CN115613083A - Titanium anode for copper plating field, preparation method and copper plating equipment - Google Patents
Titanium anode for copper plating field, preparation method and copper plating equipment Download PDFInfo
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- CN115613083A CN115613083A CN202211379476.1A CN202211379476A CN115613083A CN 115613083 A CN115613083 A CN 115613083A CN 202211379476 A CN202211379476 A CN 202211379476A CN 115613083 A CN115613083 A CN 115613083A
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- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
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- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/04—Pretreatment of the material to be coated
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1204—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material inorganic material, e.g. non-oxide and non-metallic such as sulfides, nitrides based compounds
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- C23C18/1216—Metal oxides
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1225—Deposition of multilayers of inorganic material
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- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/1229—Composition of the substrate
- C23C18/1241—Metallic substrates
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- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/02—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition
- C23C18/12—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by thermal decomposition characterised by the deposition of inorganic material other than metallic material
- C23C18/125—Process of deposition of the inorganic material
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- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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Abstract
The invention discloses a titanium anode used in the copper plating field, a preparation method and copper plating equipment, wherein the copper plating equipment comprises the titanium anode, the titanium anode comprises a titanium substrate, a coating and a protective layer, and the preparation method comprises the following steps: step one, carrying out pretreatment on a titanium substrate; step two, cleaning and drying the pretreated titanium substrate; step three, preparing an active layer containing metal oxide on the titanium substrate by a thermal decomposition method; step four, preparing a silicon dioxide or zirconium dioxide protective layer on the active coating, thereby obtaining the titanium anode with the protective layer; the titanium anode and the copper plating equipment thereof have the characteristics of stable performance and long service life.
Description
Technical Field
The invention belongs to the technical field of copper plating, and particularly relates to a titanium anode used in the field of copper plating, a preparation method and copper plating equipment.
Background
The titanium-based insoluble anode, namely a titanium anode, is an anode material which takes metal titanium as a matrix and has a catalytic active coating on the surface of the titanium matrix. In the electrochemical process, the titanium anode has good corrosion resistance and high catalytic activity, can keep the stability of size and shape in the electrolytic process, and is widely applied to the fields of electroplating, chlor-alkali industry, wastewater treatment, organic electrosynthesis, cathode protection and the like.
In the field of electrolytic copper plating, since the titanium anode itself does not generate Cu 2+ Replenishment of Cu in the plating bath 2+ There are two main ways of (1): firstly, adding CuO powder into electroplating solution, wherein the CuO powder is mixed with H in the electroplating solution + Reaction occurs to thereby generate Cu 2+ So that Cu in the plating solution 2+ So that the reaction takes place: cuO +2H + →Cu 2+ +H 2 O+2e - . Secondly, adding a certain amount of FeSO into the electroplating solution 4 ·7H 2 O, in this case, fe is generated at the anode 2+ →Fe 3+ ，2H 2 O→O 2 ↑+4H + +4e - Two reactions, meanwhile, the plating bath is communicated with a copper dissolving tank, a large amount of pure copper particles are filled in the copper dissolving tank, and the reaction occurs in the copper dissolving tank: fe 3+ +Cu→Fe 2+ +Cu 2+ +e - I.e. Fe 3+ Reacts with pure copper particles to generate Cu 2+ So that Cu in the plating solution 2+ Is supplemented, and simultaneously dissolves Fe generated in the copper groove 2+ Further oxidized at the anode, so that the whole system reaches a stable circulation state.
The titanium anode used in the field of electrolytic copper plating is generally an Ir-Ta system titanium anode, a common Ir-Ta anodeThe pole is generally divided into three stages during use: first, the activation stage, in which the catalytic activity of the titanium anode is gradually increased. And a steady operation stage, wherein the catalytic activity is in a steady state. And thirdly, in the gradual failure stage, the effective components of the coating are reduced, and the catalytic activity is gradually weakened. This results in an initial stage of Fe in the electroplating bath of the iron-containing system 2+ →Fe 3+ The reaction of (3) is accelerated to cause Cu in the plating solution 2+ The phenomenon of elevation occurs; while in the failure stage, fe 2+ →Fe 3+ Is increasingly slow, resulting in Cu in the plating bath 2+ A drop condition occurs. This results in the original stable equilibrium being broken, affecting the normal plating parameters and thus affecting production. While using CuO powder to supplement Cu 2+ In the plating method of (3), the amount of CuO powder automatically added can be adjusted to thereby make Cu in the plating solution 2+ The content was kept in a stable state.
On the other hand, in the field of electrolytic copper foil, the used titanium anode is also generally Ir-Ta system, although the field of electrolytic copper foil belongs to the category of electrolytic copper plating, the process is greatly different from the general electrolytic copper plating, wherein the current density born by the titanium anode is very high and can reach 7500-8000A/m 2 And the temperature of the electrolyte is as high as about 52 ℃, so that the service life of the titanium anode for the electrolytic copper foil is only about 6 months generally. How to prolong the service life of the titanium anode for the electrolytic copper foil and reduce the replacement frequency of the titanium anode, thereby reducing the production cost, and having important significance.
The preparation method of the electrolytic copper foil anode plate with the patent application number of CN201810529420.7 comprises the following steps: (1) selecting a titanium plate as a raw material; (6) preparing a noble metal solution; (7) Coating the noble metal solution on the surface of the titanium plate substrate subjected to heat treatment for multiple times to form a coating with the thickness of 6-10 mu m; the product obtained by coating the noble metal solution on the surface of the matrix has low electric energy efficiency caused by overhigh anode potential required by copper deposition in the copper foil electrolysis process, and the cost is increased, which is an important problem in production.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a titanium anode for the copper plating field, a preparation method and copper plating equipment, wherein an active layer with a catalytic function is effectively protected through the preparation of a protective layer, so that the corrosion of the active layer is reduced, and the service life of the titanium anode for the electrolytic copper foil and the copper plating equipment is prolonged.
In order to achieve the purpose, the invention adopts the technical scheme that:
a titanium anode used in the field of copper plating comprises a titanium substrate and a coating coated on the surface of the titanium substrate, wherein the coating is an active layer, the inner side of the active layer is closely adjacent to the titanium anode, and the outer side of the active layer is a silicon dioxide or zirconium dioxide protective layer;
the active layer acts as a catalyst and a protective layer of silicon dioxide or zirconium dioxide is used to avoid direct contact of the active layer with the solution.
The active layer is a mixture containing one or more of cobalt, tin, antimony, manganese, titanium, tantalum, iridium, ruthenium, rhodium, platinum or palladium chloride salts, nitrate, acetate or compounds in any ratio, wherein the concentration of metal ions is controlled between 0.1 and 0.5 mol/L.
A preparation method of a titanium anode used in the field of copper plating comprises the following steps;
step one, carrying out pretreatment on a titanium substrate;
step two, cleaning and drying the titanium substrate pretreated in the step one;
step three, preparing an active layer containing metal oxide on the titanium substrate by a thermal decomposition method on the titanium substrate treated in the step two;
and step four, preparing a silicon dioxide or zirconium dioxide protective layer on the active coating of the metal oxide prepared in the step three, thereby obtaining the titanium anode with the protective layer.
Further, the pretreatment in the first step comprises the following steps:
s11: carrying out sand blasting treatment on the titanium matrix;
s12: carrying out thermal correction on the titanium substrate treated in the step S11;
s13: and (3) carrying out acid treatment on the titanium substrate treated by the S12.
Further, the titanium matrix in the S11 is pure titanium; the sand mold subjected to sand blasting treatment is one or more of steel sand, brown corundum, white corundum, quartz sand, copper ore sand, carborundum and Hainan sand;
the temperature of the thermal sizing treatment in the S12 is 550-600 ℃;
the acid used in the acid treatment in S13 is one or a mixture of oxalic acid, hydrochloric acid, sulfuric acid, hydrofluoric acid and nitric acid in any ratio.
Further, the thermal decomposition in the third step comprises the following steps:
s31: dissolving one or more of chloride salt, nitrate salt, acetate salt or compound containing cobalt, tin, antimony, manganese, titanium, tantalum, iridium, ruthenium, rhodium, platinum or palladium in a solvent in any ratio to obtain a salt solution; wherein the total metal ion concentration in the salt solution is controlled between 0.1 and 0.5 mol/L;
s32: brushing or spraying the salt solution on the titanium substrate treated in the step two;
s33: drying the titanium substrate by a drying tunnel furnace or drying the titanium substrate by a blower;
s34: and (3) roasting the titanium matrix at the high temperature of 400-550 ℃ for 10-90 min to obtain an active layer of the oxide.
Further, the solvent used in step S31 is one or more of n-butanol, ethanol, isopropanol, propanol, methyl ether, ethyl ether, formamide, acetamide, n-pentanol, and turpentine.
Further, the preparation of the silicon dioxide or zirconium dioxide protective layer in the fourth step comprises the following steps:
s41: dissolving a salt or compound containing silicon or zirconium in a solvent to obtain a silicon/zirconium salt solution;
s42: coating or spraying the salt solution on the active layer of the metal oxide prepared in the third step;
s43: drying the titanium substrate by a drying tunnel furnace or drying the titanium substrate by a blower;
s44: and roasting the titanium matrix at the high temperature of 400-600 ℃ for 10-90 min to obtain the silicon dioxide or zirconium dioxide protective layer.
Further, the salt or compound containing silicon in S41 is a silane coupling agent or tetraethoxysilane; the salt or compound containing zirconium is butyl zirconate.
Further, in the silicon salt solution in S41, the concentration of Si ions is 0.01-0.4 mol/L; in the zirconium salt solution, the Zr ion concentration is 0.01-0.4 mol/L.
Further, the solvent in S41 is one or more of n-butanol, ethanol, isopropanol, propanol, methyl ether, ethyl ether, formamide, acetamide, n-pentanol and turpentine oil which are mixed in any ratio.
The copper plating equipment comprises a titanium anode, wherein the titanium anode is the titanium anode consisting of the titanium substrate, the active layer and the protective layer, or the titanium anode prepared by any method.
The invention has the beneficial effects that:
different from the conventional titanium anode, the invention prepares the silicon dioxide or zirconium dioxide protective layer on the surface of the active layer after preparing the active layer. The silicon dioxide has stable chemical property and plays a role in protecting the active layer. The titanium anode prepared by using the silicon dioxide as the protective layer has the advantages that the catalytic activity of the titanium anode is slowly and stably improved in the activation stage due to the protective effect of the silicon dioxide on the active layer, and the phenomenon that the Cu in the electroplating solution is caused by the rapid improvement of the catalytic activity when no protective layer exists is avoided 2+ Rapid increase and difficult stabilization. In the stable operation stage, due to the effect of the protective layer, the active layer is prevented from being in direct contact with the electroplating solution, so that the corrosion and the falling of the active layer are delayed, the active layer can be used for a longer time, and the service life of the titanium anode is prolonged. In the gradual failure stage, the active ingredients of the active layer are reduced, the protective layer gradually falls off to expose the active layer, so that a small amount of the active layer can fully play a role, and the Cu in the electroplating solution caused by insufficient catalytic activity of the titanium anode is avoided 2+ Insufficient stability is difficult.
Therefore, the invention can not only ensure that Cu in the electroplating solution in the whole process 2+ Is kept relativelyStable state, simultaneously, because the effect of silica protective layer, avoided the direct contact of active layer with the plating solution, improved the titanium anode greatly and copper facing equipment's life.
The existing titanium anode has no protective layer, which not only causes unstable catalytic activity, but also leads to Cu in the electroplating solution 2+ Fluctuates and the active layer deteriorates faster, resulting in a lower lifetime of the titanium anode. In the case of a titanium anode used in the field of electrolytic copper foil, after the active layer is prepared, a zirconium dioxide protective layer is prepared on the surface of the active layer. Zirconium has a corrosion resistance exceeding that of titanium, while zirconium dioxide has a corrosion resistance exceeding that of metallic zirconium. The preparation of the zirconium dioxide protective layer can effectively protect the active layer with the catalytic function, thereby reducing the corrosion of the active layer and further prolonging the service life of the titanium anode for the electrolytic copper foil and the copper plating equipment. The operation of the working procedure is simple and easy to implement, the service lives of the titanium anode and the copper plating equipment are prolonged under the condition that the content of the noble metal active layer is not increased, and the production cost is effectively reduced.
Drawings
FIG. 1 is a schematic view showing the structure of a titanium anode for electrolytic copper foil according to the present invention.
Fig. 2 is a schematic diagram of the structural change of the titanium anode prepared by the invention in the using process.
Fig. 3 is a schematic diagram of a titanium anode without a protective layer in the prior art.
FIG. 4 is a schematic diagram showing the comparison of the life of the anode of the electrolytic copper foil prepared with the protective layer of zirconium dioxide with that of the anode without the protective layer.
FIG. 5 is a schematic diagram showing the comparison of the life of the anode of the electrolytic copper foil prepared with the silica protective layer and the anode without the protective layer.
In the figure, 1-titanium substrate, 2-active layer, 3-silicon dioxide/zirconium dioxide protective layer.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
Example 1:
a titanium anode used in the field of copper plating comprises a titanium substrateAnd an active layer coated on the surface of the substrate, wherein the active layer is H 2 IrCl 6 ·xH 2 O、TaCl 5 Mixture of n-butanol, ir: ta (molar ratio) =7:3, a zirconium dioxide protective layer is arranged outside the active layer.
A preparation method of a titanium anode specifically comprises the following steps:
1) Spraying brown corundum on the TA1 titanium plate;
2) Carrying out thermal sizing treatment on the titanium plate subjected to sand blasting;
3) Carrying out acid treatment on the titanium plate after the thermal sizing for 2 hours by using a boiling oxalic acid solution with the concentration of 10%;
4) Cleaning the titanium plate subjected to acid treatment by using pure water, and airing;
5) Will H 2 IrCl 6 ·xH 2 O、TaCl 5 Dissolving the n-butanol solution in a solvent n-butanol to form a mixed metal solution, and controlling Ir: ta (molar ratio) =7:3, coating the oxidized titanium plate, drying, sintering at 500 ℃ for 10min, repeating the process for 10 times, and finally sintering at 500 ℃ for 60min to prepare an active layer;
6) Taking n-butyl alcohol as a solvent, and taking a certain amount of butyl zirconate to prepare a solution with the Zr ion concentration of 0.05 mol/L;
7) Uniformly spraying the solution on the titanium plate treated in the step 5);
8) Drying the titanium substrate;
9) And (3) roasting the titanium matrix at the high temperature of 400 ℃ for 10min to obtain a zirconium dioxide protective layer, thus obtaining the final titanium anode A for the electrolytic copper foil.
And (4) preparing the titanium anode B for the electrolytic copper foil as a control sample under the same other conditions without preparing a surface protection layer on the cleaned and dried titanium plate. And the samples A and B were subjected to life-strengthening experiments (electrode test area 2 cm) 2 The electrolyte is 1mol/L sulfuric acid solution, and the current density is 40000A/m 2 )。
Example 2:
the titanium anode comprises a titanium substrate and an active layer coated on the surface of the titanium substrate, wherein the active layer is H 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, coCl 2 ·6H 2 O in a mixture of n-butanol and isopropanol, wherein Ir: ta: co (molar ratio) =8:2:0.5, a zirconium dioxide protective layer is arranged outside the active layer.
A preparation method of a titanium anode specifically comprises the following steps:
1) Spraying white corundum on the TA1 titanium plate;
2) Carrying out thermal sizing treatment on the titanium plate subjected to sand blasting;
3) Soaking the titanium plate after the thermal sizing for 12 hours by using 10% hydrochloric acid, and then performing acid treatment for 2.5 hours by using 5% boiling oxalic acid solution;
4) Cleaning the titanium plate subjected to acid treatment by using pure water, and airing;
5) H is to be 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, coCl 2 ·6H 2 O in n-butanol: isopropyl alcohol (volume ratio) =1:1 to form a mixed metal solution, and controlling the ratio of Ir: ta: co (molar ratio) =8:2:0.5 coating the oxidized titanium plate, drying, sintering at 550 ℃ for 15min, repeating the process for 13 times, and finally sintering at 550 ℃ for 90min to prepare the active layer.
6) Taking isopropanol as a solvent, and taking a certain amount of butyl zirconate to prepare a solution with the Zr ion concentration of 0.15 mol/L;
7) Uniformly brushing the solution on the titanium plate treated in the step 5);
8) Drying the titanium substrate;
9) And (3) roasting the titanium matrix at a high temperature of 500 ℃ for 50min to obtain a zirconium dioxide protective layer, thus obtaining the final titanium anode C for the electrolytic copper foil.
And (4) preparing a titanium-based insoluble anode D serving as a control sample under the same conditions without preparing a protective layer on the cleaned and dried titanium plate. And the samples C and D were subjected to life-strengthening experiments (electrode test area 2 cm) 2 The electrolyte is 1mol/L sulfuric acid solution with current density of 40000A/m 2 )。
Example 3:
the titanium anode comprises a titanium substrate and an active layer coated on the surface of the titanium substrate, wherein the active layer is H 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, snCl 2 ·2H 2 O、SbCl 3 And ethanol, wherein Ir: ta: co (molar ratio) =9:1:0.2:0.3, a zirconium dioxide protective layer is arranged outside the active layer.
A preparation method of a titanium anode specifically comprises the following steps:
1) Spraying steel grit to the titanium plate with the TA1 mark;
2) Carrying out thermal sizing treatment on the titanium plate subjected to sand blasting;
3) Carrying out acid treatment on the titanium plate subjected to thermal sizing for 1h by using a 5% hydrofluoric acid solution;
4) Cleaning the titanium plate subjected to acid treatment by using pure water, and airing;
5) Will H 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, snCl 2 ·2H 2 O、SbCl 3 Dissolving by using ethanol as a solvent to form a mixed metal solution, and controlling Ir: ta: co (molar ratio) =9:1:0.2:0.3, coating the oxidized titanium plate, drying, sintering at 400 ℃ for 10min, repeating the process for 15 times, and finally sintering at 400 ℃ for 60min to prepare the titanium-based insoluble anode E.
6) Taking ethanol as a solvent, and taking a certain amount of butyl zirconate to prepare a solution with the Zr ion concentration of 0.3 mol/L;
7) Uniformly brushing the solution on the titanium plate treated in the step 4);
8) Drying the titanium substrate;
9) And (3) roasting the titanium matrix at the high temperature of 600 ℃ for 90min to obtain a zirconium dioxide protective layer, thus obtaining the final titanium anode E for the electrolytic copper foil.
And (4) preparing a titanium-based insoluble anode F as a reference sample by using the titanium plate which is cleaned and dried without preparing a protective layer under the same other conditions. And the samples E and F were subjected to life-strengthening experiments (electrode test area 2 cm) 2 The electrolyte is 1mol/L sulfuric acid solutionCurrent density 40000A/m 2 )。
As can be seen from the test result shown in FIG. 4, the zirconium dioxide protective layer is prepared on the titanium substrate with the prepared active layer, and the electrolytic copper foil anode prepared by adding the zirconium dioxide protective layer has better corrosion resistance, reduces the corrosion of the active layer, has longer service life, is simple and easy to implement, has low cost, improves the service life of the titanium anode without increasing the content of the noble metal active layer, and effectively reduces the production cost. Has better application prospect.
Example 4:
the titanium anode comprises a titanium substrate and an active layer coated on the surface of the titanium substrate, wherein the active layer is H 2 IrCl 6 ·xH 2 O、TaCl 5 A mixture of n-butanol solution and solvent n-butanol, ir: ta (molar ratio) =7: and 3, a silicon dioxide protective layer is arranged outside the active layer.
A preparation method of a titanium anode specifically comprises the following steps:
1) Spraying brown corundum on the TA1 titanium plate;
2) Carrying out thermal sizing treatment on the titanium plate subjected to sand blasting;
3) Carrying out acid treatment on the titanium plate after the thermal sizing for 1h by using a 5% boiling sulfuric acid solution;
4) Cleaning the titanium plate subjected to acid treatment by using pure water, and airing;
5) H is to be 2 IrCl 6 ·xH 2 O、TaCl 5 Dissolving the n-butanol solution in a solvent n-butanol to form a mixed metal solution, and controlling Ir: ta (molar ratio) =7: and 3, coating the oxidized titanium plate, drying, sintering at 500 ℃ for 10min, repeating the process for 10 times, and finally sintering at 500 ℃ for 60min to prepare the active layer.
6) Taking n-butanol as a solvent, taking a certain amount of vinyltriethoxysilane (note: belonging to one of silane coupling agents) to prepare a solution with Si ion concentration of 0.05 mol/L;
7) Uniformly spraying the solution on the titanium plate treated in the step 5);
8) Drying the titanium substrate;
9) And (3) roasting the titanium matrix at the high temperature of 400 ℃ for 10min.
And (4) repeating the steps 7) -9) for 3 times to obtain a silicon dioxide protective layer, thus obtaining the final copper-plated anode G used in the iron-containing system.
And (4) preparing a titanium anode H serving as a reference sample under the same other conditions without preparing a surface protection layer on the cleaned and dried titanium plate. And the samples G and H were subjected to life-strengthening experiments (electrode test area 2 cm) 2 The electrolyte is 1mol/L sulfuric acid solution with current density of 5000A/m 2 ). In addition, the plating bath was used to simulate on-line production and the bath solution was periodically analyzed for Cu 2+ And (4) content.
Example 5:
the titanium anode comprises a titanium substrate and an active layer coated on the surface of the titanium substrate, wherein the active layer is H 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, coCl 2 ·6H 2 O in the mixture of normal butanol and isopropanol, and a silicon dioxide protective layer is arranged outside the active layer.
A preparation method of a titanium anode specifically comprises the following steps:
1) Spraying white corundum on the TA1 titanium plate;
2) Carrying out thermal sizing treatment on the titanium plate subjected to sand blasting;
3) Soaking the titanium plate after the heat sizing for 10min by using 10% of hydrochloric acid with the temperature of 60 ℃, and then performing acid treatment for 3h by using 10% of oxalic acid solution;
4) Cleaning the titanium plate subjected to acid treatment by using pure water, and airing;
5) Will H 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, coCl 2 ·6H 2 O in n-butanol: isopropyl alcohol (volume ratio) =1:1 to form a mixed metal solution, and controlling Ir: ta: co (molar ratio) =8:2:0.5 coating the oxidized titanium plate, drying, sintering at 550 ℃ for 15min, repeating the process for 13 times, and finally sintering at 550 ℃ for 90min to prepare the active layer.
6) Using isopropanol as a solvent, taking a certain amount of vinyl trimethoxy silane (note: belonging to one of silane coupling agents) to prepare a solution with Si ion concentration of 0.15 mol/L;
7) Uniformly brushing the solution on the titanium plate treated in the step 5);
8) Drying the titanium substrate;
9) And roasting the titanium matrix at a high temperature of 500 ℃ for 50min.
And (4) repeating the steps 7) -9) for 10 times to obtain a silicon dioxide protective layer, and finally obtaining the copper-plated anode I used in the iron-containing system.
And (4) preparing a titanium-based insoluble anode J serving as a control sample under the same conditions without preparing a protective layer on the cleaned and dried titanium plate. And the samples I and J were subjected to life-prolonging test (electrode test area 2 cm) 2 The electrolyte is 1mol/L sulfuric acid solution with current density of 5000A/m 2 ). In addition, the plating bath was used to simulate on-line production and the bath solution was periodically analyzed for Cu 2+ And (4) content.
Example 6
The titanium anode comprises a titanium substrate and an active layer coated on the surface of the titanium substrate, wherein the active layer is H 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, snCl 2 ·2H 2 O、SbCl 3 And ethanol, and a silicon dioxide protective layer is arranged outside the active layer.
A preparation method of a titanium anode specifically comprises the following steps:
1) Spraying steel grit to the titanium plate with the TA1 mark;
2) Carrying out thermal sizing treatment on the titanium plate subjected to sand blasting;
3) Treating the titanium plate subjected to thermal sizing for 30min by using 5% nitric acid and 5% hydrofluoric acid solution;
4) Cleaning the titanium plate subjected to acid treatment by using pure water, and airing;
5) Will H 2 IrCl 6 ·xH 2 O、TaCl 5 N-butanol solution, snCl 2 ·2H 2 O、SbCl 3 Using ethanol as a solventAnd (4) dissolving to form a mixed metal solution, and controlling Ir: ta: sn: sb (molar ratio) =9:1:0.2:0.3, coating the oxidized titanium plate, drying, sintering at 400 ℃ for 10min, repeating the process for 15 times, and finally sintering at 400 ℃ for 60min to prepare the titanium-based insoluble anode E.
6) Taking ethanol as a solvent, and taking a certain amount of tetraethoxysilane to prepare a solution with the Si ion concentration of 0.3 mol/L;
7) Uniformly brushing the solution on the titanium plate treated in the step 4);
8) Drying the titanium substrate;
9) And (3) roasting the titanium matrix at the high temperature of 600 ℃ for 90min.
And (4) repeating the steps 7) -9) for 15 times to obtain a silicon dioxide protective layer, namely obtaining the final copper-plated anode K used in the iron-containing system.
And (4) preparing a titanium-based insoluble anode L serving as a control sample under the same conditions without preparing a protective layer on the cleaned and dried titanium plate. And the samples K and L were subjected to life-prolonging test (electrode test area 2 cm) 2 The electrolyte is 1mol/L sulfuric acid solution with current density of 5000A/m 2 ). In addition, the plating cell was used to simulate on-line production and the cell solution was analyzed periodically for Cu 2+ And (4) content.
From the test result shown in fig. 5, it can be seen that the service life of the copper-plated anode prepared by preparing the silicon dioxide protective layer on the titanium substrate with the prepared active layer and adding the silicon dioxide protective layer is longer. The method is simple and easy to implement, has low cost, prolongs the service life of the titanium anode under the condition of not increasing the content of the noble metal active layer, and effectively reduces the production cost. And can keep Cu in the electroplating solution in the using process 2+ The content stability and the application prospect are good.
In comparison with the conventional titanium anode used in the field of electrolytic copper plating, fig. 1 is a schematic view of the structure of the titanium anode according to the present invention, after the active layer is formed, by forming a silicon dioxide protective layer on the surface of the active layer. The silicon dioxide has stable chemical property and plays a role in protecting the active layer. As shown in FIG. 2, a titanium anode prepared using silicon dioxide as a protective layer was fabricated fromThe catalytic activity of the titanium anode is slowly and stably improved in the activation stage under the protection effect of the silicon dioxide on the active layer, so that the phenomenon that the Cu in the electroplating solution is caused by the rapid improvement of the catalytic activity when no protective layer exists is avoided 2+ Rapid proliferation and difficult stabilization. In the stable operation stage, due to the effect of the silicon dioxide protective layer, the active layer is prevented from being in direct contact with the electroplating solution, so that the corrosion and the falling of the active layer are delayed, the active layer can be used for a longer time, and the service life of the titanium anode is prolonged. And in the gradual failure stage, the effective components of the active layer are reduced, the silicon dioxide protective layer gradually falls off to expose the active layer, so that a small amount of the active layer can fully play a role, and the Cu in the electroplating solution caused by insufficient catalytic activity of the titanium anode is avoided 2+ Insufficient stability.
Therefore, the invention can not only ensure that Cu in the electroplating solution in the whole process 2+ The content of the titanium anode is kept in a stable state, and meanwhile, due to the action of the silicon dioxide protective layer, the direct contact between the active layer and the electroplating solution is avoided, and the service life of the titanium anode is greatly prolonged. On the other hand, comparing fig. 3, it is known that the conventional titanium anode does not have the protective layer, which results in unstable catalytic activity and further causes Cu in the plating solution 2+ Fluctuates and the active layer deteriorates faster, resulting in a lower lifetime of the titanium anode.
In the case of a titanium anode used in the field of electrolytic copper foil, as shown in fig. 1, after preparing an active layer, a protective layer of zirconium dioxide is prepared on the surface of the active layer. Zirconium has a corrosion resistance exceeding that of titanium, while zirconium dioxide has a corrosion resistance exceeding that of metallic zirconium. The preparation of the zirconium dioxide protective layer can effectively protect the active layer with the catalytic function, thereby reducing the corrosion of the active layer and further prolonging the service life of the titanium anode for the electrolytic copper foil. The operation of the working procedure is simple and easy to implement, the service life of the titanium anode is prolonged under the condition that the content of the noble metal active layer is not increased, and the production cost is effectively reduced.
The copper plating equipment assembled by the titanium anode prepared by the embodiment has the characteristics of long service life and low use cost.
Claims (10)
1. The titanium anode for the copper plating field is characterized by comprising a titanium substrate (1) and a coating coated on the surface of the titanium substrate, wherein the coating is an active layer (2), the inner side of the active layer (2) is closely adjacent to the titanium anode, and the outer side of the active layer is a silicon dioxide or zirconium dioxide protective layer (3);
the active layer (2) has a catalytic effect, and the protective layer (3) of silicon dioxide or zirconium dioxide is used to avoid direct contact of the active layer with the solution.
2. The titanium anode for copper plating field according to claim 1, characterized in that the active layer (2) is any mixture of one or more of chloride or nitrate or acetate or compound containing cobalt or tin or antimony or manganese or titanium or tantalum or iridium or ruthenium or rhodium or platinum or palladium, wherein the metal ion concentration is controlled between 0.1 and 0.5 mol/L.
3. The method for preparing the titanium anode for the copper plating field according to claim 1 or 2, characterized by comprising the following steps;
step one, pretreating a titanium substrate (1);
step two, cleaning and drying the titanium substrate (1) pretreated in the step one;
step three, preparing an active layer (2) containing metal oxide on the titanium substrate (1) by a thermal decomposition method on the titanium substrate (1) treated in the step two;
and step four, preparing a silicon dioxide or zirconium dioxide protective layer (3) on the active coating of the metal oxide prepared in the step three, thereby obtaining the titanium anode with the protective layer.
4. The method for preparing the titanium anode for the copper plating field according to claim 3, wherein the pretreatment in the first step comprises the following steps:
s11: carrying out sand blasting treatment on the titanium substrate (1);
s12: carrying out thermal sizing on the titanium substrate (1) treated by S11;
s13: carrying out acid treatment on the titanium substrate (1) treated by S12;
the titanium substrate (1) in the S11 is pure titanium; the sand mold subjected to sand blasting treatment is one or more of steel sand, brown corundum, white corundum, quartz sand, copper ore sand, carborundum and Hainan sand;
the temperature of the thermal sizing treatment in the S12 is 550-600 ℃;
and the acid used for the acid treatment in the S13 is one or more of oxalic acid, hydrochloric acid, sulfuric acid, hydrofluoric acid and nitric acid.
5. The method for preparing a titanium anode for copper plating according to claim 3, wherein the thermal decomposition in the third step comprises the following steps:
s31: dissolving one or more of chloride, nitrate or acetate or compound containing cobalt, tin, antimony, manganese, titanium, tantalum, iridium, ruthenium, rhodium, platinum or palladium in a solvent to obtain a salt solution; wherein the total metal ion concentration in the salt solution is controlled between 0.1 and 0.5 mol/L;
s32: brushing or spraying the salt solution on the titanium substrate (1) treated in the step two;
s33: drying the titanium substrate (1) by a drying tunnel furnace or drying by a blower;
s34: roasting the titanium matrix (1) at the high temperature of 400-550 ℃ for 10-90 min to obtain an active layer of an oxide;
the solvent used in step S31 is one or more of n-butanol, ethanol, isopropanol, propanol, methyl ether, ethyl ether, formamide, acetamide, n-pentanol, and turpentine.
6. The method for preparing a titanium anode for copper plating field according to claim 3, wherein the preparation of the silicon dioxide or zirconium dioxide protective layer (3) in the fourth step comprises the following steps:
s41: dissolving a salt or a compound containing silicon or zirconium in a solvent to obtain a silicon/zirconium salt solution;
s42: coating or spraying the salt solution on the active layer (2) of the metal oxide prepared in the third step;
s43: drying the titanium substrate (1) by a drying tunnel furnace or drying by a blower;
s44: and (3) roasting the titanium matrix (1) at the high temperature of 400-600 ℃ for 10-90 min to obtain the silicon dioxide or zirconium dioxide protective layer (3).
7. The method for preparing the titanium anode in the field of copper plating according to claim 6, wherein the salt or compound containing silicon in S41 is a silane coupling agent or tetraethoxysilane; the salt or compound containing zirconium is butyl zirconate.
8. The method for preparing the titanium anode for the copper plating field according to claim 6, wherein the concentration of Si ions in the salt solution of Si in S41 is 0.01-0.4 mol/L; the Zr ion concentration in the zirconium salt solution is 0.01-0.4 mol/L.
9. The method for preparing the titanium anode in the field of copper plating according to claim 6, wherein the solvent in S41 is one or more of n-butanol, ethanol, isopropanol, propanol, methyl ether, diethyl ether, formamide, acetamide, n-pentanol and turpentine.
10. A copper plating apparatus comprising a titanium anode, wherein the titanium anode is an anode according to claim 1 or 2, or an anode produced by a method according to any one of claims 3 to 9.
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