CN112007837A - Insoluble anode active coating for electroplating cobalt, nickel and rhenium and preparation method thereof - Google Patents
Insoluble anode active coating for electroplating cobalt, nickel and rhenium and preparation method thereof Download PDFInfo
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/50—Multilayers
- B05D7/56—Three layers or more
- B05D7/58—No clear coat specified
- B05D7/584—No clear coat specified at least some layers being let to dry, at least partially, before applying the next layer
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/04—Tubes; Rings; Hollow bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/30—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W)
- B05D2202/35—Metallic substrate based on refractory metals (Ti, V, Cr, Zr, Nb, Mo, Hf, Ta, W) based on Ti
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2451/00—Type of carrier, type of coating (Multilayers)
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Abstract
The invention discloses an insoluble anode active coating for electroplating cobalt, nickel and rhenium and a manufacturing method thereof. The preparation method comprises the steps of pretreating, coating the bottom layer, the middle layer and the surface layer in sequence, and repeatedly brushing, drying, baking in the atmosphere and cooling the bottom layer, the middle layer and the surface layer for multiple times by adopting corresponding coating liquid. The insoluble anode active coating used for electroplating cobalt, nickel and rhenium is not easy to fall off in the application of electroplating cobalt, nickel and rhenium, can bear high current impact, is suitable for double-pulse electrodeposition electroplating, and the electroplated crystallizer copper pipe has large steel passing amount.
Description
Technical Field
The invention relates to an insoluble anode active coating for electroplating cobalt, nickel and rhenium, and also relates to a manufacturing method of the insoluble anode active coating for electroplating cobalt, nickel and rhenium.
Background
Compared with the traditional graphite electrode and lead-based alloy electrode, the coating titanium electrode for electroplating has the advantages that the anode dimension is stable, the anode is conventionally called as dimension stable anode, the distance between the electrodes is not changed in the electrolytic process, and the electrolytic operation can be carried out under the condition of stable cell voltage; the oxygen evolution overpotential is lower than that of other anodes, the side reaction is obviously reduced, the oxygen evolution overpotential can be stably used under low electrolytic voltage for a long time, and the effects of saving energy and reducing cost are achieved; the problem of graphite anode and lead anode dissolution is solved, the pollution to electrolyte and cathode products is avoided, and the service life is long.
Chinese patent publication No. CN 106283125A discloses a coated titanium electrode for metal electrodeposition and a preparation method thereof, wherein the intermediate layer adopts a platinum coating or an intermediate layer containing a platinum tin oxide layer, and adopts one or a combination of chemical plating, thermal decomposition, electroplating or magnetron sputtering methods. The construction difficulty is high, the equipment investment is high, and the coating binding force is general.
A coating titanium electrode for metal electrodeposition and a preparation method thereof belong to the technical field of hydrometallurgy and electrochemical industry. The requirement on the anode is not high. Is not suitable for the high-quality anode requirement for electroplating cobalt, nickel and rhenium on the copper pipe of the crystallizer.
The anode used for electroplating cobalt, nickel and rhenium on the copper pipe of the crystallizer has high requirement on an active coating, and 1, the binding force of the anode coating is high; 2. the conduction current is sufficiently large, and particularly, the current is several times larger than the normal current when the impact current is adopted; 3. the anode has a complex shape, and the coating cannot be uniform by adopting a chemical plating, thermal decomposition, electroplating or magnetron sputtering method; 4. the components of the cobalt-nickel-rhenium electroplating solution for electroplating the copper pipe of the crystallizer are complex, the requirement on an anode coating is higher, and the coating in the prior art cannot be corroded; 5. the power supply for electroplating cobalt, nickel and rhenium on the copper pipe of the crystallizer adopts double-pulse electrodeposition, and the anode is a positive electrode for a moment and a negative electrode for a moment, so that the requirements of conductivity, inertia and binding force of an anode coating must be organically combined. The prior art can not achieve organic combination and is not durable.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: provides an insoluble anode active coating used for electroplating cobalt, nickel and rhenium, which has strong coating bonding force and is not easy to fall off, and provides a method for manufacturing the insoluble anode active coating used for electroplating cobalt, nickel and rhenium.
In order to solve the technical problem, the insoluble anode active coating used for electroplating cobalt, nickel and rhenium comprises a bottom layer, a middle layer and a surface layer which are sequentially arranged on a titanium substrate, wherein the bottom layer is a ruthenium-iridium-titanium coating, the middle layer is a platinum-palladium coating, and the surface layer is an iridium-tantalum-tin coating.
Preferably, the bottom layer coating liquid adopted by the bottom layer is a normal butanol solution of ruthenium chloride, iridium chloride and titanium tetrachloride, the middle layer coating liquid adopted by the middle layer is a normal butanol solution of chloroplatinic acid and palladium chloride, and the surface layer coating liquid adopted by the surface layer is a normal butanol solution of chloroiridic acid, tantalum pentachloride and tin tetrachloride.
Preferably, the bottom layer coating liquid is 20-40g of ruthenium chloride solution with ruthenium concentration of 100g/L, 20-40g of iridium chloride solution with iridium concentration of 100g/L, 40-70g of titanium tetrachloride and 920g of n-butyl alcohol 850-.
Preferably, the intermediate layer coating liquid is 20-40g of chloroplatinic acid solution with platinum concentration of 100g/L, 20-40g of palladium chloride solution with palladium concentration of 100g/L and 960g of n-butanol 920-960g, and the solvents of the chloroplatinic acid solution and the palladium chloride solution are all n-butanol.
Preferably, the surface layer coating liquid is 10-25g of chloroiridic acid solution with chloroiridic acid concentration of 100g/L, 20-40g of tantalum pentachloride solution with tantalum pentachloride concentration of 100g/L, 5-12g of stannic chloride alcohol solution with stannic chloride concentration of 100g/L, and 955g of n-butanol, and the solvents of the chloroiridic acid solution, the tantalum pentachloride solution and the stannic chloride alcohol solution are all n-butanol.
Preferably, the surface of the titanium substrate is pretreated into a concave-convex ramie yarn surface, and the bottom layer is coated on the ramie yarn surface.
Preferably, the titanium substrate is an anode titanium basket for electroplating the inner hole of the crystallizer copper pipe.
The insoluble anode active coating used for electroplating cobalt, nickel and rhenium is any one of the insoluble anode active coatings used for electroplating cobalt, nickel and rhenium.
Preferably, the titanium substrate is pretreated before being coated with the base coat: baking in the atmosphere to form an oxide coating on the surface of a titanium substrate, forming unevenness on the surface of the titanium basket by sand blasting using steel grit with an average particle size of 1mm or less, and etching the surface of the titanium basket in an etching solution at 75-85 ℃ for 4-6 hours, wherein the etching solution is an aqueous solution containing 10-20 wt% of oxalic acid, 5 wt% of sodium fluoride and 0.1 wt% of potassium phenolether phosphate.
The invention relates to a method for manufacturing an insoluble anode active coating for electroplating cobalt, nickel and rhenium, wherein the insoluble anode active coating for electroplating cobalt, nickel and rhenium is the insoluble anode active coating for electroplating cobalt, nickel and rhenium, the titanium substrate is an anode titanium basket for electroplating an inner hole of a copper pipe of a crystallizer, and the manufacturing method comprises the following steps: pretreatment: baking the titanium substrate in the atmosphere to form an oxide coating on the surface of the titanium substrate, forming concave-convex parts on the surface of the titanium basket by sand blasting treatment by using steel grit with the average particle size of less than 1mm, etching the rough surface for 4 to 6 hours in an etching solution, wherein the etching solution is an aqueous solution containing 10 to 20 weight percent of oxalic acid, 5 weight percent of sodium fluoride and 0.1 weight percent of potassium phenolether phosphate; and (3) coating a bottom layer, a middle layer and a surface layer in sequence, wherein the bottom layer, the middle layer and the surface layer are respectively coated with corresponding coating liquid and are repeatedly brushed, dried, baked in the atmosphere and cooled.
The invention has the beneficial effects that: the insoluble anode active coating used for electroplating cobalt, nickel and rhenium is not easy to fall off in the application of electroplating cobalt, nickel and rhenium, can bear high current impact, is suitable for double-pulse electrodeposition electroplating, and the electroplated crystallizer copper pipe has large steel passing amount.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention comprises a base coat, a middle coat and a surface coat which are arranged on a titanium substrate in sequence. The bottom coating is a ruthenium iridium titanium coating, the middle coating is a platinum palladium coating, and the top coating is an iridium tantalum tin coating. The titanium substrate adopts a conductive polar plate titanium basket, and the thickness of the titanium net is 2.0 mm. The titanium basket is made into an image anode according to the specification and the shape of the crystallizer copper tube.
First, bottom coating layer: the bottom coating is ruthenium iridium titanium active coating. The preparation of the base coat comprises the following steps:
pretreatment: the oxide coating was formed on the surface by baking the titanium basket at 550 ℃ for 3 hours in the atmosphere. Then, unevenness was formed on the surface of the titanium basket by sandblasting using steel grit having an average particle diameter of 1mm or less. Then, etching for 4-6 hours in an etching solution at 75-85 ℃ to wash out the ramie yarn surface. The etching solution is an aqueous solution containing 10-20 wt% of oxalic acid, 5 wt% of sodium fluoride and 0.1 wt% of phenol ether phosphate potassium salt (NP-4 PK). Table 1 shows the etching parameters for four examples.
TABLE 1
| Etching parameters | Example 1 | Example 2 | Example 3 | Example 4 |
| Etching time (hours) | 4 | 5 | 6 | 6 |
| Etching temperature (. degree.C.) | 85 | 80 | 70 | 75 |
| Oxalic acid wt% | 10 | 20 | 15 | 18 |
By removing the titanium oxide layer, fine irregularities are formed on the surface of the titanium basket. And (4) cleaning the titanium basket, and then putting the titanium basket into an ethanol solution to be coated with the bottom coating liquid.
The formulation of the bottom layer coating liquid is as follows: ruthenium trichloride solution with ruthenium concentration of 100g/L, iridium trichloride solution with iridium concentration of 100g/L, titanium tetrachloride and n-butanol. The ruthenium chloride solution and the iridium chloride solution adopt the national standard products which are purchased in the market, wherein the solvent is n-butyl alcohol. Table 2 shows the formulation of the primer coating liquid for four examples. The element concentration in the present invention means the ion concentration of the element.
TABLE 2
The preparation method of the bottom coating liquid comprises the following steps: slowly adding titanium tetrachloride into ruthenium chloride solution, cooling to 5 ℃ or lower by using dry ice, then slowly adding iridium chloride solution, and finally adding n-butyl alcohol to prepare ruthenium iridium titanium solution.
The coating liquid was applied to a titanium basket with a brush, dried at 75 ℃ for 2 minutes, baked at 475 ℃ in the atmosphere for 10 minutes, and then cooled to room temperature. The steps of brushing, drying, baking and cooling were repeated for a total of 5 times.
(II) intermediate coating: is a platinum palladium coating.
The preparation method of the intermediate coating comprises the following steps:
preparing an intermediate layer coating liquid: chloroplatinic acid (H) with a platinum concentration of 100g/L2PtCl6.6H2O) solution, Palladium chloride (PdCl) having Palladium concentration of 100g/L2) Mixing the solution with n-butanol. The chloroplatinic acid solution and the palladium chloride solution adopt the national standard products purchased in the market, wherein the solvent is n-butyl alcohol. Table 3 shows the formulations of the intermediate layer coating liquids of the four examples.
TABLE 3
The intermediate layer coating liquid was brushed on the undercoated titanium basket with a brush, dried at 75 ℃ for 2 minutes, baked at 550 ℃ for 5 minutes in the air, and then cooled to room temperature. The processes of coating, drying, baking and cooling of the intermediate layer coating liquid were repeated 5 times in total, and then the process was further coated 2 times to change the baking time to 30 minutes. Forming an intermediate layer.
(II) top coating: is an iridium tantalum tin salt coating.
The preparation method of the top coating comprises the following steps:
preparing a surface layer coating liquid layer: using a solution of chloroiridic acid (H)2IrCl6.4H2O), tantalum pentachloride solution, stannic chloride alcohol solution and n-butyl alcohol. Table 4 shows the coating liquid formulations for the top layers of the four examples.
TABLE 4
The concentrations of the chloroiridic acid solution, the tantalum pentachloride solution and the stannic chloride alcohol solution are all 100 g/L.
The top coat liquid layer was brushed on a titanium basket, dried at 75 ℃ for 2 minutes, baked at 550 ℃ for 5 minutes in the air, and then cooled to room temperature. The steps of brushing, drying, baking and cooling were repeated for a total of 8 times.
(IV) electroplating examination is carried out on the insoluble anode titanium basket with the commercially available insoluble coating and the insoluble anode titanium basket for electroplating cobalt, nickel and rhenium in the cobalt, nickel and rhenium plating solution for the inner hole of the crystallizer copper pipe
Preparing a cobalt-nickel-rhenium electroplating solution for a copper pipe of a crystallizer: 50-100g/L of nickel sulfate, 25g/L of nickel chloride, 150g/L of cobalt sulfate, 35g/L of boric acid and ammonium perrhenate: 0.5-5g/L, Dw-2012A stabilizer 5g/L, Dw-2012B hardener 5-10ml/L, Dw-2012C anti-pinhole agent 1-2ml/L, DW-2012E pressure regulator 1-5 g/L.
Dw-2012A stabilizer formulation: 50kg of sodium citrate (contributing to the fine plating layer) and 50kg of sodium gluconate (stabilizing the plating solution).
Dw-2012B hardener formulation: 100g of trimethylhydroxyethylamine boron tetrafluoride, 25g of methyl imidazole ethyl sulfate, 25g of 1-ethyl-3-methyl imidazole hexafluorophosphate and 900g of water.
Dw-2012C anti-pinhole agent formulation: 50g of sodium dodecyl sulfate, 50g of sodium 2-ethylhexyl sulfate and 900g of water.
DW-2012E pressure regulator formulation: 100g saccharin, 50g phenylurea and 850g water.
Conditions of electroplating are as follows:
the pH value of the electroplating bath solution is 3.7; the temperature of the plating bath is 60 ℃; current density 4A/dm2(ii) a Electroplating time: 3 hours; power supply: double pulses.
Four coated anode titanium baskets were made using the above four examples, each example corresponding to 50 titanium baskets. As a control, 50 commercially available insoluble coated anode baskets (denoted by a) were used. The crystallizer copper pipes are all square pipes of 150 × 900.
Four coated anode titanium baskets (indicated by B) were fabricated using the above four examples 1,2,3,4 using the above crystallizer copper tube cobalt nickel rhenium bath with a commercially available insoluble coated anode (indicated by A) and a titanium basket (indicated by B) made according to the present invention as the anode, and the anodes were of the same size.
Table 5 shows the average parameters of a 50 arms, and B shows the average parameters of 50 arms of each of 4 examples.
In Table 6, 1,2,3 and 4 represent average parameters of 50 arms for each of 4 examples of B.
TABLE 5
Through the test data, the commercial anode activated coating cannot bear high current impact, and the coating with large current is peeled off and cannot be used. The binding force of the coating is in accordance with the national standard, and the higher the grade is, the lower the binding force is.
TABLE 6
The steel passing amount is the maximum steel passing amount in the use of the crystallizer copper pipe of the continuous casting machine in the steel mill after electroplating.
The data show that the anode coating prepared by the formulas 1,2,3 and 4 has little change in performance and good stability.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (10)
1. An insoluble anodic active coating for cobalt nickel rhenium electroplating, characterized by: the coating comprises a bottom layer, a middle layer and a surface layer which are sequentially arranged on a titanium substrate, wherein the bottom layer is a ruthenium iridium titanium coating, the middle layer is a platinum palladium coating, and the surface layer is an iridium tantalum tin coating.
2. An insoluble anodic active coating for electroplating cobalt nickel rhenium according to claim 1 characterised in that: the bottom layer coating liquid adopted by the bottom layer is a normal butanol solution of ruthenium chloride, iridium chloride and titanium tetrachloride, the middle layer coating liquid adopted by the middle layer is a normal butanol solution of chloroplatinic acid and palladium chloride, and the surface layer coating liquid adopted by the surface layer is a normal butanol solution of chloroiridic acid, tantalum pentachloride and tin tetrachloride.
3. An insoluble anodic active coating for electroplating cobalt nickel rhenium according to claim 2 characterised in that: the bottom layer coating liquid is 20-40g of ruthenium chloride solution with ruthenium concentration of 100g/L, 20-40g of iridium chloride solution with iridium concentration of 100g/L, 40-70g of titanium tetrachloride and 920g of n-butyl alcohol 850-.
4. An insoluble anodic active coating for electroplating cobalt nickel rhenium according to claim 3 characterised in that: the intermediate layer coating liquid is 20-40g of chloroplatinic acid solution with platinum concentration of 100g/L, 20-40g of palladium chloride solution with palladium concentration of 100g/L and 960g of n-butyl alcohol 920-960g, and the solvents of the chloroplatinic acid solution and the palladium chloride solution are n-butyl alcohol.
5. An insoluble anodic active coating for electroplating cobalt nickel rhenium according to claim 4 characterised in that: the surface layer coating liquid is 10-25g of chloroiridic acid solution with chloroiridic acid concentration of 100g/L, 20-40g of tantalum pentachloride solution with tantalum pentachloride concentration of 100g/L, 5-12g of stannic chloride alcohol solution with stannic chloride concentration of 100g/L, 928-955g of n-butyl alcohol, and the chloroiridic acid solution, the tantalum pentachloride solution and the stannic chloride alcohol solution are all n-butyl alcohol.
6. An insoluble anodic active coating for electroplating cobalt nickel rhenium according to claim 5 characterised in that: the surface of the titanium substrate is pretreated into a concave-convex ramie yarn surface, and the bottom layer is coated on the ramie yarn surface.
7. Insoluble anodic active coating for the electroplating of cobalt nickel rhenium according to any of the claims from 1 to 6, characterized in that: the titanium substrate is an anode titanium basket for electroplating the inner hole of the crystallizer copper pipe.
8. A method for manufacturing an insoluble anode active coating used for electroplating cobalt, nickel and rhenium is characterized in that: the insoluble anodic active coating for electroplating cobalt nickel rhenium is the insoluble anodic active coating for electroplating cobalt nickel rhenium according to any one of claims 1 to 6.
9. The method of claim 8 for making an insoluble anodic active coating for cobalt nickel rhenium electroplating, wherein: the titanium matrix is pretreated before being coated with a base coat: baking in the atmosphere to form an oxide coating on the surface of a titanium substrate, forming unevenness on the surface of the titanium basket by sand blasting using steel grit with an average particle size of 1mm or less, and etching the surface of the titanium basket in an etching solution at 75-85 ℃ for 4-6 hours, wherein the etching solution is an aqueous solution containing 10-20 wt% of oxalic acid, 5 wt% of sodium fluoride and 0.1 wt% of potassium phenolether phosphate.
10. A method for manufacturing an insoluble anode active coating used for electroplating cobalt, nickel and rhenium is characterized in that: the insoluble anode active coating for electroplating cobalt, nickel and rhenium is the insoluble anode active coating for electroplating cobalt, nickel and rhenium as claimed in claim 6, the titanium substrate is an anode titanium basket for electroplating an inner hole of a copper pipe of a crystallizer, and the manufacturing method comprises the following steps: pretreatment: baking the titanium substrate in the atmosphere to form an oxide coating on the surface of the titanium substrate, forming concave-convex parts on the surface of the titanium basket by sand blasting treatment by using steel grit with the average particle size of less than 1mm, etching the rough surface for 4 to 6 hours in an etching solution, wherein the etching solution is an aqueous solution containing 10 to 20 weight percent of oxalic acid, 5 weight percent of sodium fluoride and 0.1 weight percent of potassium phenolether phosphate; and (3) coating a bottom layer, a middle layer and a surface layer in sequence, wherein the bottom layer, the middle layer and the surface layer are respectively coated with corresponding coating liquid and are repeatedly brushed, dried, baked in the atmosphere and cooled.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113151885A (en) * | 2021-03-15 | 2021-07-23 | 广州鸿葳科技股份有限公司 | Titanium anode for electroplating and preparation method thereof |
| CN115007817A (en) * | 2022-06-29 | 2022-09-06 | 济南东方结晶器有限公司 | Method for manufacturing high-pulling-speed crystallizer with cooling water guide holes |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118384A (en) * | 1994-09-08 | 1996-03-13 | 广州有色金属研究院 | Coating electrode for electrolytic metallurgic industry |
| EP2014460A2 (en) * | 2007-07-09 | 2009-01-14 | ONERA (Office National d'Etudes et de Recherches Aérospatiales) | Method for protecting the surface of an intermetallic alloy substrate with a titanium-aluminide base against corrosion |
| CN103215614A (en) * | 2013-04-27 | 2013-07-24 | 中国船舶重工集团公司第七二五研究所 | Preparation method of metallic oxide anode containing cold spraying tantalum intermediate layer |
| EP3330012A4 (en) * | 2015-07-29 | 2018-12-26 | Nippon Steel & Sumitomo Metal Corporation | Titanium composite material, and titanium material for use in hot rolling |
| CN110318068A (en) * | 2019-06-03 | 2019-10-11 | 江阴市宏泽氯碱设备制造有限公司 | Ion-exchange membrane electrolyzer anodic coating |
| CN111088493A (en) * | 2019-12-26 | 2020-05-01 | 西安泰金工业电化学技术有限公司 | Preparation method of titanium anode with titanium-based coating |
-
2020
- 2020-08-27 CN CN202010877629.XA patent/CN112007837A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1118384A (en) * | 1994-09-08 | 1996-03-13 | 广州有色金属研究院 | Coating electrode for electrolytic metallurgic industry |
| EP2014460A2 (en) * | 2007-07-09 | 2009-01-14 | ONERA (Office National d'Etudes et de Recherches Aérospatiales) | Method for protecting the surface of an intermetallic alloy substrate with a titanium-aluminide base against corrosion |
| CN103215614A (en) * | 2013-04-27 | 2013-07-24 | 中国船舶重工集团公司第七二五研究所 | Preparation method of metallic oxide anode containing cold spraying tantalum intermediate layer |
| EP3330012A4 (en) * | 2015-07-29 | 2018-12-26 | Nippon Steel & Sumitomo Metal Corporation | Titanium composite material, and titanium material for use in hot rolling |
| CN110318068A (en) * | 2019-06-03 | 2019-10-11 | 江阴市宏泽氯碱设备制造有限公司 | Ion-exchange membrane electrolyzer anodic coating |
| CN111088493A (en) * | 2019-12-26 | 2020-05-01 | 西安泰金工业电化学技术有限公司 | Preparation method of titanium anode with titanium-based coating |
Non-Patent Citations (1)
| Title |
|---|
| 黄运涛: "钛基金属氧化物阳极的研究进展", 《全面腐蚀控制》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113151885A (en) * | 2021-03-15 | 2021-07-23 | 广州鸿葳科技股份有限公司 | Titanium anode for electroplating and preparation method thereof |
| CN115007817A (en) * | 2022-06-29 | 2022-09-06 | 济南东方结晶器有限公司 | Method for manufacturing high-pulling-speed crystallizer with cooling water guide holes |
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