176.8 | 10.8 | 80.7 | 0.613 | 0.938 |
| Example 5 | 182.3 | 11.3 | 85.6 | 0.517 | 0.756 |
| Comparative example 1 | 95.4 | 3.4 | 22.5 | 6.258 | 12.589 |
| Comparative example 2 | 110.9 | 4.8 | 38.5 | 4.729 | 6.015 |
| Comparative example 3 | 128.4 | 6.9 | 52.1 | 3.218 | 5.275 |
| Comparative example 4 | 145.6 | 8.5 | 61.8 | 2.765 | 4.484 |
| Comparative example 5 | 135.7 | 7.9 | 58.4 | 1.258 | 2.037 |
According to the detection results of the comparative tests, the ceramic barrel used by the ceramic anode has excellent mechanical property and conductivity, and can isolate metal ions dissolved by plating metal in the ceramic barrel, but does not influence free movement of charges in a ceramic anode plating tank, so that the service life of the ceramic anode is prolonged, and the production cost is reduced; titanium oxide is added into the ceramic barrel material, so that the bending strength, the conductivity and the corrosion resistance of the ceramic barrel are improved; titanium powder is added into the ceramic barrel material, so that the bending strength and the conductivity of the ceramic barrel are greatly improved; the yttrium oxide is added into the ceramic barrel material, so that the bending strength of the ceramic barrel is greatly improved, and the conductivity of the ceramic barrel is improved; copper oxide is added into the ceramic barrel material, so that the corrosion resistance of the ceramic barrel is greatly improved.
While the foregoing description illustrates and describes the preferred embodiments of the present application, it is to be understood that the application is not limited to the forms disclosed herein, but is not to be construed as limited to other embodiments, and is capable of numerous other combinations, modifications and environments and is capable of changes or modifications within the scope of the inventive concept as expressed herein, either as a result of the foregoing teachings or as a result of the knowledge or technology of the relevant art. And that modifications and variations which do not depart from the spirit and scope of the application are intended to be within the scope of the appended claims.
Claims (5)
1. The utility model provides a ceramic anode plating bath for zinc plating product, includes a plurality of ordinary plating tank (2), plating bath, cladding metal and electroplate sub-tank (3), cladding metal and plating bath set up in ordinary plating tank (2), its characterized in that still includes ceramic anode plating tank (1), positive pole pipeline (6) and ceramic anode sub-tank (4), ordinary plating tank (2) and ceramic anode plating tank (1) all are through connecting pipe (7) with electroplate sub-tank (3), be provided with ceramic anode and plating bath in ceramic anode plating tank (1), ceramic anode is fixed ceramic anode plating tank's (1) positive pole department, ceramic anode is provided with a plurality of ceramic barrels, ceramic barrel (8) are connected with ceramic anode sub-tank (4) through positive pole pipeline (6), be provided with positive pole liquid and cladding metal in ceramic barrel (8).
The ceramic barrel is Ti/TiO 2 -NiFe 2 O 4 Ceramics, the Ti/TiO 2 -NiFe 2 O 4 The ceramic is prepared from the following raw materials in parts by weight: 15-30 parts of nickel oxide, 30-50 parts of ferric oxide, 10-30 parts of titanium oxide, 5-20 parts of titanium powder, 1-3 parts of organic binder, 3-6 parts of yttrium oxide and 3-6 parts of copper oxide.
2. A ceramic anode plating tank according to claim 1, characterised in that the anode pipe (6) is provided with a circulation pump.
3. A ceramic anode plating tank according to claim 1, characterized in that the ceramic tank (8) is fixed on both side tank walls at the anode of the ceramic anode plating tank (1).
4. A ceramic anode plating bath according to claim 1, wherein said Ti/TiO 2 -NiFe 2 O 4 The preparation method of the ceramic comprises the following specific steps:
(1) Weighing the raw materials according to the weight parts, and then vacuum drying the raw materials for 4 hours at 110 ℃;
(2) Uniformly mixing ferric oxide and nickel oxide, placing the mixture in a ball mill, adding 3wt% of absolute ethyl alcohol into the ball mill, performing ball milling for 1-2h, adding titanium oxide, performing ball milling for 2h, adding 200wt% of absolute ethyl alcohol, and performing ball milling for 10h to obtain ceramic slurry; wherein the ball milling speed is 320r/min, and the ball-material ratio is 3:1;
(3) Drying the slurry at 110 ℃ for 8-10h, cooling, and sieving with 120 meshes to obtain powder;
(4) Placing the dried and sieved powder into a high-temperature sintering furnace, performing normal-pressure high-temperature sintering under the air atmosphere, wherein the sintering temperature is 1200-1300 ℃, the heat preservation time is 2 hours, cooling to room temperature along with the furnace, grinding, and sieving with a 120-mesh sieve to obtain ceramic powder;
(5) Uniformly mixing the ceramic powder, titanium powder, yttrium oxide and copper oxide, adding an organic binder and 300wt% absolute ethyl alcohol, ball-milling for 12 hours to obtain ceramic anode slurry, drying the ceramic anode slurry at 120 ℃ for 3-4 hours, cooling, and sieving with a 120-mesh sieve to obtain ceramic anode powder;
(6) Putting ceramic anode powder into a hot-pressing mold with a required shape, sintering at 110-1200deg.C under 2-3MPa, holding for 4 hr, cooling to room temperature, taking out, coarse grinding, fine grinding, polishing, and cleaning to obtain Ti/TiO 2 -NiFe 2 O 4 And (3) ceramics.
5. The ceramic anode plating bath according to claim 1, wherein the organic binder is one or more of polyvinyl alcohol, polymethyl methacrylate, stearic acid, methylcellulose, and organosilane.
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