CN111472028A - High-sulfur-resistance silver plating solution, use method thereof and high-sulfur-resistance silver plating layer - Google Patents
High-sulfur-resistance silver plating solution, use method thereof and high-sulfur-resistance silver plating layer Download PDFInfo
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- CN111472028A CN111472028A CN202010311159.0A CN202010311159A CN111472028A CN 111472028 A CN111472028 A CN 111472028A CN 202010311159 A CN202010311159 A CN 202010311159A CN 111472028 A CN111472028 A CN 111472028A
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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
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
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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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
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Abstract
The invention provides a silver plating solution with high sulfur resistance, which comprises AgNO325～40g/L、KI 370～420g/L、K2CO31～5g/L、K2C2O41 to 5 g/L, water, and Cu (NO)3)2·3H2O、C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2And NiI2At least two of them. In the silver plating process, the silver plating solution provided by the invention enables metal ions such as copper, gold, aluminum, molybdenum, tungsten, zinc or nickel to enter the silver plating layer in a compounding way through multi-metal ion compounding so as to form a new composite oxide surface layer, thereby improving the anti-sulfuration performance of the surface of the silver plating layer. The experimental result shows that the coating provided by the invention contains 5% of Na2And the change of the contact resistance is small after the S is soaked for 5 days.
Description
Technical Field
The invention belongs to the field of composite electroplating, and particularly relates to a high-sulfur-resistance silver plating solution, a using method thereof and a high-sulfur-resistance silver plating layer.
Background
The southeast coastal area of China belongs to a high-temperature, high-humidity and high-salinity atmosphere environment, and the industrial development causes severe atmosphere environment of a transformer substation in the area, and the problems of corrosion and failure of conductor materials are serious. The silver coating layer of the electrical contact for the high-voltage isolating switch has serious corrosion and failure problems. The corrosion seriously threatens the service safety of equipment such as a high-voltage isolating switch, a circuit breaker and the like, and the main reason is that the contact resistance is increased due to the vulcanization of an electric contact silver coating in a high-temperature, high-humidity and high-salt atmosphere environment, and the contact part fails due to sudden increase of heat productivity or direct non-conduction. Therefore, the research on the sulfur resistance of the silver-based electric contact material at home and abroad is not interrupted.
There are a number of treatment methods for the industrial resistance of silver-based electrical contact materials to sulfidation, according to whichThe method for improving the sulfur resistance of the silver-based electric contact material is a cyanide-free silver plating solution, the components of which are AgNO silver plating solution, wherein the additives are FS122, FS123 and graphite, and the FS122 and FS123 contents are 10-50m L/L, and the graphite content is 30-80 g/L, and the silver plating solution is introduced in Chinese patent CN108193240A310～50g/L，KI 260～480g/L，K2CO310 to 20 g/L and K2C2O410-20 g/L. although the sulfur resistance of the silver plating solution is improved, the sulfur resistance of the silver plating solution is difficult to meet the requirement with the development of industry.
Disclosure of Invention
The invention aims to provide a silver plating solution with high sulfur resistance, a using method thereof and a silver plating layer with high sulfur resistance. The high-sulfur-resistance silver plating layer provided by the invention has excellent sulfur resistance.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a high-sulfur-resistance silver plating solution comprising AgNO325～40g/L、KI 370～420g/L、K2CO31～5g/L、K2C2O41 to 5 g/L, water, and Cu (NO)3)2·3H2O、C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2And NiI2At least two of them.
Preference is given toEarth, the Cu (NO)3)2·3H2The concentration of O is 0.1-2 g/L, and C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2Or NiI2Independently in a concentration of 0.1 to 1 g/L.
Preferably, the Cu (NO)3)2·3H2The concentration of O is 0.5-1.5 g/L, and C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2Or NiI2Independently in a concentration of 0.3 to 0.7 g/L.
The invention also provides a using method of the silver plating solution with high sulfur resistance, which comprises the following steps:
(1) pre-plating silver on the substrate to obtain a pre-plated silver substrate;
(2) silver plating is carried out on the pre-plated silver substrate obtained in the step (1) to obtain a silver-plated substrate;
(3) and (3) putting the silver-plated substrate obtained in the step (2) into a high-sulfur-resistance silver plating solution for electroplating to obtain the high-sulfur-resistance silver plating layer.
Preferably, the substrate in step (1) further comprises a surface treatment before the pre-silver plating.
Preferably, the time for pre-silvering in the step (1) is 60-180 s.
Preferably, the time for plating silver in the step (2) is less than or equal to 1 h.
Preferably, the time of electroplating in the step (3) is less than or equal to 3 min.
Preferably, the current density of electroplating in the step (3) is 0.15-1.5A/dm2。
The invention also provides a high-sulfur-resistance silver coating and a coating prepared by the technical scheme.
The invention provides a high-sulfur-resistance silver plating solution, which is characterized in that a plurality of metal ions are added, and in the silver plating process, the metal ions of copper, gold, aluminum, molybdenum, tungsten, zinc or nickel can enter a silver plating layer in a compounding way through multi-metal ion compounding, so that a new compound oxide surface layer is formed, and the sulfuration resistance of the surface of the silver plating layer is further improved. Experimental results show that the coating prepared by the silver plating solution provided by the application contains 5% of Na in volume fraction2And the change of the contact resistance is small after the S is soaked for 5 days, which shows that the high-sulfur-resistance silver coating has excellent sulfuration resistance.
Detailed Description
The invention provides a high-sulfur-resistance silver plating solution comprising AgNO325～40g/L、KI 370～420g/L、K2CO31～5g/L、K2C2O41 to 5 g/L, water, and Cu (NO)3)2·3H2O、C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2And NiI2At least two of them.
The silver plating solution with high sulfur resistance provided by the invention comprises AgNO325-40 g/L, preferably 30-40 g/L, more preferably 35-37 g/L, in the invention, the AgNO3Can provide silver ions required by the silver plating layer; the AgNO3The silver plating layer prepared when the concentration is within the above range has strong binding force.
The high-sulfur-resistance silver plating solution provided by the invention comprises KI 370-420 g/L, preferably 390-410 g/L, more preferably 400-405 g/L. in the invention, the KI can replace potassium cyanide in the traditional silver plating solution, the damage of cyanide to human bodies is avoided, and when the KI concentration is in the range, the complexing capacity with metal silver ions can be improved, and the binding force between the silver plating layer and a substrate is further improved.
The silver plating solution with high sulfur resistance provided by the invention comprises K2CO31 to 5 g/L, preferably 1 to 5 g/L2-4 g/L, more preferably 3 g/L. in the invention, the K is2CO3The conductive salt in the silver plating solution can improve the conductivity of the plating solution; said K2CO3When the concentration of (A) is within the above range, the appearance of the silver plating layer can be improved because the addition of potassium carbonate increases the conductivity of the solution, but when the concentration of potassium carbonate is too high, the potassium carbonate crystallizes out in the plating solution, so that K is considered from the viewpoint of the appearance of the plating layer and the stability of the plating solution2CO3The concentration of (3) is set in the above range.
The silver plating solution with high sulfur resistance provided by the invention comprises K2C2O41-5 g/L, preferably 2-4 g/L, more preferably 3 g/L. in the invention, the K is2C2O4As an auxiliary complexing agent, the current efficiency can be improved, and the surface of the prepared silver coating has no impure phase; said K2C2O4When the concentration of (b) is within the above range, the surface property of the silver plating layer can be further improved and the presence of a heterogeneous phase can be reduced.
The purity of water is not particularly limited in the present invention, and water for preparing a silver plating solution well known in the art may be used. In the present invention, the water is preferably deionized water. In the present invention, water is used as a solvent to dissolve other raw materials.
The silver plating solution with high sulfur resistance also comprises Cu (NO)3)2·3H2O、C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2And NiI2Preferably comprises Cu (NO)3)2·3H2O、C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2And NiI2Two to four ofMore preferably, Cu (NO) is included3)2·3H2O and C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2Or NiI2Any of the above combinations. In the present invention, the Cu (NO) is3)2·3H2When being matched with any one of the other six materials, the O can be matched with the other six materials to enter the silver coating in a compounding manner, so that the sulfuration resistance of the surface of the silver coating is greatly improved.
In the present invention, the Cu (NO) is3)2·3H2The concentration of O is preferably 0.1-2 g/L, more preferably 0.5-1.5 g/L, and even more preferably 0.75-1 g/L, and the C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2Or NiI2Independently, the concentration of (A) is preferably 0.1 to 1 g/L, more preferably 0.3 to 0.7 g/L, and still more preferably 0.5 to 0.6 g/L3)2·3H2O、C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2And NiI2When the concentration of the silver oxide is within the range, the silver oxide can enter the silver plating layer in a compounding way to form a new composite oxide surface layer, so that the anti-vulcanization performance of the surface of the silver plating layer is improved; when the concentration of these metal compounds is controlled within the above range, the effect of each metal ion can be sufficiently exhibited, and the sulfidation resistance of the silver plating surface can be further improved.
In the process of silver electroplating, the high-sulfur-resistance silver plating solution provided by the invention can enable metal ions such as copper, gold, aluminum, molybdenum, tungsten, zinc or nickel to enter the silver plating layer in a compounding manner through multi-metal ion compounding, so as to form a new composite oxide surface layer, and further improve the sulfuration resistance of the surface of the silver plating layer.
The preparation method of the high-sulfur-resistance silver plating solution is not specially limited, and all the components are uniformly mixed and can reach the required concentration content.
The invention also provides a using method of the silver plating solution with high sulfur resistance, which comprises the following steps:
(1) pre-plating silver on the substrate to obtain a pre-plated silver substrate;
(2) silver plating is carried out on the pre-plated silver substrate obtained in the step (1) to obtain a silver-plated substrate;
(3) and (3) putting the silver-plated substrate obtained in the step (2) into a high-sulfur-resistance silver plating solution for electroplating to obtain the high-sulfur-resistance silver plating layer.
The invention has no special limitation on the type or size of the matrix, and the matrix can be selected according to actual needs. In the present invention, the substrate is preferably a copper substrate.
The invention pre-silvers the substrate to obtain the pre-silvered substrate. In the present invention, pre-silver plating is performed before silver plating, so that direct contact between the base metal and silver can be prevented, and some of sulfur, oxygen, and the like present in the base metal can be separated from the silver layer, thereby preventing the possibility of oxidation of the silver plating layer from the inside.
In the present invention, the substrate preferably further comprises a surface treatment before the pre-silver plating. The present invention is not particularly limited to the specific operation of the surface treatment, and a surface treatment process known to those skilled in the art may be used. In the present invention, the surface treatment preferably includes polishing, alkali degreasing and acid washing in this order. In the invention, the oil removing time of the strong base is preferably 0.5-2 h; the pickling time is preferably 10-60 s. In the invention, the polishing can remove burrs, difficult objects, corrosion marks and oxide scales on the surface of the substrate, ensure the surface of the substrate to be smooth, and simultaneously can properly roughen the surface of the copper base, thereby being beneficial to improving the bonding force between the substrate and the plating layer; the oil removal of the strong base can remove grease on the surface of the substrate, so that the substrate is completely exposed, and electroplating is facilitated; the acid cleaning can remove the oxide scale on the surface of the substrate and neutralize the adsorbed alkaline liquid, so that the surface of the substrate is bright.
The composition of the silver pre-plating solution is not particularly limited in the invention, and the silver pre-plating solution known to those skilled in the art can be adopted. In the present invention, the pre-silvering solution preferably comprises AgNO30.5-3 g/L, KI 300-400 g/L and water, and further preferably AgNO31-2.5 g/L, KI 320-380 g/L and water, more preferably AgNO3The pre-plating solution comprises 1.5-2 g/L, KI 350-370 g/L and water, wherein the purity of the water is not specially limited, and the water for preparing the silver plating solution well known in the art is adopted.
In the invention, the time for pre-silvering is preferably 60-180 s, more preferably 80-150 s, and more preferably 100-120 s; the current density of the pre-silvering is preferably 0.2-0.4A/dm2More preferably 0.3 to 0.35A/dm2More preferably 0.35A/dm2(ii) a The temperature of the pre-silver plating is preferably 20 ℃. In the present invention, the pre-silvering is preferably carried out in an electrically charged lower tank. In the invention, the groove can prevent poor binding force caused by silver replacement layer generation under electrification.
After the silver pre-plated matrix is obtained, the silver pre-plated matrix is subjected to silver plating to obtain the silver-plated matrix. According to the invention, the silver is directly plated without washing after the pre-plated silver substrate is obtained, so that the replacement reaction can be prevented, and the bonding force between the substrate and the plating layer is prevented from being deteriorated.
The composition of the silver plating solution is not particularly limited in the present invention, and a silver plating solution known to those skilled in the art may be used. In the present invention, the silver plating solution preferably includes AgNO325～40g/L、KI 370～420g/L、K2CO31～5g/L、K2C2O41-5 g/L and water, preferably AgNO330～35g/L、KI 390～410g/L、K2CO32～4g/L、K2C2O42-4 g/L and water, more preferably AgNO332～35g/L、KI 395～400g/L、K2CO32～3g/L、K2C2O42-3 g/L and water, wherein the purity of the water is not particularly limited, and the water is used for preparing the silver plating solution, which is well known in the art.
In the invention, the time for silver plating is preferably not more than 1 hour, more preferably 0.5-1 hour, and still more preferably 0.75-1 hour; the current density of the silver plating is preferably 0.15-1.5A/dm2More preferably 0.3 to 1A/dm2More preferably 0.5 to 0.75A/dm2(ii) a The temperature of the silver plating is preferably 20-90 ℃, more preferably 40-80 ℃, and even more preferably 50-60 ℃. In the invention, when the silver plating parameters are in the range, the binding force between the silver plating layer and the substrate can be improved.
After the silver-plated substrate is obtained, the silver-plated substrate is put into a high-sulfur-resistance silver plating solution for electroplating to obtain the high-sulfur-resistance silver plating layer. In the invention, the high-sulfur-resistance silver plating solution is added for electroplating, so that the surface of the silver plating layer can be prevented from being vulcanized, and the sulfuration resistance of the surface of the plating layer is improved.
The source of each raw material in the high sulfur-resistant silver plating solution is not particularly limited in the present invention, and commercially available products well known to those skilled in the art can be used.
In the invention, the electroplating time is preferably not more than 3min, more preferably 0.5-2 min, and more preferably 1 min; the current density of the electroplating is preferably 0.15-1.5A/dm2More preferably 0.3 to 1A/dm2More preferably 0.35 to 0.42A/dm2(ii) a The temperature of the silver plating is preferably 20-90 ℃, more preferably 40-80 ℃, and even more preferably 50-60 ℃. In the present invention, when the parameter of the plating is within the above range, it can be mentionedThe high-strength anti-sulfur silver plating layer has the binding force with the substrate, and the anti-sulfuration performance is further improved.
Compared with the silver coating prepared by the prior art, the using method provided by the invention has stronger binding force with the substrate, and the silver coating has higher anti-vulcanization performance.
The invention also provides a high-sulfur-resistance silver coating and a coating prepared by the technical scheme. In the present invention, the coating is preferably applied to an electrical contact material for a high-voltage disconnector. In the invention, the high-sulfur-resistance silver plating solution is electroplated on the surface of the electrical contact material for the high-voltage isolating switch, so that the formed plating layer improves the surface sulfuration resistance and avoids the risk that a pure silver layer is easily sulfurated.
The technical solution of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is to be understood that the described embodiments are merely exemplary of the invention, and not restrictive of the full scope of the invention. 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.
Example 1
Surface treatment
Polishing: firstly, coarse grinding is carried out by using 800-mesh sand paper, and then fine grinding is carried out by using 1000-mesh sand paper.
Chemical degreasing by strong alkali: table 1-1 shows the strong base degreasing process.
TABLE 1-1 Strong base deoiling technical table
| Composition (I) | Content (wt.) | Unit of |
| NaOH | 60 | g/L |
| Operating temperature | 20 | ℃ |
| Time of day | 1 | h |
Acid washing: the copper matrix after the chemical degreasing of the strong base is firstly washed by distilled water, then soaked in an acid washing solution and then taken out. Tables 1-2 are pickling process tables.
Table 1-2 shows the pickling process table
| Composition (I) | Content (wt.) | Unit of |
| HNO3 | 300 | g/L |
| Operating temperature | 20 | ℃ |
| Time of day | 20 | s |
Pre-silvering
And putting the treated copper substrate into silver plating liquid for pre-plating silver. Tables 1-3 are tables of the silver pre-plating process.
Tables 1-3 are pre-silvering process tables
| Composition (I) | Content (wt.) | Unit of |
| AgNO3 | 1 | g/L |
| KI | 350 | g/L |
| Deionized water | - | - |
| Temperature of | 20 | ℃ |
| Time of day | 120 | s |
| Current density | 0.35 | A/dm2 |
Silver plating
And putting the sample body after the pre-silvering into silvering liquid. Tables 1-4 are tables of silver plating process.
Tables 1-4 are silver plating process tables
(4) High sulfur resistance silver plating solution electroplating
And putting the silver-plated sample body into a silver plating solution with high sulfur resistance. Tables 1-5 are tables of silver plating process.
Tables 1-5 are silver plating process tables
| Composition (I) | Content (wt.) | Unit of |
| AgNO3 | 30 | g/L |
| KI | 400 | g/L |
| K2CO3 | 2 | g/L |
| K2C2O4 | 4.5 | g/L |
| Temperature of | 20 | ℃ |
| Time of day | 1.5 | min |
| Current density | 0.4 | A/dm2 |
| Cu(NO3)2·3H2O | 0.3 | g/L |
| C25H22Au2Cl2P2 | 0.5 | g/L |
| Al[CH3(CH2)16CO2]3 | 0.15 | g/L |
| Na3O40PW12·xH2O | 0.13 | g/L |
| Deionized water | - | - |
Example 2
Surface treatment
Polishing: firstly, coarse grinding is carried out by using 800-mesh sand paper, and then fine grinding is carried out by using 1000-mesh sand paper.
Chemical degreasing by strong alkali: table 2-1 shows the degreasing process with strong base.
TABLE 2-1 Strong base deoiling technical watch
| Composition (I) | Content (wt.) | Unit of |
| NaOH | 60 | g/L |
| Operating temperature | 20 | ℃ |
| Time of day | 1.5 | h |
Acid washing: the copper matrix after the chemical degreasing of the strong base is firstly washed by distilled water, then soaked in an acid washing solution and then taken out. Table 2-2 shows the pickling process table.
Table 2-2 shows the pickling process table
| Composition (I) | Content (wt.) | Unit of |
| HNO3 | 300 | g/L |
| Operating temperature | 20 | ℃ |
| Time of day | 30 | s |
Pre-silvering
And putting the treated copper substrate into silver plating liquid for pre-plating silver. Tables 2-3 are tables of the silver pre-plating process.
Tables 2-3 are pre-silvering process tables
| Composition (I) | Content (wt.) | Unit of |
| AgNO3 | 2 | g/L |
| KI | 380 | g/L |
| Deionized water | - | - |
| Temperature of | 20 | ℃ |
| Time of day | 180 | s |
| Current density | 0.35 | A/dm2 |
Silver plating
And putting the sample body after the pre-silvering into silvering liquid. Tables 2-4 are tables of silver plating process.
Tables 2-4 are silver plating process tables
| Composition (I) | Content (wt.) | Unit of |
| AgNO3 | 35 | g/L |
| KI | 385 | g/L |
| K2CO3 | 2.5 | g/L |
| K2C2O4 | 3.5 | g/L |
| Deionized water | - | - |
| Temperature of | 20 | ℃ |
| Time of day | 0.4 | h |
| Current density | 0.25 | A/dm2 |
(4) High sulfur resistance silver plating solution electroplating
Putting the silver-plated sample body into a high-sulfur-resistance silver plating solution with the current density of A/dm2. Tables 2-5 are tables of silver plating process.
Tables 2-5 are silver plating process tables
Example 3
Surface treatment
Polishing: firstly, coarse grinding is carried out by using 800-mesh sand paper, and then fine grinding is carried out by using 1000-mesh sand paper.
Chemical degreasing by strong alkali: table 3-1 shows the strong base degreasing process.
TABLE 3-1 Strong base deoiling technical watch
| Composition (I) | Content (wt.) | Unit of |
| NaOH | 60 | g/L |
| Operating temperature | 20 | ℃ |
| Time of day | 1.2 | h |
Acid washing: the copper matrix after the chemical degreasing of the strong base is firstly washed by distilled water, then soaked in an acid washing solution and then taken out. Table 3-2 shows the pickling process table.
Table 3-2 shows the pickling process table
| Composition (I) | Content (wt.) | Unit of |
| HNO3 | 300 | g/L |
| Operating temperature | 20 | ℃ |
| Time of day | 35 | s |
Pre-silvering
And putting the treated copper substrate into silver plating liquid for pre-plating silver. Tables 3-3 are tables of the silver pre-plating process.
Tables 3-3 are pre-silvering process tables
| Composition (I) | Content (wt.) | Unit of |
| AgNO3 | 1.8 | g/L |
| KI | 355 | g/L |
| Deionized water | - | - |
| Temperature of | 20 | ℃ |
| Time of day | 60 | s |
| Current density | 0.35 | A/dm2 |
Silver plating
And putting the sample body after the pre-silvering into silvering liquid. Tables 3-4 are tables of silver plating process.
Tables 3-4 are silver plating process tables
| Composition (I) | Content (wt.) | Unit of |
| AgNO3 | 38 | g/L |
| KI | 395 | g/L |
| K2CO3 | 1.5 | g/L |
| K2C2O4 | 3.5 | g/L |
| Deionized water | - | - |
| Temperature of | 20 | ℃ |
| Time of day | 0.8 | h |
| Current density | 0.25 | A/dm2 |
(4) High sulfur resistance silver plating solution electroplating
And putting the silver-plated sample body into a silver plating solution with high sulfur resistance. Tables 3-5 are tables of silver plating process.
Tables 3-5 are silver plating process tables
| Composition (I) | Content (wt.) | Unit of |
| AgNO3 | 37 | g/L |
| KI | 415 | g/L |
| K2CO3 | 2.8 | g/L |
| K2C2O4 | 3.2 | g/L |
| Temperature of | 20 | ℃ |
| Time of day | 0.5 | min |
| Current density | 0.42 | A/dm2 |
| Al[CH3(CH2)16CO2]3 | 0.15 | g/L |
| Na3O40PW12·xH2O | 0.25 | g/L |
| ZnI2 | 0.3 | g/L |
| NiI2 | 0.6 | g/L |
| Deionized water | - | - |
The coating prepared in the examples 1 to 3 contains 5% of Na by volume fraction2And soaking the substrate in the S solution for 5 days to perform a contact resistance test, wherein test values are shown in table 1.
In the experiment, a DMR-4 contact resistance tester is adopted to test the sample, and the test precision is 0.01 mu omega (the applied torque is 10 N.m).
The instrument needs to be preheated for five minutes before testing, a power supply is firstly turned on, then a test fixture is connected, and after preheating is completed, a proper resistance value range is selected for measurement. The test method comprises the steps of fixing a test sample on a desktop during testing, connecting a clamp at a proper position, reading out a resistance value in a display screen, causing measurement errors due to the fact that the clamp and the test sample touch during testing, and measuring for multiple times to obtain an average value.
Table 1 examples 1-3 contact resistance before and after plating immersion
| Examples | Contact resistance/mu omega before soaking | 5％Na2Contact resistance/mu omega after S soaking for 10 days |
| Example 1 | 20.6 | 21.3 |
| Example 2 | 23.8 | 30.9 |
| Example 3 | 21.6 | 28.5 |
As can be seen from Table 1, the plating layers of examples 1 to 3 contained 5% by volume of Na2S is small in contact resistance change after being soaked for 5 days, which shows that the high-sulfur-resistance silver plating layer has excellent anti-vulcanization performance, and mainly because metal ions added into the high-sulfur-resistance silver plating solution used in the invention can enter a silver plating layer in a compounding manner to form a new composite oxide surface layer, so that the anti-vulcanization performance of the surface of the silver plating layer is improved; when the concentration of the metal compound is within the range of the present invention, the effect of each metal ion can be sufficiently exerted, and the anti-sulfidation performance of the silver plating surface can be further improved. In addition, KI used by the invention can replace potassium cyanide in the traditional silver plating solution, thereby avoiding the situation that the KI is used for replacing potassium cyanide in the traditional silver plating solutionThe use of cyanide is harmful to human body.
From the above examples, it can be seen that the high sulfur resistant silver plating solution of the present invention has excellent sulfur resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. The silver plating solution with high sulfur resistance is characterized by comprising AgNO325～40g/L、KI 370～420g/L、K2CO31～5g/L、K2C2O41 to 5 g/L, water, and Cu (NO)3)2·3H2O、C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2And NiI2At least two of them.
2. The silver plating solution with high sulfur resistance according to claim 1, wherein the Cu (NO) is3)2·3H2The concentration of O is 0.1-2 g/L, and C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2Or NiI2Independently in a concentration of 0.1 to 1 g/L.
3. The silver plating solution with high sulfur resistance according to claim 2, wherein the Cu (NO) is3)2·3H2The concentration of O is 0.5-1.5 g/L, and C25H22Au2Cl2P2、Al[CH3(CH2)16CO2]3、(NH4)2Mo2O7、Na3O40PW12·xH2O、ZnI2Or NiI2Independently in a concentration of 0.3 to 0.7 g/L.
4. The method for using the silver plating solution with high sulfur resistance as defined in any one of claims 1 to 3, comprising the following steps:
(1) pre-plating silver on the substrate to obtain a pre-plated silver substrate;
(2) silver plating is carried out on the pre-plated silver substrate obtained in the step (1) to obtain a silver-plated substrate;
(3) and (3) putting the silver-plated substrate obtained in the step (2) into a high-sulfur-resistance silver plating solution for electroplating to obtain the high-sulfur-resistance silver plating layer.
5. The use method according to claim 4, wherein the substrate in step (1) further comprises surface treatment before the pre-silvering.
6. The use method according to claim 4, wherein the time for pre-silvering in the step (1) is 60-180 s.
7. The use method according to claim 4, wherein the time for silver plating in the step (2) is less than or equal to 1 h.
8. The use method according to claim 4, wherein the time of electroplating in the step (3) is less than or equal to 3 min.
9. The use method according to claim 4 or 8, wherein the electroplating in step (3) is carried out at a current density of 0.15-1.5A/dm2。
10. A highly sulfur-resistant silver coating prepared by the method of any one of claims 4 to 9.
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|---|---|---|---|---|
| JPS6070197A (en) * | 1983-09-28 | 1985-04-20 | Yaskawa Electric Mfg Co Ltd | Silver alloy plating method |
| CN103806054A (en) * | 2012-11-12 | 2014-05-21 | 无锡三洲冷轧硅钢有限公司 | Pulse plating method of Ag-Ni alloy for electric contact material |
| CN106906499A (en) * | 2017-03-28 | 2017-06-30 | 佛山市宇光电气有限公司 | Silver-based multicomponent alloy composite solution and the method that functional coating is prepared using it |
| CN108193240A (en) * | 2018-01-12 | 2018-06-22 | 南昌航空大学 | A kind of method that vacuum cyanideless electro-plating prepares high resistance to SO_2 fine silver coating |
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2020
- 2020-04-20 CN CN202010311159.0A patent/CN111472028B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6070197A (en) * | 1983-09-28 | 1985-04-20 | Yaskawa Electric Mfg Co Ltd | Silver alloy plating method |
| CN103806054A (en) * | 2012-11-12 | 2014-05-21 | 无锡三洲冷轧硅钢有限公司 | Pulse plating method of Ag-Ni alloy for electric contact material |
| CN106906499A (en) * | 2017-03-28 | 2017-06-30 | 佛山市宇光电气有限公司 | Silver-based multicomponent alloy composite solution and the method that functional coating is prepared using it |
| CN108193240A (en) * | 2018-01-12 | 2018-06-22 | 南昌航空大学 | A kind of method that vacuum cyanideless electro-plating prepares high resistance to SO_2 fine silver coating |
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