CN113699565B - High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid - Google Patents
High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid Download PDFInfo
- Publication number
- CN113699565B CN113699565B CN202111146585.4A CN202111146585A CN113699565B CN 113699565 B CN113699565 B CN 113699565B CN 202111146585 A CN202111146585 A CN 202111146585A CN 113699565 B CN113699565 B CN 113699565B
- Authority
- CN
- China
- Prior art keywords
- nickel
- palladium
- layer
- plating
- plating layer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
Abstract
The invention relates to the technical field of electroplating, and particularly discloses a high-corrosion-resistance palladium-nickel alloy coating, which comprises a non-porous nickel bottom layer arranged on the surface of a substrate, wherein a palladium-nickel coating is arranged on the upper surface of the non-porous nickel bottom layer, a hard gold layer is arranged on the upper surface of the palladium-nickel coating, and the palladium content of the palladium-nickel coating is 90-98wt%. The upper surface of the hard gold layer is also provided with a lubricating protective coating. Compared with the traditional 70-90wt% palladium-nickel plating layer with the same thickness, the anode electrolytic corrosion resistance of the palladium-nickel plating layer is improved by more than 1.5 times. The invention also provides an electroplating solution for obtaining the high-corrosion-resistance palladium-nickel alloy plating layer and an electroplating method for obtaining the high-corrosion-resistance palladium-nickel alloy plating layer, and the method can provide the high-corrosion-resistance palladium-nickel alloy plating layer which is well combined with a connector terminal base material, and has strong corrosion resistance and wear resistance.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a high-corrosion-resistance palladium-nickel alloy plating layer, an electroplating method thereof and palladium-nickel plating layer electroplating solution.
Background
The palladium-nickel alloy plating layer for engineering is widely used in the electronic industry for about 40 years, is mainly used as a substitute plating layer to reduce the electroplating cost, and provides excellent electrical performance and wear resistance for the contact area of an electronic device.
At present, the industrial palladium-nickel alloy plating layer is mostly adopted by American society for testing and materials standard-ASTM B867-95"Standard Specification for Electrodeposied Coatings of Palladium Nickel for Engineering Use, namely the engineering palladium-nickel plating layer standard, and the palladium (Pd) content in the alloy plating layer is specified to be 70-95wt%. At present, the Pd-Ni (PdNi) alloy electroplating specification of all manufacturers in the domestic and foreign electronic industry is 70-90wt% of Pd-Ni coating, so that the Pd-Ni alloy liquid medicine for domestic and foreign business and the Pd-Ni alloy coating obtained by the electroplating process are 70-90wt%.
70-90wt% of palladium-nickel alloy coating can be used as a substitute gold coating to provide the same traditional corrosion resistance as the gold coating, such as salt mist, mixed acid gas, constant temperature and humidity and the like. However, in the charging application of Type C and Micro-USB charging port connectors, if water, sweat or brine enters into the liquid corrosive medium, the palladium-nickel alloy plated signal pin terminal used as the anode will also undergo very obvious anodic electrolytic corrosion until the nickel bottom layer and the copper alloy substrate are severely corroded to affect the charging function. Although the palladium nickel plating layer has better resistance to anodic electrolytic corrosion than the gold layer of the same thickness, the palladium nickel plating layer still does not meet the application requirements far enough and needs further improvement.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a high corrosion resistance palladium-nickel alloy coating composition with excellent brine anodic electrolytic corrosion resistance, and compared with a palladium-nickel coating with the same thickness, the anodic electrolytic corrosion resistance of the palladium-nickel coating is obviously improved.
Another object of the present invention is to provide a plating method of a highly corrosion-resistant palladium-nickel alloy plating layer and a palladium-nickel plating layer plating solution.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
the high corrosion resistance palladium-nickel alloy plating layer comprises a non-porous nickel bottom layer arranged on the surface of a substrate, wherein the high corrosion resistance palladium-nickel plating layer is arranged on the upper surface of the non-porous nickel bottom layer, a hard gold layer is arranged on the upper surface of the palladium-nickel plating layer, and the palladium content of the palladium-nickel plating layer is 90-98wt%.
The nickel bottom layer used in the invention is different from the traditional semi-bright or bright nickel, and is required to be sulfur-free and completely pore-free, so that pores in the palladium-nickel coating on the surface of the nickel bottom layer are completely eliminated, and further the corrosion resistance of the palladium-nickel coating, particularly the brine-resistant anodic electrolytic corrosion resistance, is obviously improved. The thickness of the non-porous nickel bottom layer is 1-6 mu m; preferably 2.0-5.0 μm.
The high corrosion resistance palladium-nickel plating layer is different from the traditional 70-90wt% palladium-nickel plating layer, the palladium content of the palladium-nickel plating layer obtained by the method is required to be 90-98 wt% palladium-nickel plating layer with high palladium content, and the palladium-nickel plating layer is completely pore-free, so that the brine anode electrolytic corrosion resistance can be greatly improved. The thickness of the high corrosion resistance palladium nickel plating layer is 0.8-5 mu m. The thicker the palladium nickel coating is, the stronger the brine anodic electrolytic corrosion resistance is. However, excessive thickness tends to result in excessive cost and product size. By adopting the palladium-nickel plating layer with the thickness, the product has good corrosion resistance and simultaneously has good production cost and product size. When the palladium content in the plating layer exceeds 95wt%, the brine anodic electrolytic corrosion resistance is more excellent. When the thickness of the electroplated high corrosion-resistant palladium-nickel coating is 1.5 mu m,2 mu m,2.5 mu m and 3 mu m, the high corrosion-resistant palladium-nickel coating is subjected to a brine anodic electrolytic corrosion test with the traditional 70-90wt% palladium-nickel coating with the same thickness, and the result shows that the corrosion resistance is obviously improved, so that the high corrosion-resistant palladium-nickel coating is particularly suitable for being used in applications requiring the brine anodic electrolytic corrosion resistance.
The hard gold layer on the surface layer has the main functions of: the passivation of palladium and nickel under the high-temperature application environment is prevented, and the low and stable contact resistance is kept as the same as that of the traditional hard gold electroplating; as a solid lubricant, the catalyst is attached to the surface of palladium nickel, so that the grinding and inserting coefficient is reduced, and excellent wear resistance is obtained; since palladium and palladium-nickel alloys have strong catalytic activity, if they are directly used as the outermost layer of an electronic device, organic polymers are easily generated on the surface of the electronic device during long-term sliding grinding and micro-grinding, so that the electrical performance is gradually deteriorated, and the application failure may be caused. After a thin layer of flash gold is plated on the surface of palladium nickel, the generation of organic polymers in the sliding grinding and micro grinding and inserting processes can be minimized, and the good electrical performance under long-term use can be maintained. The hard gold layer has a thickness of 0.025 to 0.25. Mu.m, preferably 0.05 to 0.08. Mu.m.
Furthermore, the upper surface of the hard gold layer is also provided with a lubrication protective coating. The lubricating protective coating is arranged on the upper surface of the hard gold layer. The use of the lubricating oil coating also leads the wear resistance of the palladium-nickel alloy coating to be obviously improved, and the good corrosion resistance of the brine anodic electrolytic corrosion can be still maintained after a plurality of plugging tests or use.
The high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 3-30g/L of palladium ions, 0.3-15g/L of nickel ions, 30-80g/L of conductive salt and 1-10g/L of additive B.
Further, the additive B is olefin sulfonate or olefin sulfonate derivative.
The palladium ions used in the raw materials of the palladium-nickel plating layer plating solution can be derived from 2 palladium salts of tetraammine palladium chloride and tetraammine palladium sulfate, and the 2 palladium salts can be used independently and cannot be used simultaneously in the same plating solution. For low-speed roll-coating, low palladium ion concentration of 3-10g/L can be used; for high speed continuous plating applications, it is generally recommended to use high palladium ion concentrations above 15 g/L.
The nickel ions used in the raw materials of the palladium-nickel plating layer plating solution can be nickel sulfate or nickel chloride, and 2 nickel salts can be used independently or can not be used simultaneously in the same plating solution. The range of nickel ion concentration used depends on the palladium ion concentration and the palladium content of the plating layer.
The conductive salt used in the raw material of the palladium-nickel plating layer plating solution can be one or 2 of ammonium sulfate, ammonium chloride, potassium sulfate and potassium chloride. The conductive salt has the function of increasing the conductivity of the plating solution and can be used for high-current density electroplating. After addition of the conductive salt, the plating solution conductivity must > =80 ms/cm.
The additive B used in the raw material of the palladium-nickel plating solution can be olefin sulfonate and derivatives thereof, such as alpha-olefin sodium sulfonate, vinyl sodium sulfonate, propenyl sodium sulfonate and the like. The main function of the additive B is to widen the cathode current density, reduce the internal stress of the palladium-nickel coating, especially reduce the high internal stress of the palladium-nickel coating with high palladium content, and obtain a soft semi-bright to bright palladium-nickel coating suitable for engineering application.
An electroplating method for obtaining the high corrosion resistance palladium-nickel alloy plating layer comprises the following steps:
step one: pretreating the base material, and electroplating a non-porous nickel bottom layer on the surface of the base material by adopting a non-porous nickel bottom layer plating solution;
step two: plating a high corrosion resistance palladium-nickel plating layer on the surface of the nickel bottom layer by adopting a high corrosion resistance palladium-nickel plating layer plating solution;
step three: and (3) flash plating a hard gold layer on the surface of the high corrosion resistance palladium-nickel plating layer to prepare the high corrosion resistance palladium-nickel alloy plating layer.
Further, in the first step, the substrate is a copper substrate, a copper alloy substrate, a stainless steel substrate, a tungsten alloy substrate, a magnesium alloy substrate, an aluminum alloy substrate, a zinc substrate or a zinc alloy substrate.
Further, in the first step, the step of pretreating the substrate includes: and (3) carrying out nickel preplating, zinc dipping or alkaline copper preplating treatment on the surface of the substrate to obtain good binding force. If the base material is copper and copper alloy, a nickel bottom layer can be directly electroplated on the surface of the base material; if the base materials such as stainless steel or tungsten alloy are required to be plated with nickel, good binding force can be ensured; the magnesium alloy or aluminum alloy substrate needs to be subjected to corresponding zinc dipping treatment and then nickel plating to obtain good binding force; and the zinc or zinc alloy die casting base material needs to be pre-plated with alkali copper cyanide and then plated with nickel, so that good binding force can be obtained.
Further, in the first step, the non-porous nickel bottom layer plating solution comprises the following components: 40-130g/L of nickel ions, 0-45g/L of nickel chloride, 30-50g/L of boric acid and 0.05-0.2g/L of additive A.
Further, in the first step, the cathode current density of the plating is 0.5-15A/dm 2 (ASD), pH of the non-porous nickel plating solution is 2.5-4.5, and electroplating temperature is 50-65 ℃.
The nickel ions used in the plating solution composition can be nickel sulfamate or nickel sulfate;
the additive A used in the composition of the plating solution can be alkyl sulfate, alkyl sulfonate and derivatives thereof, such as sodium dodecyl sulfate, sodium hexadecyl sulfate, sodium dodecyl sulfonate, sodium hexadecyl sulfonate and the like, and the main function is to obtain the nickel plating without sulfur and pores even in low-speed stirring such as roll-to-roll plating application.
The current density of the electroplating cathode is mainly determined by the electroplating mode and the stirring intensity. Such as low-speed roll-on plating applications, because the plating solution is less agitated, a current density in the range of 0.5-3ASD can be used; in the high-speed continuous plating application, the plating product walks in the plating solution at a high speed, and the plating solution is stirred at a high speed by adopting a pump with a large flow rate and impacted, so that the current density range which can be used can reach 5-15ASD, and the required plating thickness can be obtained in a short time. The high-speed stirring is also beneficial to the rapid separation of the hydrogen separated out from the surface of the plating piece and the nickel plating layer, so that the porosity of the nickel layer can be obviously reduced and the corrosion resistance can be improved.
Further, in the second step, the cathode current density of the electroplating is 0.2-20A/dm 2 The (ASD) corrosion-resistant palladium-nickel alloy plating solution has the pH value of 7.5-8.5 and the electroplating temperature of 40-55 ℃.
The current density of the electroplating cathode is mainly determined by the electroplating mode and the stirring intensity. Such as low-speed roll-on plating applications, because the plating solution is less agitated, a current density in the range of 0.2-3ASD can be used; in the high-speed continuous plating application, the plating product walks in the plating solution at a high speed, and the plating solution is stirred at a high speed by adopting a pump with a large flow rate and impacted, so that the current density range which can be used can reach 5-20ASD, and the required plating thickness can be obtained in a short time. The high-speed stirring is also favorable for separating out hydrogen precipitated on the surface of the plating piece from the palladium-nickel plating layer, so that the porosity of the palladium-nickel layer can be obviously reduced and the corrosion resistance can be improved.
The pH can be adjusted by using chemical pure or analytically pure ammonia water, and the pH needs to be measured and adjusted in time periodically, and the pH is recommended to be controlled to be more than 7.5 so as to ensure the stability of the plating solution and the faster deposition speed.
The palladium-nickel plating solution adopted by the invention can be suitable for full dip plating, and can also be suitable for local selective plating modes, such as brush plating, wheel plating, spot plating, free spray plating and the like. If a local plating mode is adopted, the palladium-nickel plating layer can be selectively plated only in the contact function area, so that the consumption of noble metal palladium is greatly reduced, and the electroplating cost is obviously reduced.
Further, the third step further includes the following steps: and coating a layer of lubricating oil on the surface of the hard gold layer to form a lubricating protective coating. So that the wear resistance of the palladium-nickel coating is obviously improved.
Further, the lubricating oil comprises one of perfluoropolyethers, polyphenylene ethers, long-chain hydrocarbon oil and fluorocarbon ethers, the concentration range is 1-10wt%, and the coating mode is soaking, brushing or spraying. The local coating mode in the contact functional area can save the consumption and reduce the cost.
The invention has the beneficial effects that: the invention provides a high corrosion resistance palladium-nickel alloy plating layer composition with excellent brine anode electrolytic corrosion resistance, which is provided by arranging a sulfur-free pore-free high corrosion resistance nickel bottom layer, a palladium-nickel plating layer with high palladium content and a hard gold layer with excellent wear resistance, and compared with the traditional 70-90wt% palladium-nickel plating layer with the same thickness, the anode electrolytic corrosion resistance of the palladium-nickel plating layer is improved by more than 1.5 times. The plating method and the plating solution provided by the invention can be used for obtaining a plating layer which is well combined with a connector terminal base material, has strong corrosion resistance and is wear-resistant.
Drawings
Fig. 1 is a schematic structural diagram of a palladium-nickel alloy plating layer with high corrosion resistance in example 1.
Fig. 2 is a schematic structural diagram of a palladium-nickel alloy plating layer with high corrosion resistance in example 5.
FIG. 3 is a schematic diagram of a 3-electrode system for measuring corrosion current (Tafel curve).
FIG. 4 is a graph showing the results of a test for measuring corrosion current (Tafel).
The reference numerals are: 1-substrate layer, 2-non-porous nickel bottom layer, 3-high corrosion resistance palladium nickel plating layer, 4-hard gold layer and 5-lubrication protective coating.
Detailed Description
The invention will be further described with reference to examples and drawings, to which reference is made, but which are not intended to limit the scope of the invention.
In a typical embodiment of the invention, a high corrosion resistance palladium-nickel alloy plating layer comprises an nonporous nickel bottom layer 2 arranged on the surface of a substrate 1, wherein the upper surface of the nonporous nickel bottom layer 2 is provided with a high corrosion resistance palladium-nickel plating layer 3, the upper surface of the palladium-nickel plating layer 3 is provided with a hard gold layer 4, and the palladium content of the palladium-nickel plating layer 3 is 90-98wt%.
Further, the non-porous nickel underlayer 2 is preferably a non-porous sulfur-free nickel underlayer.
The thickness of the non-porous nickel bottom layer 2 is 1-6 mu m; preferably 2.0-5.0 μm. The thickness of the high corrosion resistance palladium nickel plating layer 3 is 0.8-5 mu m. The hard gold layer 4 has a thickness of 0.025-0.25 μm, preferably 0.05-0.08 μm.
Further, the upper surface of the hard gold layer 4 is also provided with a lubrication protective coating 5.
The high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 3-30g/L of palladium ions, 0.3-15g/L of nickel ions, 30-80g/L of conductive salt and 1-10g/L of additive B.
Further, the additive B is olefin sulfonate or olefin sulfonate derivative.
An electroplating method for obtaining the high corrosion resistance palladium-nickel alloy plating layer comprises the following steps:
step one: pretreating a substrate 1, and electroplating an nonporous nickel bottom layer 2 on the surface of the substrate by adopting an nonporous nickel bottom layer plating solution;
step two: plating a high corrosion resistance palladium-nickel plating layer 3 on the surface of the nickel bottom layer 2 by adopting a high corrosion resistance palladium-nickel plating layer plating solution;
step three: and (3) flash plating a hard gold layer 4 on the surface of the high corrosion resistance palladium-nickel plating layer 3 to prepare the high corrosion resistance palladium-nickel alloy plating layer.
Further, in the first step, the substrate 1 is a copper substrate, a copper alloy substrate, a stainless steel substrate, a tungsten alloy substrate, a magnesium alloy substrate, an aluminum alloy substrate, a zinc substrate or a zinc alloy substrate.
Further, in the first step, the step of pretreating the substrate 1 includes: the surface of the substrate 1 is subjected to nickel plating, zinc dipping, or alkali copper cyanide plating. If the substrate is copper or copper alloy, a nickel underlayer can be directly electroplated on the surface of the substrate 1; if the base materials such as stainless steel or tungsten alloy are required to be plated with nickel, good binding force can be ensured; the magnesium alloy or aluminum alloy substrate needs to be subjected to corresponding zinc dipping treatment and then nickel plating to obtain good binding force; and the zinc or zinc alloy die casting base material needs to be pre-plated with alkali copper cyanide and then plated with nickel, so that good binding force can be obtained.
Further, in the first step, the non-porous nickel bottom layer plating solution comprises the following components: 40-130g/L of nickel ions, 0-45g/L of nickel chloride, 30-50g/L of boric acid and 0.05-0.2g/L of additive A.
Further, in the first step, the cathode current density of the electroplating is 0.5-15A/dm2 (ASD), the pH of the non-porous nickel plating solution is 2.5-4.5, and the electroplating temperature is 50-65 ℃.
Further, in the second step, the cathode current density of the electroplating is 0.2-20A/dm2 (ASD), the pH value of the corrosion-resistant palladium-nickel alloy plating solution is 7.5-8.5, and the electroplating temperature is 40-55 ℃.
Further, the third step further includes the following steps: and coating a layer of lubricating oil on the surface of the hard gold layer to form a lubricating protective coating.
Further, the lubricating oil is at least one of perfluoropolyethers, polyphenylene ethers, long-chain hydrocarbon oil and fluorocarbon ethers, and the coating mode is soaking, brushing or spraying.
Example 1
As shown in fig. 1, the high corrosion resistance palladium-nickel alloy plating layer comprises an nonporous nickel bottom layer 2 arranged on the surface of a substrate 1, wherein the upper surface of the nonporous nickel bottom layer 2 is provided with a high corrosion resistance palladium-nickel plating layer 3, the upper surface of the palladium-nickel plating layer 3 is provided with a hard gold layer 4, and the palladium content of the palladium-nickel plating layer 3 is 90-98wt%. Further, the non-porous nickel underlayer 2 is preferably a non-porous sulfur-free nickel underlayer.
In this example, the thickness of the non-porous nickel underlayer 2 was 3.8. Mu.m, the thickness of the high corrosion resistance palladium nickel plating layer 3 was 1.5. Mu.m, and the thickness of the hard gold layer 4 was 0.08. Mu.m. The palladium content in the plating layer is tested by an XRF film thickness instrument: 91.5wt%.
The high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 15g/L of palladium ion (added as tetraammine palladium chloride), 2g/L of nickel ion (added as nickel sulfate), 40g/L of conductive salt (ammonium sulfate) and 1.5g/L of additive B (sodium vinyl sulfonate).
An electroplating method for obtaining the high corrosion resistance palladium-nickel alloy plating layer comprises the following steps:
step one: pretreating a substrate 1, and electroplating an nonporous nickel bottom layer 2 on the surface of the substrate by adopting an nonporous nickel bottom layer plating solution;
step two: plating a high corrosion resistance palladium-nickel plating layer 3 on the surface of the nickel bottom layer 2 by adopting a high corrosion resistance palladium-nickel plating layer plating solution;
step three: and (3) flash plating a hard gold layer 4 on the surface of the high corrosion resistance palladium-nickel plating layer 3 to prepare the high corrosion resistance palladium-nickel alloy plating layer.
Further, in this embodiment, the substrate layer 1 is a phosphor bronze substrate, and may be directly plated on the surface of the substrate.
Further, in the first step, the non-porous nickel bottom layer plating solution comprises the following components: 110g/L nickel ion (added as nickel sulfamate concentrate), 5g/L nickel chloride (NiCl2.6H2O), 45g/L boric acid (H3 BO 3), 0.05g/L additive A (sodium dodecyl sulfate).
Further, in the first step, the cathode current density of the plating was 5A/dm2 (ASD), pH4.0, temperature 60℃and magnetic stirring of the 4cm rotor, 1300RPM.
Further, in the second step, the cathode current density of the plating was 5A/dm2 (ASD), pH7.5, the temperature was 45℃and the rotor was magnetically stirred for 4cm at 1300RPM.
Further, step three was prepared by electroplating with commercial hard Gold liquid-technical Gold 1020C EG at 60℃with a current density of 5ASD, a 4cm rotor, and magnetic stirring at 1300RPM.
Example 2
The palladium-nickel alloy plating layer with high corrosion resistance comprises a non-porous nickel bottom layer 2 arranged on the surface of a base material 1, wherein the high corrosion resistance palladium-nickel plating layer 3 is arranged on the upper surface of the non-porous nickel bottom layer 2, a hard gold layer 4 is arranged on the upper surface of the palladium-nickel plating layer 3, and the palladium content of the palladium-nickel plating layer 3 is 90-98wt%. Further, the non-porous nickel underlayer 2 is preferably a non-porous sulfur-free nickel underlayer.
In this example, the thickness of the non-porous nickel underlayer 2 was 3.8 μm, the thickness of the high corrosion resistance palladium nickel plating layer 3 was 2.0 μm, and the thickness of the hard gold layer 4 was 0.08 μm. The palladium content in the plating layer is tested by an XRF film thickness instrument: 95.5wt%.
The high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 20g/L of palladium ion (added as tetraammine palladium chloride), 2g/L of nickel ion (added as nickel sulfate), 60g/L of conductive salt (ammonium sulfate) and 3.5g/L of additive B (sodium vinyl sulfonate).
An electroplating method for obtaining the high corrosion resistance palladium-nickel alloy plating layer comprises the following steps:
step one: pretreating a substrate 1, and electroplating an nonporous nickel bottom layer 2 on the surface of the substrate by adopting an nonporous nickel bottom layer plating solution;
step two: plating a high corrosion resistance palladium-nickel plating layer 3 on the surface of the nickel bottom layer 2 by adopting a high corrosion resistance palladium-nickel plating layer plating solution;
step three: and (3) flash plating a hard gold layer 4 on the surface of the high corrosion resistance palladium-nickel plating layer 3 to prepare the high corrosion resistance palladium-nickel alloy plating layer.
Further, in this embodiment, the substrate layer 1 is a phosphor bronze substrate, and may be directly plated on the surface of the substrate.
Further, in the first step, the non-porous nickel bottom layer plating solution comprises the following components: 110g/L nickel ion (added as nickel sulfamate concentrate), 5g/L nickel chloride (NiCl2.6H2O), 45g/L boric acid (H3 BO 3), 0.05g/L additive A (sodium dodecyl sulfate).
Further, in the first step, the cathode current density of the plating was 5A/dm2 (ASD), pH4.0, temperature 60℃and magnetic stirring of the 4cm rotor, 1300RPM.
Further, in the second step, the cathode current density of the plating was 8A/dm2 (ASD), pH8.0, temperature 50℃and magnetic stirring of the 4cm rotor, 1300RPM.
Further, step three was prepared by electroplating with commercial hard Gold liquid-technical Gold 1020C EG at 60℃with a current density of 5ASD, a 4cm rotor, and magnetic stirring at 1300RPM.
Example 3
The palladium-nickel alloy plating layer with high corrosion resistance comprises a non-porous nickel bottom layer 2 arranged on the surface of a base material 1, wherein the high corrosion resistance palladium-nickel plating layer 3 is arranged on the upper surface of the non-porous nickel bottom layer 2, a hard gold layer 4 is arranged on the upper surface of the palladium-nickel plating layer 3, and the palladium content of the palladium-nickel plating layer 3 is 90-98wt%. Further, the non-porous nickel underlayer 2 is preferably a non-porous sulfur-free nickel underlayer.
In this example, the thickness of the non-porous nickel underlayer 2 was 3.8 μm, the thickness of the high corrosion resistance palladium nickel plating layer 3 was 2.5 μm, and the thickness of the hard gold layer 4 was 0.08 μm. The palladium content in the plating layer is tested by an XRF film thickness instrument: 96.5wt%.
The high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 25g/L of palladium ion (added as tetraammine palladium chloride), 2.5g/L of nickel ion (added as nickel sulfate), 50g/L of conductive salt (ammonium sulfate) and 3g/L of additive B (sodium propenyl sulfonate).
An electroplating method for obtaining the high corrosion resistance palladium-nickel alloy plating layer comprises the following steps:
step one: pretreating a substrate 1, and electroplating an nonporous nickel bottom layer 2 on the surface of the substrate by adopting an nonporous nickel bottom layer plating solution;
step two: plating a high corrosion resistance palladium-nickel plating layer 3 on the surface of the nickel bottom layer 2 by adopting a high corrosion resistance palladium-nickel plating layer plating solution;
step three: and (3) flash plating a hard gold layer 4 on the surface of the high corrosion resistance palladium-nickel plating layer 3 to prepare the high corrosion resistance palladium-nickel alloy plating layer.
Further, in this embodiment, the substrate layer 1 is a phosphor bronze substrate, and may be directly plated on the surface of the substrate.
Further, in the first step, the non-porous nickel bottom layer plating solution comprises the following components: 110g/L nickel ion (added as nickel sulfamate concentrate), 5g/L nickel chloride (NiCl2.6H2O), 45g/L boric acid (H3 BO 3), 0.05g/L additive A (sodium dodecyl sulfate).
Further, in the first step, the cathode current density of the plating was 5A/dm2 (ASD), pH4.0, temperature 60℃and magnetic stirring of the 4cm rotor, 1300RPM.
Further, in the second step, the cathode current density of the plating is 12A/dm2 (ASD), the pH is 8.5, and the temperature is: the rotor was magnetically stirred at 40℃for 4cm at 1300RPM.
Further, step three was prepared by electroplating with commercial hard Gold liquid-technical Gold 1020C EG at 60℃with a current density of 5ASD, a 4cm rotor, and magnetic stirring at 1300RPM.
Example 4
The palladium-nickel alloy plating layer with high corrosion resistance comprises a non-porous nickel bottom layer 2 arranged on the surface of a base material 1, wherein the high corrosion resistance palladium-nickel plating layer 3 is arranged on the upper surface of the non-porous nickel bottom layer 2, a hard gold layer 4 is arranged on the upper surface of the palladium-nickel plating layer 3, and the palladium content of the palladium-nickel plating layer 3 is 90-98wt%. Further, the non-porous nickel underlayer 2 is preferably a non-porous sulfur-free nickel underlayer.
In this example, the thickness of the non-porous nickel underlayer 2 was 3.8. Mu.m, the thickness of the high corrosion resistance palladium nickel plating layer 3 was 3.0. Mu.m, and the thickness of the hard gold layer 4 was 0.08. Mu.m. The palladium content of the coating was 97.5wt% as measured by XRF film thickness tester.
The high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 20g/L of palladium ion (added as tetraammine palladium chloride), 1.5g/L of nickel ion (added as nickel sulfate), 55g/L of conductive salt (ammonium sulfate) and 2.5g/L of additive B (sodium propenyl sulfonate).
An electroplating method for obtaining the high corrosion resistance palladium-nickel alloy plating layer comprises the following steps:
step one: pretreating a substrate 1, and electroplating an nonporous nickel bottom layer 2 on the surface of the substrate by adopting an nonporous nickel bottom layer plating solution;
step two: plating a high corrosion resistance palladium-nickel plating layer 3 on the surface of the nickel bottom layer 2 by adopting a high corrosion resistance palladium-nickel plating layer plating solution;
step three: and (3) flash plating a hard gold layer 4 on the surface of the high corrosion resistance palladium-nickel plating layer 3 to prepare the high corrosion resistance palladium-nickel alloy plating layer.
Further, in this embodiment, the substrate layer 1 is a phosphor bronze substrate, and may be directly plated on the surface of the substrate.
Further, in the first step, the non-porous nickel bottom layer plating solution comprises the following components: 110g/L nickel ion (added as nickel sulfamate concentrate), 5g/L nickel chloride (NiCl2.6H2O), 45g/L boric acid (H3 BO 3), 0.05g/L additive A (sodium dodecyl sulfate).
Further, in the first step, the cathode current density of the plating was 5A/dm2 (ASD), pH4.0, temperature 60℃and magnetic stirring of the 4cm rotor, 1300RPM.
Further, in the second step, the cathode current density of the plating was 10A/dm2 (ASD), pH7.8, the temperature was 48℃and the magnetic stirring was performed on a 4cm rotor at 1300RPM.
Further, step three was prepared by electroplating with commercial hard Gold liquid-technical Gold 1020C EG at 60℃with a current density of 5ASD, a 4cm rotor, and magnetic stirring at 1300RPM.
Example 5
As shown in fig. 2, the high corrosion resistance palladium-nickel alloy plating layer comprises an nonporous nickel bottom layer 2 arranged on the surface of a substrate 1, wherein the high corrosion resistance palladium-nickel plating layer 3 is arranged on the upper surface of the nonporous nickel bottom layer 2, a hard gold layer 4 is arranged on the upper surface of the palladium-nickel plating layer 3, and the palladium content of the palladium-nickel plating layer 3 is 90-98wt%. Further, the non-porous nickel underlayer is preferably a non-porous sulfur-free nickel underlayer.
In this example, the thickness of the non-porous nickel underlayer 2 was 3.8 μm, and the thickness of the high corrosion resistance palladium nickel plating layer 3 was 3.0 μm. The hard gold layer 4 has a thickness of 0.08 μm. The palladium content of the coating was 97.5wt% as measured by XRF film thickness tester.
Further, the surface layer further comprises a lubrication protective coating 5, and the lubrication protective coating 5 is arranged on the upper surface of the hard gold layer 4. The use of the lubricating protective coating can obviously improve the wear resistance of the palladium-nickel coating, and can still maintain good corrosion resistance of the brine anodic electrolytic corrosion after multiple plugging tests or use.
The high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 20g/L of palladium ion (added as tetraammine palladium chloride), 1.5g/L of nickel ion (added as nickel sulfate), 55g/L of conductive salt (ammonium sulfate) and 2.5g/L of additive B (sodium propenyl sulfonate).
An electroplating method for obtaining the high corrosion resistance palladium-nickel alloy plating layer comprises the following steps:
step one: pretreating a substrate 1, and electroplating an nonporous nickel bottom layer 2 on the surface of the substrate by adopting an nonporous nickel bottom layer plating solution;
step two: plating a high corrosion resistance palladium-nickel plating layer 3 on the surface of the nickel bottom layer 2 by adopting a high corrosion resistance palladium-nickel plating layer plating solution;
step three: and (3) flash plating a hard gold layer 4 on the surface of the high corrosion resistance palladium-nickel plating layer 3 to prepare the high corrosion resistance palladium-nickel alloy plating layer.
Further, in this embodiment, the substrate layer 1 is a phosphor bronze substrate, and may be directly plated on the surface of the substrate.
Further, in the first step, the non-porous nickel bottom layer plating solution comprises the following components: 110g/L nickel ion (added as nickel sulfamate concentrate), 5g/L nickel chloride (NiCl2.6H2O), 45g/L boric acid (H3 BO 3), 0.05g/L additive A (sodium dodecyl sulfate).
Further, in the first step, the cathode current density of the plating was 5A/dm2 (ASD), pH4.0, temperature 60℃and magnetic stirring of the 4cm rotor, 1300RPM.
Further, in the second step, the cathode current density of the plating was 10A/dm2 (ASD), pH7.8, the temperature was 48℃and the magnetic stirring was performed on a 4cm rotor at 1300RPM.
Further, step three was prepared by electroplating with commercial hard Gold liquid-technical Gold 1020C EG at 60℃with a current density of 5ASD, a 4cm rotor, and magnetic stirring at 1300RPM.
Further, the third step further includes the following steps: a layer of lubricating oil is coated on the surface of the hard gold layer 4 to form a lubricating protective coating 5. So that the wear resistance of the palladium-nickel coating is obviously improved.
Further, the lubricating oil is at least one of perfluoropolyethers, polyphenylene ethers, long-chain hydrocarbon oil and fluorocarbon ethers, and the coating mode is soaking, brushing or spraying, and the concentration range is 1-10wt%. This example uses dip coating to coat 5% polyphenylene ether (PPE) lube on the sample.
Example 6
Compared with the traditional 70-90wt% palladium-nickel coating, the high corrosion-resistant palladium-nickel coating obtained by the invention is also subjected to Tafel curve test in 5% sodium chloride neutral brine electrolyte by using a 3-electrode system of an electrochemical workstation, and the corrosion potential and the corrosion current are measured. The corrosion potential of the high corrosion resistance palladium nickel plating layer (Pd% @95.5 wt%) obtained by the invention is corrected to be-0.07V, the corrosion current is lower than 4.689 x 10-6A, the corrosion potential of the traditional 77wt% palladium nickel alloy plating layer is more negative to be-0.09V, and the corrosion current is larger than 7.491 x 10-6A, so that the palladium nickel plating layer of the invention has stronger inertia, is more stable and has more excellent anodic electrolytic corrosion resistance. The schematic diagram of the 3-electrode system is shown in fig. 3, and the Tafel curve test result is shown in fig. 4. In the test, the model of the electrochemical analyzer is CHI604A, the auxiliary electrode is a platinum sheet, the reference electrode is a mercurous sulfate electrode, a calomel electrode and the research electrode are different palladium-nickel alloy plating samples.
Comparative examples 1 to 4
70-90wt% palladium nickel electroplating solution Technic Pallaspeed Palladium Nickel TC widely used in the electronic industry is used for directly electroplating palladium nickel plating layers with the thickness of 1.5 mu m,2.0 mu m,2.5 mu m and 3.0 mu m on a 3.8 mu m common semi-bright nickel bottom layer, and the palladium nickel plating layers are respectively recorded as comparative examples 1-4. The actual palladium content in the coating was 77wt% as measured by XRF film thickness meter. The common semi-bright nickel plating solution uses Enthone-OMI OXR-1300C. The composition of the plating solution for the bottom layers of hard gold, palladium nickel and the electroplating conditions are recommended by the supplier technology, and the test sample is obtained by electroplating on the phosphor bronze substrate under the magnetic stirring conditions of a current density of 5ASD, a rotor of 4cm and 1300RPM at the temperature of 60 ℃.
Comparative example 5
The difference between this comparative example and example 5 is that:
the surface of this comparative example was not coated with lubricant oil for protection.
The samples of examples 1-4 and the samples of comparative examples 1-4 were tested for corrosion resistance according to the brine anodic electrolytic corrosion test conditions, wherein the test conditions were 5wt% sodium chloride, the temperature was 40 ℃, the magnetic stirring was 200RPM, the cathode was a platinum titanium sheet, the anode was a tested sample, the test functional area was exposed, and the other areas were blocked with nail polish or epoxy resin; the distance between the anode and the cathode is 10-20mm, and the anode voltage is constant voltage of 5V. When the first corrosion point exceeding 0.05mm was observed in the sample functional area, the test was ended and the time was recorded, which means that the palladium nickel plating was penetrated by corrosion and corrosion of the underlying nickel layer or substrate occurred, which is the brine anodic electrolytic corrosion resistance time.
The composition of the palladium nickel plating layers of examples 1-4 and comparative examples 1-4 and the brine anodic electrolytic corrosion resistance are shown in the following table:
TABLE 1 comparison of brine anodic electrolytic Corrosion resistance of different Palladium Nickel coatings
The time for brine-resistant anodic electrolytic corrosion of example 1 reached 5min, which is significantly higher than 2min of the common palladium-nickel coating of 77wt% of the same thickness. The time for brine-resistant anodic electrolytic corrosion of example 2 reached 7min, which is significantly higher than 3min of the 77wt% palladium-nickel coating of the same thickness. The time for brine-resistant anodic electrolytic corrosion of example 3 reached 9min, which is significantly higher than 6min of a 77% palladium-nickel coating of the same thickness. The time for brine-resistant anodic electrolytic corrosion of example 4 reached 12min, which is significantly higher than 8min of the 77% palladium-nickel coating of the same thickness.
The sample of the embodiment 5 coated with the lubricating oil is assembled into a Type C male end connector, and is inserted and matched with the Type C female end connector, 1000 times of insertion and extraction tests are manually carried out, and the fact that a sample contact functional area has no obvious grinding and insertion trace or abrasion is found; and the contact function area of the Type C male connector sample of comparative example 5, which was not coated with lubricating oil, was subjected to the same 1000 grinding inserts, and very obvious grinding marks and abrasion were generated. The brine electrolytic corrosion test result shows that corrosion points appear after 1000 times of plugging of the sample coated with the lubricating oil for 8 minutes; and after 1000 times of plugging of the sample without the lubricating oil, corrosion points appear in 4 minutes. This shows that after the lubricating oil is coated, the wear resistance is obviously improved, the wear and damage degree to the functional area is less, and the electrolytic corrosion resistance of the brine anode after plugging can be better maintained. The test results are shown in the following table:
TABLE 2 Effect of lubricating oils on wear resistance of palladium-nickel alloy coatings
Finally, it should be noted that the above embodiments are only for illustrating the technical solution of the present invention, and not for limiting the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions can be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (6)
1. A palladium-nickel alloy plating layer with high corrosion resistance is characterized in that: the high corrosion resistance palladium-nickel coating is arranged on the upper surface of the non-porous nickel bottom layer, a hard gold layer is arranged on the upper surface of the palladium-nickel coating, the palladium content of the palladium-nickel coating is 90-98wt%, and the thickness of the palladium-nickel coating is 0.8-5 mu m; the non-porous nickel bottom plating solution comprises the following components: 40-130g/L of nickel ions, 5-45g/L of nickel chloride, 30-50g/L of boric acid and 0.05-0.2g/L of additive A; the additive A is sodium dodecyl sulfonate; the nickel ions are nickel sulfamate; the cathode current density of the non-void nickel bottom layer electroplating is 0.5-15ASD, the pH value of the non-void nickel plating solution is 2.5-4.5, and the electroplating temperature is 50-65 ℃.
2. The high corrosion resistant palladium nickel alloy plating according to claim 1, wherein: the upper surface of the hard gold layer is also provided with a lubricating protective coating.
3. The plating method of a high corrosion resistance palladium-nickel alloy plating layer according to claim 1 to 2, characterized in that the plating method comprises the steps of:
step one: pretreating the base material, and electroplating a non-porous nickel bottom layer on the surface of the base material by adopting a non-porous nickel bottom layer plating solution; the cathode current density of the electroplating is 0.5-15ASD, the pH value of the non-porous nickel plating solution is 2.5-4.5, and the electroplating temperature is 50-65 ℃; the non-porous nickel bottom plating solution comprises the following components: 40-130g/L of nickel ions, 5-45g/L of nickel chloride, 30-50g/L of boric acid and 0.05-0.2g/L of additive A; the additive A is sodium dodecyl sulfonate, and the nickel ions are nickel sulfamate;
step two: plating a high corrosion resistance palladium-nickel plating layer on the surface of the nickel bottom layer by adopting a high corrosion resistance palladium-nickel plating layer plating solution; the high corrosion resistance palladium nickel plating layer electroplating solution comprises the following raw materials in concentration: 3-30g/L of palladium ions, 0.3-15g/L of nickel ions, 30-80g/L of conductive salt and 1-10g/L of additive B; the conductive salt is one or two of ammonium sulfate, ammonium chloride, potassium sulfate and potassium chloride; the additive B is one of alpha-olefin sodium sulfonate, vinyl sodium sulfonate and propenyl sodium sulfonate, and palladium ions adopt one of tetraammine palladium chloride or tetraammine palladium sulfate;
step three: and (3) flash plating a hard gold layer on the surface of the high corrosion resistance palladium-nickel plating layer to prepare the high corrosion resistance palladium-nickel alloy plating layer.
4. The plating method of a highly corrosion-resistant palladium-nickel alloy plating layer according to claim 3, characterized in that: in the first step, the step of preprocessing the base material comprises the following steps: the surface of the base material is pre-plated with nickel, zinc or alkali copper cyanide.
5. The plating method of a highly corrosion-resistant palladium-nickel alloy plating layer according to claim 3, characterized in that: the third step further comprises the following steps: and coating a layer of lubricating oil on the surface of the hard gold layer to form a lubricating protective coating.
6. The method for electroplating a high corrosion resistance palladium nickel alloy plating layer resistant to anodic electrolytic corrosion according to claim 5, wherein: the lubricating oil is at least one of perfluoropolyethers, polyphenylene ethers, long-chain hydrocarbon oil and fluorocarbon ethers, and the coating mode is soaking, brushing or spraying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111146585.4A CN113699565B (en) | 2021-09-28 | 2021-09-28 | High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111146585.4A CN113699565B (en) | 2021-09-28 | 2021-09-28 | High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113699565A CN113699565A (en) | 2021-11-26 |
| CN113699565B true CN113699565B (en) | 2023-07-04 |
Family
ID=78662242
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111146585.4A Active CN113699565B (en) | 2021-09-28 | 2021-09-28 | High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113699565B (en) |
Family Cites Families (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE3108508C2 (en) * | 1981-03-06 | 1983-06-30 | Langbein-Pfanhauser Werke Ag, 4040 Neuss | Bath for the electrodeposition of a palladium / nickel alloy |
| GB2115440A (en) * | 1982-02-25 | 1983-09-07 | Engelhard Ind Ltd | Electroplating bath for the production of palladium-nickel alloy contact material |
| US4463060A (en) * | 1983-11-15 | 1984-07-31 | E. I. Du Pont De Nemours And Company | Solderable palladium-nickel coatings and method of making said coatings |
| JPS60248892A (en) * | 1984-05-24 | 1985-12-09 | Electroplating Eng Of Japan Co | High-purity palladium-nickel alloy plating liquid and method thereof and alloy coated parts thereof and gold or gold alloy coated parts thereof |
| FR2695259B1 (en) * | 1992-09-03 | 1994-10-28 | Souriau & Cie | Nickel electrical contact terminal for connector, connector and manufacturing process. |
| JPH10289975A (en) * | 1997-04-14 | 1998-10-27 | Denso Corp | Wire bonding terminal and manufacture thereof |
| JP3297861B2 (en) * | 1998-06-29 | 2002-07-02 | 日本航空電子工業株式会社 | Plating material |
| JP2000077589A (en) * | 1998-09-03 | 2000-03-14 | Hitachi Cable Ltd | Lead wire |
| WO2001063007A1 (en) * | 2000-02-24 | 2001-08-30 | Ibiden Co., Ltd. | Nickel-gold plating exhibiting high resistance to corrosion |
| JP2004190064A (en) * | 2002-12-09 | 2004-07-08 | Matsushita Electric Works Ltd | Method for surface-treating metallic terminal, and metallic terminal |
| CN101323961A (en) * | 2007-06-14 | 2008-12-17 | 沈阳黎明航空发动机(集团)有限责任公司 | Heat resistant corrosion resistant low stress nickel plating process |
| JP2011208175A (en) * | 2010-03-29 | 2011-10-20 | Asahi Plating Co Ltd | Method for producing plated article, and plated article |
| CN109038007A (en) * | 2018-09-27 | 2018-12-18 | 北京小米移动软件有限公司 | The electro-plating method of the electrical connection module of connector, connector and electrical connection module |
-
2021
- 2021-09-28 CN CN202111146585.4A patent/CN113699565B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN113699565A (en) | 2021-11-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101525711B (en) | Magnesium alloy with zinc and nickel compound plating layers and preparation method thereof | |
| KR101502804B1 (en) | Pd and Pd-Ni electrolyte baths | |
| CN101298200B (en) | Magnesium alloy composite material and preparation thereof | |
| US4789437A (en) | Pulse electroplating process | |
| CN101748451A (en) | Electroplating technology for bearing quaternary alloy | |
| CN110158126A (en) | A kind of method that metal surface prepares ternary metal hydrogen-precipitating electrode | |
| US20040195107A1 (en) | Electrolytic solution for electrochemical deposition gold and its alloys | |
| CN113699566B (en) | Palladium-nickel combined plating layer resistant to anodic electrolytic corrosion and electroplating method thereof | |
| CN113699565B (en) | High corrosion resistance palladium-nickel alloy plating layer, electroplating method thereof and palladium-nickel plating layer electroplating liquid | |
| US3500537A (en) | Method of making palladium coated electrical contacts | |
| US3150065A (en) | Method for plating palladium | |
| CN114182315B (en) | Corrosion-resistant combined electroplated layer and electroplating method | |
| CN110923757B (en) | Cyanide-free alkali copper electroplating solution and use method thereof | |
| Krishnan et al. | Electroplating of Copper from a Non-cyanide Electrolyte | |
| Dimitrijević et al. | Temperature effect on decorative gold coatings obtained from electrolyte based on mercaptotriazole–comparison with cyanide | |
| CN113789558B (en) | Plug-resistant non-porous nickel-based composite coating and preparation method thereof | |
| CN113737236B (en) | High-corrosion-resistance composite coating and preparation method and application thereof | |
| CN101343760A (en) | Microelectron packaging metal cover plate electroplating nickel phosphor alloy production technology | |
| EP3816326B1 (en) | Acidic aqueous binary silver-bismuth alloy electroplating compositions and methods | |
| CN114411215B (en) | Platinum electroplating solution and electroplating method | |
| CN113774446B (en) | Nickel coating with high corrosion resistance, preparation method thereof and electroplating liquid | |
| Wilkinson | The replacement of gold by palladium-nickel on connectors | |
| US20200240029A1 (en) | Indium electroplating compositions and methods for electroplating indium on nickel | |
| KR20190001427A (en) | Hybrid nickel electrodeposition method and solution used therein exhibiting improved chemical resistance | |
| Baumgärtner et al. | Palladium-Iron alloy electrodeposition. part I single metal systems |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |