CN215856392U - Corrosion-resistant palladium-nickel combined coating - Google Patents
Corrosion-resistant palladium-nickel combined coating Download PDFInfo
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- CN215856392U CN215856392U CN202122372640.3U CN202122372640U CN215856392U CN 215856392 U CN215856392 U CN 215856392U CN 202122372640 U CN202122372640 U CN 202122372640U CN 215856392 U CN215856392 U CN 215856392U
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Abstract
The utility model provides a corrosion-resistant palladium-nickel combined coating which comprises a bottom layer, a middle layer and a surface layer, wherein the middle layer is arranged on the upper surface of the bottom layer, the surface layer is arranged on the upper surface of the middle layer, the bottom layer is a nickel bottom layer, the middle layer is a platinum coating, the surface layer comprises a palladium-nickel coating and a hard gold layer arranged on the upper surface of the palladium-nickel coating, and the lower surface of the palladium-nickel coating is attached to the platinum coating. The palladium-nickel composite plating layer has simple structure, only uses the nickel layer as the bottom layer, does not use a complex composite middle layer, only uses single platinum as the middle layer, and does not need to use an expensive rhodium-ruthenium plating layer, thereby having easy industrialized implementation, low plating cost, and good anode electrolytic corrosion resistance and wear resistance.
Description
Technical Field
The utility model relates to the technical field of electroplating, and particularly discloses a corrosion-resistant palladium-nickel composite plating layer.
Background
In the electronic industry, especially in the mobile phone industry, the charging application of Type C and Micro-USB charging port connectors, the problem of application failure that the charging function is affected due to the serious corrosion of the nickel base layer and the copper alloy substrate is recently focused by the industry because the anode signal pin terminal undergoes very obvious anodic electrolytic corrosion when liquid corrosive media such as moisture, sweat or brine enter.
Since 2016, rhodium ruthenium plating (RhRu) is introduced into the terminal electroplating process of Type C and Micro-USB charging port connectors, and electrolytic corrosion resistance of brine anode is greatly improved. However, the price of rhodium (Rh) is continuously rising, and the rising range is more than 300 percent from the average value USD663/Ounce in 2016 to the average value USD2066/Ounce in 2021, so that the electroplating cost is greatly influenced. In order to reduce the electroplating cost and maintain the electrolytic corrosion resistance of the brine anode unchanged, the mobile phone industry introduces a platinum (Pt) coating and uses a platinum combined coating, or platinum (Pt) and rhodium ruthenium (RhRu) to reduce the electroplating cost, the adopted composite plating layer is complex, generally more than 5 plating layers, some prior arts do not use rhodium ruthenium alloy at all, the different compositions of copper (Cu), nickel (Ni), nickel-tungsten (NiW), gold (Au), silver (Ag), palladium-nickel (PdNi) and platinum (Pt) or platinum-ruthenium (PtRu) alloy plating layers are adopted to realize cost reduction and maintain good brine anode electrolytic corrosion resistance, the adopted combined plating layers are complex, generally more than 5 plating layers, even the complex process of multilayer platinum of more than 7 plating layers is adopted, thus the design of an electroplating production line is complex, the process flow is very long, and the industrial implementation is difficult.
Although the nickel bottom layer is the cheapest and simplest bottom plating layer in the electronic industry, the commonly used semi-bright nickel has high porosity, so that the rhodium-ruthenium, platinum-gold or platinum-ruthenium alloy plating layer cannot be ensured to be free of pores, and further, the electrolytic corrosion resistance of the brine anode is obviously influenced. Thus, in the prior art, very complex underlayer combinations such as NiW, Cu + NiW, or Cu + Ni + NiW are used as the underlayer. NiW is an amorphous non-porous coating, but requires the use of NiW plating solution and additives from the company Xtalic Corporation, which is expensive in terms of the double pulse technique and the corresponding double pulse rectifier. In the prior art, Au, Ag, PdNi and the like or different combinations thereof are also used as intermediate plating layers, however, the intermediate plating layers except PdNi are not resistant to brine anodic electrolytic corrosion at all. The Pd content in the PdNi plating layer used in the electronic industry is only 70-90 wt%, generally controlled at 75-85 wt%, and the capability of resisting brine anodic electrolytic corrosion is limited. Therefore, the specifications of these patented technologies and their plating combinations are too complicated from the viewpoint of cost control and process simplification to be further improved.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the utility model aims to provide the corrosion-resistant palladium-nickel composite plating layer which is simple in structure, can be attached to the surface of a base material of a product, has good saline anode electrolytic corrosion resistance, is high in industrialization feasibility and can obviously reduce the electroplating cost.
In order to solve the technical problems, the utility model adopts the following technical scheme:
the utility model provides a corrosion-resistant palladium-nickel combined plating layer, includes bottom, intermediate level and top layer, the intermediate level sets up in the upper surface of bottom, the top layer sets up in the upper surface in intermediate level, the bottom is the nickel bottom, the intermediate level is the platinum cladding material, the top layer includes palladium-nickel cladding material and sets up in the hard gold layer of palladium-nickel cladding material upper surface, the lower surface and the platinum cladding material laminating of palladium-nickel cladding material.
Further, the surface layer also comprises a lubricating coating arranged on the upper surface of the hard gold layer.
Further, the nickel bottom layer is a nonporous nickel bottom layer.
Furthermore, the thickness of the nonporous nickel bottom layer is 1.0-10.0 μm. Furthermore, the thickness of the nonporous nickel bottom layer is 2.0-5.0 μm.
Further, the thickness of the platinum plating layer is 0.25-0.5 μm.
Further, the thickness of the palladium-nickel alloy plating layer is 0.8-3 mu m.
Furthermore, the thickness of the hard gold layer is 0.025-0.25 μm. Furthermore, the thickness of the hard gold layer is 0.05-0.08 mu m.
Furthermore, the corrosion-resistant palladium-nickel composite plating layer further comprises a connecting layer, the lower surface of the connecting layer is used for being attached to a base material, and the upper surface of the connecting layer is attached to the bottom layer.
Further, the connecting layer is a nickel connecting layer, a zinc connecting layer or an alkali copper cyanide connecting layer.
The utility model has the beneficial effects that: the palladium-nickel composite plating layer has simple structure, only uses the nickel layer as the bottom layer, does not use a complex composite middle layer, only uses single platinum as the middle layer, and does not need to use an expensive rhodium-ruthenium plating layer, thereby having easy industrialized implementation, low plating cost, and good anode electrolytic corrosion resistance and wear resistance.
Drawings
Fig. 1 is a schematic structural diagram of the corrosion-resistant palladium-nickel composite plating layer of example 1.
Fig. 2 is a schematic structural diagram of the corrosion-resistant palladium-nickel composite plating layer of example 2.
Fig. 3 is a schematic structural diagram of the corrosion-resistant palladium-nickel composite plating layer of example 3.
The reference signs are: 1-a substrate layer, 2-a nickel bottom layer, 3-a platinum plating layer, 4-a palladium nickel plating layer, 5-a hard gold layer, 6-a lubricating coating and 7-a connecting layer.
Detailed Description
For the understanding of those skilled in the art, the present invention will be further described with reference to the following examples and drawings, which are not intended to limit the present invention.
Example 1
As shown in fig. 1, the corrosion-resistant palladium-nickel composite plating layer comprises a bottom layer, a middle layer and a surface layer, wherein the middle layer is arranged on the upper surface of the bottom layer, the surface layer is arranged on the upper surface of the middle layer, the bottom layer is a nickel bottom layer 2, the middle layer is a platinum plating layer 3, the surface layer comprises a palladium-nickel plating layer 4 and a hard gold layer 5 arranged on the upper surface of the palladium-nickel plating layer 4, and the lower surface of the palladium-nickel plating layer 4 is attached to the platinum plating layer 3. The bottom layer is used for being attached to the base material layer.
The palladium-nickel combined plating layer simplifies the bottom layer and the combined bottom layer, only uses the nickel layer as the bottom layer, does not use a complex combined middle layer, only uses single platinum as the middle layer, and does not use an expensive rhodium-ruthenium plating layer at all, so the specification is simplified, the industrial implementation is easy, and the plating cost is reduced; the palladium-nickel composite plating layer has good anodic electrolytic corrosion resistance and wear resistance, and can be arranged on the surface of a base material of an electronic product or other products, so that the corrosion resistance of the product is improved, and the service life of the product is prolonged.
The bottom layer is the nonporous nickel bottom layer 2, and the nonporous nickel has excellent corrosion resistance, so that the nonporous nickel layer is beneficial to completely eliminating the pores of the middle plating layer-platinum plating layer 4 on the nonporous nickel layer, and further the electrolytic corrosion resistance of the brine anode is obviously improved. The thickness of the non-porous nickel base layer 2 is 1.0-10.0 μm, preferably 2.0-5.0 μm. Further, the nonporous nickel substrate 2 is a sulfur-free nonporous nickel substrate 2.
The utility model only uses a single platinum plating layer 3 as the intermediate plating layer, and the thickness range can be very thin, preferably 0.25-0.5 μm. Since the non-porous bottom nickel is used, even if the platinum plating layer 3 is only 0.25 μm, it can be made completely non-porous, thereby providing very excellent resistance to electrolytic corrosion by brine anode. Taking terminals of a TypeC and a Micro-USB charging port in the mobile phone industry as an example: for continuous high-speed electroplating application of terminals of TypeC and Micro-USB charging ports in the mobile phone industry, the thickness of the platinum layer 3 is recommended to be as low as possible, preferably less than 0.5 μm, otherwise, a platinum electroplating sub tank with an effective length exceeding 15m needs to be designed (the total length of a platinum electroplating station reaches 26m) to obtain the required high thickness, such as 0.8-1.2 μm. Therefore, the whole continuous plating production line is very long, the required field is also very long, the pulling force required by the product in the electroplating walking process is large, the borne tension is also large, the product is easy to deform, and the subsequent automatic injection molding and assembly are not facilitated. The utility model only uses the low-thickness platinum with the thickness of 0.5 mu m as the intermediate coating, thereby not only obtaining longer brine anode electrolytic corrosion with high tolerance performance, but also reducing the effective length of the platinum electroplating sub-tank to 7.5m (the total length of the platinum electroplating station is 13m), avoiding the defects of site limitation, high tension and easy deformation and the like, not influencing the subsequent automatic injection molding and assembling process, and simultaneously remarkably reducing the electroplating cost.
The utility model uses high corrosion-resistant palladium-nickel alloy as the surface layer. The palladium-nickel plating layer 4 has good brine anode electrolytic corrosion resistance. The thickness range of the palladium-nickel plating layer 4 is 0.8-3 mu m, the thicker the palladium-nickel plating layer is, the stronger the electrolytic corrosion resistance of the brine anode is, but the overlarge thickness easily causes the overhigh cost and the overlarge product size.
The utility model improves and maintains the electrical properties required during application by plating a hard gold layer 5 on the surface of the palladium-nickel plating layer 4. Because the palladium plating layer and the palladium-nickel plating layer are both metals with high catalytic activity, in the application of the electronic connector, in the use process of high-order sliding grinding insertion and micro-grinding insertion of the connector, an organic polymer can be rapidly generated due to the strong catalytic activity of the palladium-nickel plating layer to cause the electrical property to gradually lose, and further cause the application failures such as open circuit and the like finally, in the embodiment, the hard gold layer 5 is attached to the surface of the palladium-nickel plating layer 4, so that the nickel plating layer 4 is not directly used as the outermost layer for electric contact. The thickness of the hard gold layer 5 is 0.025 to 0.25 μm, preferably 0.05 to 0.08 μm. By adopting the above structure, the present embodiment mainly functions as follows: the passivation of palladium and nickel in a high-temperature application environment is prevented, and the low and stable contact resistance which is the same as that of the traditional hard gold electroplating is kept; the palladium-nickel alloy is used as a solid lubricant to be attached to the surface of a palladium-nickel plating layer, so that the grinding insertion coefficient is reduced, and excellent wear resistance is obtained; the palladium-nickel plating layer is prevented from being directly exposed to a grinding and inserting interface, the generation of organic polymers in the processes of sliding grinding and inserting and micro-moving grinding and inserting can be minimized, and good electrical property in the long-time application process can be maintained.
Example 2
As shown in fig. 2, the corrosion-resistant palladium-nickel composite plating layer comprises a bottom layer, a middle layer and a surface layer, wherein the middle layer is arranged on the upper surface of the bottom layer, the surface layer is arranged on the upper surface of the middle layer, the bottom layer is a nickel bottom layer 2, the middle layer is a platinum plating layer 3, the surface layer comprises a palladium-nickel plating layer 4 and a hard gold layer 5 arranged on the upper surface of the palladium-nickel plating layer 4, and the lower surface of the palladium-nickel plating layer 4 is attached to the platinum plating layer 3.
Further, the nickel bottom layer is a non-porous nickel bottom layer 2. Further, the thickness of the nonporous nickel bottom layer 2 is 1.0-10.0 μm. Preferably 2.0 to 5.0 μm. The non-porous nickel has excellent corrosion resistance, and can remarkably improve the electrolytic corrosion resistance of the brine anode.
Further, the thickness of the platinum plating layer 3 is 0.25-0.5 μm. The thickness range of the electrolytic solution can be very thin, so that long brine anode electrolytic corrosion high resistance can be obtained, and the electroplating cost is also obviously reduced.
Further, the thickness of the palladium-nickel alloy plating layer 4 is 0.8-3 μm. The palladium nickel plating layer 4 has good brine anode electrolytic corrosion resistance, and the thicker the thickness, the stronger the brine anode electrolytic corrosion resistance.
Further, the thickness of the hard gold layer 5 is 0.025 to 0.25 μm. Preferably 0.05 to 0.08 μm. The hard gold layer 5 can prevent the passivation of palladium and nickel in a high-temperature application environment; and excellent wear resistance is obtained; the palladium-nickel plating layer is prevented from being directly exposed to a grinding and inserting interface, the generation of organic polymers in the processes of sliding grinding and inserting and micro-moving grinding and inserting can be minimized, and good electrical property in the long-time application process can be maintained.
Further, the surface layer also comprises a lubricating coating 6 arranged on the upper surface of the hard gold layer. The lubricating coating 6 is coated on the surface of the hard gold layer 5, so that the wear resistance can be further improved and improved, and fretting corrosion can be prevented. The lubricating oil adopted by the lubricating coating 6 can be perfluoropolyethers (PFPE), polyphenylene ethers (PPE), long-chain hydrocarbon oil, fluorocarbon ethers (FCE) and the like. The perfluoropolyethers (PFPE), the polyphenylene ethers (PPE), the long-chain hydrocarbon oil and the fluorocarbon ethers (FCE) are materials existing in the prior art and are used as the materials. After the lubricating oil is coated, the corrosion resistance of the brine anode after plugging can be better maintained due to the obvious improvement of the wear resistance and the less abrasion and damage degree of the functional area.
Example 3
As shown in fig. 3, the corrosion-resistant palladium-nickel composite plating layer comprises a bottom layer, a middle layer and a surface layer, wherein the middle layer is arranged on the upper surface of the bottom layer, the surface layer is arranged on the upper surface of the middle layer, the bottom layer is a nickel bottom layer 2, the middle layer is a platinum plating layer 3, the surface layer comprises a palladium-nickel plating layer 4 and a hard gold layer 5 arranged on the upper surface of the palladium-nickel plating layer 4, and the lower surface of the palladium-nickel plating layer 4 is attached to the platinum plating layer 3.
Further, the nickel bottom layer is a non-porous nickel bottom layer 2. Further, the thickness of the nonporous nickel bottom layer 2 is 1.0-10.0 μm. Preferably 2.0 to 5.0 μm. The non-porous nickel has excellent corrosion resistance, and can remarkably improve the electrolytic corrosion resistance of the brine anode.
Further, the thickness of the platinum plating layer 3 is 0.25-0.5 μm. The thickness range of the electrolytic solution can be very thin, so that long brine anode electrolytic corrosion high resistance can be obtained, and the electroplating cost is also obviously reduced.
Further, the thickness of the palladium-nickel alloy plating layer 4 is 0.8-3 μm. The palladium nickel plating layer 4 has good brine anode electrolytic corrosion resistance, and the thicker the thickness, the stronger the brine anode electrolytic corrosion resistance.
Further, the thickness of the hard gold layer 5 is 0.025 to 0.25 μm. Preferably 0.05 to 0.08 μm. The hard gold layer 5 can prevent the passivation of palladium and nickel in a high-temperature application environment; and excellent wear resistance is obtained; the palladium-nickel plating layer is prevented from being directly exposed to a grinding and inserting interface, the generation of organic polymers in the processes of sliding grinding and inserting and micro-moving grinding and inserting can be minimized, and good electrical property in the long-time application process can be maintained.
Further, the surface layer also comprises a lubricating coating 6 arranged on the upper surface of the hard gold layer. The lubricating coating 6 is coated on the surface of the hard gold layer 5, so that the wear resistance can be further improved and improved, and fretting corrosion can be prevented.
Further, the corrosion-resistant palladium-nickel composite plating layer further comprises a connecting layer 7, the lower surface of the connecting layer 7 is attached to the base material, and the upper surface of the connecting layer 7 is attached to the bottom layer.
In this embodiment, the adopted substrate is a stainless steel or tungsten alloy substrate, and the connection layer 7 is a nickel connection layer. The substrate is pre-plated with the nickel connecting layer and then plated with the nickel bottom layer 2, so that the substrate layer 1 and the nickel bottom layer 2 can have good bonding force.
Example 4
The utility model provides a corrosion-resistant palladium-nickel combined plating layer, includes bottom, intermediate level and top layer, the intermediate level sets up in the upper surface of bottom, the top layer sets up in the upper surface in intermediate level, the bottom is nickel bottom 2, the intermediate level is platinum cladding material 3, the top layer includes palladium-nickel cladding material 4 and sets up in the hard gold layer 5 of palladium-nickel cladding material 4 upper surface, the lower surface and the 3 laminating of platinum cladding material of palladium-nickel cladding material 4.
Further, the nickel bottom layer is a non-porous nickel bottom layer 2. Further, the thickness of the nonporous nickel bottom layer 2 is 1.0-10.0 μm. Preferably 2.0 to 5.0 μm. The nonporous nickel bottom layer adopts a nonporous nickel layer, has excellent corrosion resistance, and can obviously improve the electrolytic corrosion resistance of the brine anode.
Further, the thickness of the platinum plating layer 3 is 0.25-0.5 μm. The thickness range is thinner, so that longer brine anode electrolytic corrosion high resistance can be obtained, and the electroplating cost is also obviously reduced.
Further, the thickness of the palladium-nickel alloy plating layer 4 is 0.8-3 μm. The palladium nickel plating layer 4 has good brine anode electrolytic corrosion resistance, and the thicker the thickness, the stronger the brine anode electrolytic corrosion resistance.
Further, the thickness of the hard gold layer 5 is 0.025 to 0.25 μm. Preferably 0.05 to 0.08 μm. The hard gold layer 5 can prevent the passivation of palladium and nickel in a high-temperature application environment; and excellent wear resistance is obtained; the palladium-nickel plating layer is prevented from being directly exposed to a grinding and inserting interface, the generation of organic polymers in the processes of sliding grinding and inserting and micro-moving grinding and inserting can be minimized, and good electrical property in the long-time application process can be maintained.
Further, the surface layer also comprises a lubricating coating 6 arranged on the upper surface of the hard gold layer. The lubricating coating 6 is coated on the surface of the hard gold layer 5, so that the wear resistance can be further improved and improved, and fretting corrosion can be prevented.
Further, the corrosion-resistant palladium-nickel composite plating layer further comprises a connecting layer 7, the lower surface of the connecting layer 7 is attached to the base material, and the upper surface of the connecting layer 7 is attached to the bottom layer.
In this embodiment, the adopted substrate is a magnesium alloy or aluminum alloy substrate, and the connection layer 7 is a zinc connection layer. During preparation, zinc dipping treatment is carried out on the base material in advance, a zinc connecting layer is formed on the surface of the base material in advance, and the nickel-plated bottom layer 2 can ensure that the base material layer 1 and the nickel bottom layer 2 have good bonding force.
Example 5
The utility model provides a corrosion-resistant palladium-nickel combined plating layer, includes bottom, intermediate level and top layer, the intermediate level sets up in the upper surface of bottom, the top layer sets up in the upper surface in intermediate level, the bottom is nickel bottom 2, the intermediate level is platinum cladding material 3, the top layer includes palladium-nickel cladding material 4 and sets up in the hard gold layer 5 of palladium-nickel cladding material 4 upper surface, the lower surface and the 3 laminating of platinum cladding material of palladium-nickel cladding material 4.
Further, the nickel bottom layer is a non-porous nickel bottom layer 2. Further, the thickness of the nonporous nickel bottom layer 2 is 1.0-10.0 μm. Preferably 2.0 to 5.0 μm. The non-porous nickel has excellent corrosion resistance, and can remarkably improve the electrolytic corrosion resistance of the brine anode.
Further, the thickness of the platinum plating layer 3 is 0.25-0.5 μm. The thickness range is thinner, so that longer brine anode electrolytic corrosion high resistance can be obtained, and the electroplating cost is also obviously reduced.
Further, the thickness of the palladium-nickel alloy plating layer 4 is 0.8-3 μm. The palladium nickel plating layer 4 has good brine anode electrolytic corrosion resistance, and the thicker the thickness, the stronger the brine anode electrolytic corrosion resistance.
Further, the thickness of the hard gold layer 5 is 0.025 to 0.25 μm. Preferably 0.05 to 0.08 μm. The hard gold layer 5 can prevent the passivation of palladium and nickel in a high-temperature application environment; and excellent wear resistance is obtained; the palladium-nickel plating layer is prevented from being directly exposed to a grinding and inserting interface, the generation of organic polymers in the processes of sliding grinding and inserting and micro-moving grinding and inserting can be minimized, and good electrical property in the long-time application process can be maintained.
Further, the surface layer also comprises a lubricating coating 6 arranged on the upper surface of the hard gold layer. The lubricating coating 6 is coated on the surface of the hard gold layer 5, so that the wear resistance can be further improved and improved, and fretting corrosion can be prevented.
Further, the corrosion-resistant palladium-nickel composite plating layer further comprises a connecting layer 7, the lower surface of the connecting layer 7 is attached to the base material, and the upper surface of the connecting layer 7 is attached to the bottom layer.
In this embodiment, the adopted base material is a zinc or zinc alloy die-casting base material, and the connection layer 7 is an alkali copper cyanide connection layer. During preparation, the base material is pre-plated with the alkali cyanide copper, the alkali cyanide copper connecting layer is pre-formed on the surface of the base material, and the nickel-plated bottom layer 2 can ensure that the base material layer 1 and the nickel bottom layer 2 have good bonding force.
The above description is only a preferred embodiment of the present invention, and for those skilled in the art, the present invention should not be limited by the description of the present invention, which should be interpreted as a limitation.
Claims (10)
1. A corrosion-resistant palladium-nickel composite plating layer is characterized in that: including bottom, intermediate level and top layer, the intermediate level sets up in the upper surface of bottom, the top layer sets up in the upper surface in intermediate level, the bottom is the nickel bottom, the intermediate level is the platinum cladding material, the top layer includes palladium nickel cladding material and sets up in the hard gold layer of palladium nickel cladding material upper surface, the lower surface and the platinum cladding material laminating of palladium nickel cladding material.
2. The corrosion-resistant palladium-nickel composite plating layer according to claim 1, wherein: the surface layer also comprises a lubricating coating arranged on the upper surface of the hard gold layer.
3. The corrosion-resistant palladium-nickel composite plating layer according to claim 1, wherein: the nickel bottom layer is a nonporous nickel bottom layer.
4. The corrosion-resistant palladium-nickel composite plating layer according to claim 3, wherein: the thickness of the nickel bottom layer is 1.0-10.0 μm.
5. The corrosion-resistant palladium-nickel composite plating layer according to claim 3, wherein: the thickness of the nickel bottom layer is 2.0-5.0 μm.
6. The corrosion-resistant palladium-nickel composite plating layer according to claim 1, wherein: the thickness of the platinum coating is 0.25-0.5 mu m.
7. The corrosion-resistant palladium-nickel composite plating layer according to claim 1, wherein: the thickness of the palladium-nickel plating layer is 0.8-3 mu m.
8. The corrosion-resistant palladium-nickel composite plating layer according to claim 1, wherein: the thickness of the hard gold layer is 0.025-0.25 μm.
9. The corrosion-resistant palladium-nickel composite plating layer according to claim 1, wherein: still include the articulamentum, the lower surface of articulamentum is used for with the substrate laminating, the upper surface and the bottom laminating of articulamentum.
10. The corrosion-resistant palladium-nickel composite plating layer according to claim 9, wherein: the connecting layer is a nickel connecting layer, a zinc connecting layer or an alkali copper cyanide connecting layer.
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