CN112048744A - Process for improving platinum plating uniformity on surface of titanium substrate - Google Patents
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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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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- C—CHEMISTRY; METALLURGY
- 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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F1/00—Etching metallic material by chemical means
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- C23F1/14—Aqueous compositions
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- C23F1/26—Acidic compositions for etching refractory metals
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- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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Abstract
The application relates to the field of titanium substrate surface treatment, and particularly discloses a process for improving the platinum plating uniformity on the surface of a titanium substrate, which comprises the following steps: firstly, pretreating the surface of a titanium substrate; (II) coating a modifying solution; (III) sintering treatment; (IV) electroplating treatment; the metal chloride comprises the following components in parts by weight: 10-30 parts of ruthenium trichloride; 1-10 parts of iridium chloride; 5-15 parts of palladium chloride; 5-30 parts of tantalum pentachloride; 20-50 parts of titanium tetrachloride. According to the method, the sintering layer is formed on the surface of the titanium substrate, and then platinum is electroplated on the surface of the titanium substrate with the sintering layer, so that the conductivity of the titanium substrate can be improved through the sintering layer, and the platinum plating uniformity on the surface of the titanium substrate is improved.
Description
Technical Field
The application relates to the field of titanium substrate surface treatment, in particular to a process for improving the platinum plating uniformity of the surface of a titanium substrate.
Background
Platinum is widely applied to the fields of electroplating, electrolytic synthesis, electrochemical wastewater treatment, fuel cells and the like as an electrode material, and the platinum electrode has the characteristics of strong corrosion resistance, high catalytic performance, high oxygen evolution potential, low hydrogen evolution potential and the like, and is an anode material with excellent performance and a cathode material with excellent performance. Platinum exhibits excellent corrosion resistance in hydrochloric acid, nitric acid, sulfuric acid, hydrofluoric acid, phosphoric acid, and most electrolyte solutions, except a few mixed acids. The titanium-based platinum electrode is the most promising electrode material in the platinum-plated electrode due to the excellent corrosion resistance.
At present, the platinum salt electroplating process is mainly adopted in the titanium substrate platinum electroplating process, and the titanium substrate platinum electroplating method in the center of the related technology comprises the following steps: (a) activating titanium, namely heating 5-15% of oxalic acid and 10-20% of sulfuric acid serving as acid until the acid is boiled, and keeping for 2-3 hours; (b) decomposing titanium hydride, namely adding platinum liquid into crystal nucleus precipitation liquid, connecting a titanium-based workpiece with a positive electrode to decompose the titanium hydride, (c) precipitating the crystal nucleus, and converting the electrifying direction after 70-90% of the titanium hydride is decomposed to form platinum crystal nuclei on the surface of the titanium-based workpiece; (d) and (4) platinizing the titanium-based workpiece after the crystal nucleus is precipitated. Wherein the PH value of the crystal nucleus precipitation liquid is 2-4, the platinum content is 3-5g/L, and the temperature is 60-80 ℃; connecting the titanium workpiece with a positive electrode, and enabling the current density of titanium hydride decomposition to be 2-4A/dm2 for 1-2 minutes; the current density after switching the electrifying direction is 5-15A/dm2, and the time is 4-8 minutes.
In view of the above-described related art, the inventors thought that there was a defect in which the platinum layer was not uniform.
Disclosure of Invention
In order to improve the uniformity of platinum plating on the surface of a titanium substrate, the application provides a process for improving the uniformity of platinum plating on the surface of the titanium substrate.
The application provides a process for improving the platinum plating uniformity on the surface of a titanium substrate, which adopts the following technical scheme:
a process for improving the platinum plating uniformity of the surface of a titanium substrate comprises the following steps:
firstly, surface pretreatment of a titanium substrate: pretreating the surface of the titanium substrate to remove impurities and dirt on the surface of the titanium substrate;
(II) coating a modifying solution: dissolving metal chlorides such as ruthenium trichloride, iridium chloride, palladium chloride, tantalum pentachloride and titanium tetrachloride in water to obtain a modified solution, wherein the weight ratio of the metal chlorides to the water is (3-5): 100, uniformly coating the modifying solution on the surface of the pretreated titanium substrate;
(III) sintering treatment: drying the titanium substrate coated with the modification liquid and then sintering to obtain a titanium substrate with a sintered layer;
(IV) electroplating treatment: electroplating platinum on the surface of the titanium substrate with the sintering layer to obtain the titanium substrate with the platinum electroplating layer;
the metal chloride comprises the following components in parts by weight:
10-30 parts of ruthenium trichloride;
1-10 parts of iridium chloride;
5-15 parts of palladium chloride;
5-30 parts of tantalum pentachloride;
20-50 parts of titanium tetrachloride.
By adopting the technical scheme, because ruthenium trichloride, iridium chloride, palladium chloride, tantalum pentachloride and titanium tetrachloride are adopted as raw materials of the modification solution and are matched with each other, a sintering layer is formed on the surface of the titanium substrate after sintering, the main component of the sintering layer is oxide of noble metal, and the conductivity of the oxide of noble metal is stronger than that of the titanium substrate, therefore, the platinum is electroplated on the surface of the titanium substrate with the sintering layer, a platinum layer with uniform thickness can be obtained, and the platinum electroplating uniformity on the surface of the titanium substrate is improved.
Preferably, the surface pretreatment of the titanium substrate (I) comprises the following specific steps:
(a) oil removal: putting the titanium substrate into deoiling liquid for deoiling, washing with water and drying;
(b) sand blasting: carrying out sand blasting on the dried titanium base material, and controlling the roughness Ra of the surface of the titanium base material to be 1-2 mu m;
(c) acid etching: placing the titanium substrate subjected to sand blasting into an acid etching solution, heating to 80-90 ℃, and preserving heat for 40-60 min;
(d) washing and drying: and washing the acid-etched titanium substrate with water, and drying.
By adopting the technical scheme, the surface roughness of the titanium substrate is increased after oil removal and sand blasting, and the surface area of the titanium substrate is further increased after acid etching, so that the modification liquid is favorably attached to the surface of the titanium substrate, and a sintering layer with uniform thickness and difficult shedding is formed.
Preferably, the acid etching solution comprises 5-8% of oxalic acid and 10-15% of hydrochloric acid in percentage by weight.
By adopting the technical scheme, the strong acid and the weak acid are compounded to carry out acid etching on the titanium substrate, so that the micron-sized pit structure on the surface of the titanium substrate is more uniform and finer.
Preferably, the sintering temperature in the (third) sintering treatment is 300-600 ℃, and the sintering time is 30-90 min.
By adopting the technical scheme, the metal chloride can be sintered more completely within the temperature and time range, and a compact and uniform sintered layer is formed.
Preferably, the thickness of the sintered layer is 0.1 to 0.2 μm.
By adopting the technical scheme, the sintering layer with the thickness can reasonably control the cost and ensure better conductivity.
Preferably, the specific steps of the (iv) electroplating treatment are as follows: electroplating in 85-90 deg.C chloroplatinic acid solution with platinum as anode and sintered titanium substrate as cathode to obtain titanium substrate with electroplated platinum layer.
By adopting the technical scheme, the surface of the titanium substrate is provided with the sintering layer with better conductivity, and the platinum layer with uniform thickness can be obtained by electroplating on the surface of the sintering layer.
Preferably, the chloroplatinic acid solution is 6-10mol/L HCL and 10-30g/L H in a volume ratio of 1:12PtCl26H2And (4) mixed solution of O solution.
By adopting the technical scheme, the platinum layer with uniform thickness can be obtained by electroplating in the mixed solution.
Preferably, the thickness of the platinum electroplating layer is 0.5-15 μm.
By adopting the technical scheme, the electroplating platinum layer with the thickness can reasonably control the cost, improve the corrosion resistance of the titanium substrate and prolong the service life.
In summary, the present application has the following beneficial effects:
1. according to the method, ruthenium trichloride, iridium chloride, palladium chloride, tantalum pentachloride and titanium tetrachloride are used as raw materials of the modification solution, and after sintering, a sintering layer is formed on the surface of the titanium substrate, the main component of the sintering layer is an oxide of a noble metal, and the oxide of the noble metal has higher conductivity than the titanium substrate, so that a platinum layer with uniform thickness can be obtained by electroplating platinum on the surface of the titanium substrate with the sintering layer, and the platinum plating uniformity on the surface of the titanium substrate is improved.
2. The titanium substrate in this application is after deoiling and sandblast, and roughness increases, has further increased the surface area of titanium substrate after carrying out the acid etching, is favorable to the modified liquid to adhere to on titanium substrate surface to form the sintering layer that thickness is even, be difficult for droing.
Detailed Description
The present application will be described in further detail with reference to examples.
Examples
Example 1
A process for improving the platinum plating uniformity of the surface of a titanium substrate comprises the following steps:
firstly, surface pretreatment of a titanium substrate:
(a) oil removal: putting the titanium substrate into deoiling liquid for deoiling, wherein the deoiling liquid is a sodium hydroxide aqueous solution with the mass concentration of 10%, the deoiling time is 10min, and drying after washing;
(b) sand blasting: carrying out sand blasting on the dried titanium base material, and controlling the roughness Ra of the surface of the titanium base material to be 0.5 mu m;
(c) acid etching: placing the titanium substrate subjected to sand blasting into an acid etching solution, wherein the acid etching solution comprises 10% oxalic acid and 8% hydrochloric acid in percentage by weight, heating to 75 ℃, and preserving heat for 70 min;
(d) washing and drying: and washing the acid-etched titanium substrate with water, and drying. Wherein, deionized water is adopted in the water washing step.
(II) coating a modifying solution: dissolving metal chlorides such as ruthenium trichloride, iridium chloride, palladium chloride, tantalum pentachloride and titanium tetrachloride in deionized water to obtain a modification solution, wherein the total weight of the metal chlorides is 80g, and the weight of the deionized water is 2667g, and uniformly coating the modification solution on the surface of the pretreated titanium substrate;
(III) sintering treatment: drying the titanium substrate coated with the modification liquid, and then sintering at 650 ℃ for 20min to obtain the titanium substrate with a sintered layer, wherein the thickness of the sintered layer is 0.3 mu m;
(IV) electroplating treatment: in thatElectroplating platinum on the surface of the titanium substrate with the sintering layer, taking the platinum as an anode and the titanium substrate with the sintering layer as a cathode, and electroplating in a chloroplatinic acid solution at 85 ℃ to obtain the titanium substrate with the platinum electroplating layer, wherein the thickness of the platinum electroplating layer is 18 mu m, and the current density is 100A/m2The chloroplatinic acid solution is 5mol/L HCL and 35g/L H in a volume ratio of 1:12PtCl26H2And (4) mixed solution of O solution.
The weight of the metal chloride is as follows:
10g of ruthenium trichloride;
10g of iridium chloride;
5g of palladium chloride;
5g of tantalum pentachloride;
50g of titanium tetrachloride.
Example 2
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in example 1 in that the weight of the metal chlorides is as follows:
20g of ruthenium trichloride;
6g of iridium chloride;
10g of palladium chloride;
20g of tantalum pentachloride;
titanium tetrachloride 35 g.
Example 3
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in example 1 in that the weight of the metal chlorides is as follows:
30g of ruthenium trichloride;
1g of iridium chloride;
15g of palladium chloride;
30g of tantalum pentachloride;
titanium tetrachloride 20 g.
Example 4
The difference between the process for improving the platinum plating uniformity on the surface of a titanium substrate and the process in example 1 is that the total weight of metal chloride is 80g, and the weight of deionized water is 1600 g.
Example 5
The process for improving the platinum plating uniformity of the surface of the titanium base material is different from the process of the embodiment 1 in that the roughness Ra of the surface of the titanium base material is controlled to be 1 mu m after sand blasting.
Example 6
The process for improving the platinum plating uniformity of the surface of the titanium base material is different from the process of the embodiment 1 in that the roughness Ra of the surface of the titanium base material is controlled to be 2 mu m after sand blasting.
Example 7
The process for improving the platinum plating uniformity of the surface of the titanium substrate is different from that of the embodiment 1 in that the acid etching solution comprises 5 weight percent of oxalic acid and 10 weight percent of hydrochloric acid.
Example 8
The process for improving the platinum plating uniformity of the surface of the titanium substrate is different from that of the embodiment 1 in that the acid etching solution comprises 8 weight percent of oxalic acid and 15 weight percent of hydrochloric acid.
Example 9
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in the embodiment 1 in that in the acid etching step, the temperature is heated to 80 ℃, and the temperature is kept for 60 min.
Example 10
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in the embodiment 1 in that in the acid etching step, the temperature is heated to 90 ℃, and the temperature is kept for 40 min.
Example 11
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from that of the example 1 in that the sintering temperature is 300 ℃ and the sintering time is 90 min.
Example 12
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in the embodiment 1 in that the sintering temperature is 600 ℃, and the sintering time is 30 min.
Example 13
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in the embodiment 1 in that the thickness of the sintering layer is 0.05 mu m.
Example 14
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in the embodiment 1 in that the thickness of the sintering layer is 0.1 mu m.
Example 15
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in the embodiment 1 in that the thickness of the sintering layer is 0.2 mu m.
Example 16
The process for improving the platinum plating uniformity of the surface of the titanium base material is different from the process of the embodiment 1 in that the thickness of the platinum plating layer is 0.5 mu m.
Example 17
The process for improving the platinum plating uniformity of the surface of the titanium base material is different from the process of the embodiment 1 in that the thickness of the platinum plating layer is 15 mu m.
Example 18
The process for improving the platinum plating uniformity of the surface of the titanium substrate is different from that of the example 1 in that the chloroplatinic acid solution is 6mol/L HCL and 10g/L H in a volume ratio of 1:12PtCl26H2And (4) mixed solution of O solution.
Example 19
The process for improving the platinum plating uniformity of the surface of the titanium substrate is different from that of the example 1 in that the chloroplatinic acid solution is 10mol/L HCL and 30g/L H in a volume ratio of 1:12PtCl26H2And (4) mixed solution of O solution.
Example 20
A process for improving the platinum plating uniformity of the surface of a titanium substrate comprises the following steps:
firstly, surface pretreatment of a titanium substrate:
(a) oil removal: putting the titanium substrate into deoiling liquid for deoiling, wherein the deoiling liquid is a sodium hydroxide aqueous solution with the mass concentration of 10%, the deoiling time is 10min, and drying after washing;
(b) sand blasting: carrying out sand blasting on the dried titanium base material, and controlling the roughness Ra of the surface of the titanium base material to be 1 mu m;
(c) acid etching: placing the titanium substrate subjected to sand blasting into an acid etching solution, wherein the acid etching solution comprises 5% oxalic acid and 10% hydrochloric acid in percentage by weight, heating to 80 ℃, and preserving heat for 60 min;
(d) washing and drying: and washing the acid-etched titanium substrate with water, and drying. Wherein, deionized water is adopted in the water washing step.
(II) coating a modifying solution: dissolving metal chlorides such as ruthenium trichloride, iridium chloride, palladium chloride, tantalum pentachloride and titanium tetrachloride in deionized water to obtain a modification solution, wherein the total weight of the metal chlorides is 80g, and the weight of the deionized water is 2667g, and uniformly coating the modification solution on the surface of the pretreated titanium substrate;
(III) sintering treatment: drying the titanium substrate coated with the modification liquid and then sintering, wherein the sintering temperature is 600 ℃, and the sintering time is 30min, so that the titanium substrate with a sintering layer is obtained, and the thickness of the sintering layer is 0.1 mu m;
(IV) electroplating treatment: electroplating platinum on the surface of the titanium substrate with the sintering layer, taking the platinum as an anode and the titanium substrate with the sintering layer as a cathode, and electroplating in a chloroplatinic acid solution at 85 ℃ to obtain the titanium substrate with the platinum electroplating layer, wherein the thickness of the platinum electroplating layer is 0.5 mu m, and the current density is 100A/m2The chloroplatinic acid solution is 6mol/L HCL and 10g/L H in a volume ratio of 1:12PtCl26H2And (4) mixed solution of O solution.
The weight of the metal chloride is as follows:
10g of ruthenium trichloride;
10g of iridium chloride;
5g of palladium chloride;
5g of tantalum pentachloride;
50g of titanium tetrachloride.
Comparative example
Comparative example 1
A process for improving the platinum plating uniformity of the surface of a titanium substrate comprises the following steps:
firstly, surface pretreatment of a titanium substrate:
(a) oil removal: putting the titanium substrate into deoiling liquid for deoiling, wherein the deoiling liquid is a sodium hydroxide aqueous solution with the mass concentration of 10%, the deoiling time is 10min, and drying after washing;
(b) sand blasting: carrying out sand blasting on the dried titanium base material, and controlling the roughness Ra of the surface of the titanium base material to be 0.5 mu m;
(c) acid etching: placing the titanium substrate subjected to sand blasting into an acid etching solution, wherein the acid etching solution comprises 10% oxalic acid and 8% hydrochloric acid in percentage by weight, heating to 75 ℃, and preserving heat for 70 min;
(d) washing and drying: and washing the acid-etched titanium substrate with water, and drying.
(IV) electroplating treatment: electroplating platinum on the surface of a titanium substrate, taking the platinum as an anode and the titanium substrate as a cathode, and electroplating in a chloroplatinic acid solution at 85 ℃ to obtain the titanium substrate with a platinum electroplating layer, wherein the thickness of the platinum electroplating layer is 18 mu m, and the current density is 100A/m2The chloroplatinic acid solution is 5mol/L HCL and 35g/L H in a volume ratio of 1:12PtCl26H2And (4) mixed solution of O solution.
Comparative example 2
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in example 1 in that the weight of the metal chlorides is as follows:
10g of iridium chloride;
5g of palladium chloride;
5g of tantalum pentachloride;
50g of titanium tetrachloride.
Comparative example 3
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in example 1 in that the weight of the metal chlorides is as follows:
10g of ruthenium trichloride;
5g of palladium chloride;
5g of tantalum pentachloride;
50g of titanium tetrachloride.
Comparative example 4
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in example 1 in that the weight of the metal chlorides is as follows:
10g of iridium chloride;
5g of tantalum pentachloride;
50g of titanium tetrachloride.
Comparative example 5
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in example 1 in that the weight of the metal chlorides is as follows:
10g of ruthenium trichloride;
5g of palladium chloride;
50g of titanium tetrachloride.
Comparative example 6
The process for improving the platinum plating uniformity on the surface of the titanium substrate is different from the process in example 1 in that the weight of the metal chlorides is as follows:
40g of ruthenium trichloride;
10g of iridium chloride;
5g of palladium chloride;
5g of tantalum pentachloride;
50g of titanium tetrachloride.
Comparative example 7
The difference between the process for improving the platinum plating uniformity on the surface of a titanium substrate and the process in example 1 is that the total weight of metal chlorides is 80g, and the weight of deionized water is 8000 g.
Performance testing test samples: 27 pure titanium plates with the length, width and thickness of 20 x 10 x 3mm respectively are taken as a titanium base material, and platinum is plated on the surface of the titanium base material according to the processes of examples 1-20 and comparative examples 1-7 respectively to obtain a platinum-plated workpiece.
The detection method comprises the following steps:
(1) uniformly selecting 5 points with the same position on each platinum-plated workpiece, measuring the thickness of the platinum layer of the 5 points of each platinum-plated workpiece by using a metal plating thickness meter, recording the thickness as A1-A5, and calculating the relative average deviation of A1-A5.
(2) The platinum-plated workpiece is tested by referring to the 2.8 scribing and marking test in the test method comments of the electro-deposition and chemical deposition layer adhesion strength of the metal covering layer on the metal substrate of GB/T5270-2005, and the peeling condition of the platinum layer on the surface of the platinum-plated workpiece is observed and recorded.
TABLE 1 relative mean deviation test results for platinum layer thickness of platinized workpieces
| Example/comparative example numbering | Relative mean deviation/%) |
| Example 1 | 5.20 |
| Example 2 | 5.10 |
| Example 3 | 5.00 |
| Example 4 | 4.90 |
| Example 5 | 4.50 |
| Example 6 | 4.40 |
| Example 7 | 4.60 |
| Example 8 | 4.70 |
| Example 9 | 4.80 |
| Example 10 | 4.70 |
| Example 11 | 5.00 |
| Example 12 | 4.90 |
| Example 13 | 6.10 |
| Example 14 | 5.00 |
| Example 15 | 5.10 |
| Example 16 | 5.30 |
| Example 17 | 5.20 |
| Example 18 | 4.90 |
| Example 19 | 4.80 |
| Example 20 | 0.95 |
| Comparative example 1 | 10.20 |
| Comparative example 2 | 8.50 |
| Comparative example 3 | 8.40 |
| Comparative example 4 | 7.90 |
| Comparative example 5 | 7.80 |
| Comparative example 6 | 7.20 |
| Comparative example 7 | 5.80 |
TABLE 2 Cross-cut test results for platinized work pieces
Combining examples 1-20 and comparative examples 1-7 and combining tables 1-2, it can be seen that example 1 significantly improves the uniformity of the platinum layer compared to comparative example 1, which shows that the uniformity of platinum plating on the surface of the titanium substrate can be improved by plating platinum on the surface of the titanium substrate with the sintered layer. Comparative examples 2-5 respectively delete any one or two metal chlorides, the platinum layer uniformity is better than comparative example 1, but inferior to example 1, show that ruthenium trichloride, iridium chloride, palladium chloride, tantalum pentachloride, titanium tetrachloride are mutually matched, the formed sintering layer can improve the platinum plating uniformity, and the defect is that one is not enough; the metal chloride ratio of comparative example 6 is out of the range of the present application, and the uniformity of the platinum layer is reduced compared with that of example 1, which shows that the metal chloride ratio can influence the uniformity of platinum plating; comparative example 7 the weight ratio of metal chloride to water is outside the range of the present application and the uniformity of the platinum layer is reduced relative to example 1, indicating that the weight ratio of metal chloride to water affects the uniformity of the platinization.
Examples 5 to 6 control the surface roughness Ra of the titanium substrate to be 1 to 2 μm, and the uniformity of the platinum layer is improved, which shows that the surface roughness of the titanium substrate can influence the uniformity of platinizing; examples 7 to 8 control the proportion of the acid etching solution, improve the uniformity of the platinum layer, and examples 9 to 10 control the temperature and time of the acid etching, improve the uniformity of the platinum layer, which shows that the proportion, time and temperature of the acid etching solution can affect the uniformity of the platinum layer; the sintering temperatures and times for examples 11-12 are within the range of the present application and the uniformity of the platinized layer is slightly improved, indicating that the sintering temperatures and times have a smaller effect on the uniformity of the platinum layer; the thickness of the sintered layer of example 13 is too small, the uniformity of the platinum layer is reduced, the thickness of the sintered layers of examples 14 to 15 is within the range of the present application, the uniformity of the platinum layer is slightly improved, the thickness of the sintered layer of example 1 is larger, but the uniformity is not improved, and the cost is increased; examples 16-17 varied the thickness of the platinum layer, and the uniformity of the platinum layer did not change significantly; the chloroplatinic acid solutions of examples 18 to 19 are proportioned within the range of the present application to improve the uniformity of the platinum layer, which indicates that the chloroplatinic acid solution affects the uniformity of platinum plating, and the steps and parameters of example 20 are all within the preferred range of the present application to significantly improve the uniformity of the platinum layer, which indicates that the steps and parameters in the process of the present application cooperate with each other to improve the uniformity of platinum plating on the surface of the titanium substrate.
The platinum layers of the embodiments 1 to 12 and 14 to 20 are not peeled off, which shows that the platinum layer electroplated by the process of the application has strong binding force with the sintering layer, is not easy to fall off, and can prolong the service life of the titanium substrate; the platinum layer of example 13 was slightly exfoliated mainly because the thickness of the sintered layer was too small, the conductivity was not significantly improved, the uniformity of the platinum layer was decreased, and severe exfoliation occurred in comparative examples 1 to 6, indicating that the presence or absence of the sintered layer, the raw material and the compounding ratio of the sintered layer had a large influence on the bonding force of the platinum layer, and slight exfoliation occurred in the platinum layer of comparative example 7 indicating that the weight ratio of the metal chloride to water had a small influence on the uniformity of platinum plating.
The present embodiment is only for explaining the present application, and it is not limited to the present application, and those skilled in the art can make modifications of the present embodiment without inventive contribution as needed after reading the present specification, but all of them are protected by patent law within the scope of the claims of the present application.
Claims (8)
1. A process for improving the platinum plating uniformity on the surface of a titanium substrate is characterized by comprising the following steps:
firstly, surface pretreatment of a titanium substrate: pretreating the surface of the titanium substrate to remove impurities and dirt on the surface of the titanium substrate;
(II) coating a modifying solution: dissolving metal chlorides such as ruthenium trichloride, iridium chloride, palladium chloride, tantalum pentachloride and titanium tetrachloride in water to obtain a modified solution, wherein the weight ratio of the metal chlorides to the water is (3-5): 100, uniformly coating the modifying solution on the surface of the pretreated titanium substrate;
(III) sintering treatment: drying the titanium substrate coated with the modification liquid and then sintering to obtain a titanium substrate with a sintered layer;
(IV) electroplating treatment: electroplating platinum on the surface of the titanium substrate with the sintering layer to obtain the titanium substrate with the platinum electroplating layer;
the metal chloride comprises the following components in parts by weight:
10-30 parts of ruthenium trichloride;
1-10 parts of iridium chloride;
5-15 parts of palladium chloride;
5-30 parts of tantalum pentachloride;
20-50 parts of titanium tetrachloride.
2. The process of claim 1 for improving the uniformity of platinum plating on the surface of a titanium substrate, wherein the process comprises the following steps: the surface pretreatment method of the titanium substrate comprises the following specific steps:
(a) oil removal: putting the titanium substrate into deoiling liquid for deoiling, washing with water and drying;
(b) sand blasting: carrying out sand blasting on the dried titanium base material, and controlling the roughness Ra of the surface of the titanium base material to be 1-2 mu m;
(c) acid etching: placing the titanium substrate subjected to sand blasting into an acid etching solution, heating to 80-90 ℃, and preserving heat for 40-60 min;
(d) washing and drying: and washing the acid-etched titanium substrate with water, and drying.
3. The process of claim 2 for improving the uniformity of platinum plating on the surface of a titanium substrate, wherein the process comprises the following steps: the acid etching solution comprises 5-8% of oxalic acid and 10-15% of hydrochloric acid in percentage by weight.
4. The process of claim 1 for improving the uniformity of platinum plating on the surface of a titanium substrate, wherein the process comprises the following steps: the sintering temperature in the sintering treatment (III) is 300-600 ℃, and the sintering time is 30-90 min.
5. The process of claim 1 for improving the uniformity of platinum plating on the surface of a titanium substrate, wherein the process comprises the following steps: the thickness of the sintering layer is 0.1-0.2 μm.
6. The process of claim 1 for improving the uniformity of platinum plating on the surface of a titanium substrate, wherein the process comprises the following steps: the specific steps of the electroplating treatment (IV) are as follows: electroplating in 85-90 deg.C chloroplatinic acid solution with platinum as anode and sintered titanium substrate as cathode to obtain titanium substrate with electroplated platinum layer.
7. The process of claim 6, wherein the step of improving the uniformity of the platinum plating on the surface of the titanium substrate comprises the following steps: the chloroplatinic acid solution is 6-10mol/L HCL and 10-30g/L H in a volume ratio of 1:12PtCl26H2And (4) mixed solution of O solution.
8. The process of claim 1 for improving the uniformity of platinum plating on the surface of a titanium substrate, wherein the process comprises the following steps: the thickness of the platinum electroplating layer is 0.5-15 μm.
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