CN111411359B - Composite coating structure formed on substrate and workpiece - Google Patents

Composite coating structure formed on substrate and workpiece Download PDF

Info

Publication number
CN111411359B
CN111411359B CN201910016063.9A CN201910016063A CN111411359B CN 111411359 B CN111411359 B CN 111411359B CN 201910016063 A CN201910016063 A CN 201910016063A CN 111411359 B CN111411359 B CN 111411359B
Authority
CN
China
Prior art keywords
nickel
binary alloy
phosphorus
plating layer
coating
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
Application number
CN201910016063.9A
Other languages
Chinese (zh)
Other versions
CN111411359A (en
Inventor
张代琼
朱振宇
黄忠喜
周建坤
金继旺
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tyco Electronics Shanghai Co Ltd
Original Assignee
Tyco Electronics Shanghai Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Tyco Electronics Shanghai Co Ltd filed Critical Tyco Electronics Shanghai Co Ltd
Priority to CN201910016063.9A priority Critical patent/CN111411359B/en
Publication of CN111411359A publication Critical patent/CN111411359A/en
Application granted granted Critical
Publication of CN111411359B publication Critical patent/CN111411359B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C30/00—Coating with metallic material characterised only by the composition of the metallic material, i.e. not characterised by the coating process
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/02—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material
    • C23C28/021—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings only including layers of metallic material including at least one metal alloy layer
    • 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
    • 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
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers

Abstract

A composite plating structure formed on a substrate and a workpiece including the composite plating structure are disclosed. The composite coating structure comprises at least two nickel-phosphorus binary alloy coatings, wherein the phosphorus content in two adjacent nickel-phosphorus binary alloy coatings in the at least two nickel-phosphorus binary alloy coatings is different. In the invention, the composite coating structure has very good wear resistance and corrosion resistance, and has higher heat conduction durability and good weldability.

Description

Composite coating structure formed on substrate and workpiece
Technical Field
The present invention relates to a composite plating structure formed on a substrate of a workpiece and a workpiece having the composite plating structure.
Background
The multi-layer nickel (sulfur) plating is widely used in the industry for corrosion prevention of the plating layer with lower iron-based equipotential, and the technology is limited in that the plating layer is not wear-resistant, is not corrosion-resistant and is easy to oxidize and change color, and porous nickel and chromium are often plated on the multi-layer nickel (sulfur) plating to increase corrosion resistance and hardness, but the weldability of the chromium is poor.
The prior multilayer electroplating sulfur-containing nickel electroplating technology comprises the following steps: the corrosion prevention principle of the prior multilayer electroplating sulfur-containing nickel is that a nickel coating with low corrosion potential due to high sulfur content is used as an outermost layer, a nickel coating without sulfur and/or with low sulfur content and high corrosion potential is used as a bottom layer or an intermediate layer, and electrochemical corrosion easily occurs on a transverse low-potential coating of the outermost layer, thereby inhibiting longitudinal corrosion of a low-potential iron substrate or a bottom layer coating and the like. The limitation of the application is not suitable for wear resistance and the like, is not corrosion-resistant and is easy to oxidize and change color, and porous nickel and chromium are often plated on multiple layers of sulfur and nickel to increase corrosion resistance and hardness.
Disclosure of Invention
The present invention is directed to solving at least one of the above-mentioned problems and disadvantages of the prior art.
According to one aspect of the present invention, there is provided a composite plating layer structure formed on a substrate, the composite plating layer structure including at least two nickel-phosphorus binary alloy plating layers, the phosphorus content in adjacent two nickel-phosphorus binary alloy plating layers of the at least two nickel-phosphorus binary alloy plating layers being different.
According to an exemplary embodiment of the present invention, the composite plating structure includes a three-layer nickel-phosphorus binary alloy plating including: a first nickel-phosphorus binary alloy coating formed on the surface of the substrate; a second nickel-phosphorus binary alloy coating layer formed on the surface of the first nickel-phosphorus binary alloy coating layer; and a third nickel-phosphorus binary alloy plating layer formed on a surface of the second nickel-phosphorus binary alloy plating layer.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is 2 to 4wt%, the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is more than 10wt%, and the content of phosphorus in the third nickel-phosphorus binary alloy plating layer is 2 to 5wt%.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is 2 to 4wt%, the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is more than 10wt%, and the content of phosphorus in the third nickel-phosphorus binary alloy plating layer is 5 to 9wt%.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is 2 to 4wt%, the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is 5 to 9wt%, and the content of phosphorus in the third nickel-phosphorus binary alloy plating layer is 2 to 5wt%.
According to another exemplary embodiment of the present invention, the composite plating structure includes two nickel-phosphorus binary alloy plating layers including: a first nickel-phosphorus binary alloy coating formed on the surface of the substrate; and a second nickel-phosphorus binary alloy plating layer formed on a surface of the first nickel-phosphorus binary alloy plating layer.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is more than 10wt%, and the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is 2 to 5wt%.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is more than 10wt%, and the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is 5 to 9wt%.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is 5 to 9wt% and the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is 2 to 5wt%.
According to another exemplary embodiment of the present invention, the composite plating structure includes one nickel plating layer and two nickel-phosphorus binary alloy plating layers, the nickel plating layer being formed on a surface of a substrate; the two-layer nickel-phosphorus binary alloy coating comprises: a first nickel-phosphorus binary alloy coating formed on a surface of the nickel coating; and a second nickel-phosphorus binary alloy plating layer formed on a surface of the first nickel-phosphorus binary alloy plating layer.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is more than 10wt%, and the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is 2 to 5wt%.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is more than 10wt%, and the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is 5 to 9wt%.
According to another exemplary embodiment of the present invention, the content of phosphorus in the first nickel-phosphorus binary alloy plating layer is 5 to 9wt% and the content of phosphorus in the second nickel-phosphorus binary alloy plating layer is 2 to 5wt%.
According to another aspect of the present invention, there is provided a workpiece comprising: a substrate; and the aforementioned composite plating layer structure formed on the surface of the substrate.
According to an exemplary embodiment of the present invention, the workpiece further includes a protective agent layer formed on an outer surface of an outermost one of the plating layers of the composite plating structure.
According to another exemplary embodiment of the present invention, the substrate is a metal substrate or a non-metal substrate.
In the foregoing respective exemplary embodiments according to the present invention, a plurality of nickel-phosphorus binary alloy plating layers are formed on the base material of the workpiece, and the phosphorus content in adjacent two nickel-phosphorus binary alloy plating layers is different. The composite coating structure comprising the multi-layer nickel-phosphorus binary alloy coating has very good wear resistance and corrosion resistance, higher heat conduction durability and good weldability.
Other objects and advantages of the present invention will become apparent from the following description of the invention with reference to the accompanying drawings, which provide a thorough understanding of the present invention.
Drawings
FIG. 1 shows a schematic view of a composite plating structure formed on a substrate according to a first embodiment of the invention;
FIG. 2 shows a schematic view of a composite plating structure formed on a substrate according to a second embodiment of the invention;
FIG. 3 shows a schematic view of a composite plating structure formed on a substrate according to a third embodiment of the invention;
FIG. 4 shows a schematic view of a composite plating structure formed on a substrate according to a fourth embodiment of the invention;
FIG. 5 shows a schematic view of a composite plating structure formed on a substrate according to a fifth embodiment of the invention;
FIG. 6 shows a schematic view of a composite plating structure formed on a substrate according to a sixth embodiment of the invention;
fig. 7 shows a schematic view of a composite plating structure formed on a substrate according to a seventh embodiment of the invention;
FIG. 8 shows a schematic view of a composite plating layer structure formed on a substrate according to an eighth embodiment of the invention;
fig. 9 shows a schematic view of a composite plating structure formed on a substrate according to a ninth embodiment of the invention.
Detailed Description
The technical scheme of the invention is further specifically described below through examples and with reference to the accompanying drawings. In the specification, the same or similar reference numerals denote the same or similar components. The following description of embodiments of the present invention with reference to the accompanying drawings is intended to illustrate the general inventive concept and should not be taken as limiting the invention.
Furthermore, in the following detailed description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the embodiments of the present disclosure. It may be evident, however, that one or more embodiments may be practiced without these specific details. In other instances, well-known structures and devices are shown in the drawings in order to simplify the drawings.
According to one general technical concept of the present invention, there is provided a composite plating layer structure formed on a substrate, the composite plating layer structure including at least two nickel-phosphorus binary alloy plating layers, the contents of phosphorus in adjacent two nickel-phosphorus binary alloy plating layers of the at least two nickel-phosphorus binary alloy plating layers being different.
First embodiment
Fig. 1 shows a schematic view of a composite plating structure formed on a substrate according to a first embodiment of the present invention.
As shown in fig. 1, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 100 and a composite plating structure formed on a surface of the substrate 100.
As shown in fig. 1, in the illustrated embodiment, the foregoing composite plating structure includes three nickel-phosphorus binary alloy plating layers 110, 120, 130, and the three nickel-phosphorus binary alloy plating layers 110, 120, 130 include: a first nickel-phosphorus binary alloy plating layer 110 formed on the surface of the substrate 100; a second nickel-phosphorus binary alloy plating layer 120 formed on a surface of the first nickel-phosphorus binary alloy plating layer 110; and a third nickel-phosphorus binary alloy plating layer 130 formed on a surface of the second nickel-phosphorus binary alloy plating layer 120.
As shown in fig. 1, in the illustrated embodiment, the first nickel-phosphorous binary alloy coating 110 has a phosphorous content of 2-4 wt%, the second nickel-phosphorous binary alloy coating 120 has a phosphorous content of greater than 10wt%, and the third nickel-phosphorous binary alloy coating 130 has a phosphorous content of 2-5 wt%.
As shown in fig. 1, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy plating layer 110 and the second nickel phosphorus binary alloy plating layer 120 are different; the second nickel-phosphorus binary alloy plating layer 120 and the third nickel-phosphorus binary alloy plating layer 130 differ in the phosphorus content. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 1, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy coating may exhibit different corrosion potential differences, and thus, electrochemical corrosion tendencies preferentially occur between the multi-layered nickel-phosphorus binary alloy coatings 110, 120, 130 or on the outermost nickel-phosphorus binary alloy coating 130 having a smaller potential. In this way, electrochemical corrosion does not occur on the substrate 100 first, and the substrate 100 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is generally 480-700 HV, and can reach 800HV after heat hardening, which is very similar to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 1, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 110 with a phosphorus content of 2-4 wt% is used as a bottom plating layer of the composite plating layer structure, the first nickel-phosphorus binary alloy plating layer 110 may be formed on the surface of the substrate 100 in an alkaline electroless plating manner at room temperature, and the thickness of the first nickel-phosphorus binary alloy plating layer 110 is about 0.5um for increasing the bonding force between the plating layer and the substrate.
As shown in fig. 1, in the illustrated embodiment, the second nickel-phosphorus binary alloy plating layer 120 with a phosphorus content greater than 10wt% is used as an intermediate plating layer of the composite plating layer structure, and is mainly used for improving stress and corrosion resistance, and the thickness is determined according to practical applications, for example, the thickness can be 2-4um when the application is generally performed indoors, the thickness can be 4-10um when the application is performed indoors, the thickness can be greater than 10um when the application is performed outdoors, the application is performed industrially, automobile, etc., and the thickness can be greater than 20um when the application is performed by navigation aviation military industry, etc.
As shown in fig. 1, in the illustrated embodiment, a third nickel-phosphorus binary alloy plating layer 130 having a phosphorus content of 2 to 5wt% is used as an outermost plating layer of the composite plating structure for improving the wear resistance and solderability of the plating layer. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 1, in the illustrated embodiment, a nano-scale protective agent layer 140 may be selectively coated on the outer surface of the outermost plating layer (the third nickel-phosphorus binary alloy plating layer 130 in fig. 1) of the composite plating structure according to various applications, and the protective agent layer 140 may serve as lubrication, high temperature resistance, oxidation resistance, soldering aid, etc.
As shown in fig. 1, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 110 having a phosphorus content of 2 to 4wt% and the third nickel-phosphorus binary alloy plating layer 130 having a phosphorus content of 2 to 5wt% have a low heat hardening temperature, and may be heat-treated at a low temperature of about 200 ℃ in a vacuum environment to further increase the hardness and bonding force with a substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Second embodiment
Fig. 2 shows a schematic view of a composite plating structure formed on a substrate according to a second embodiment of the present invention.
As shown in fig. 2, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 200 and a composite plating structure formed on a surface of the substrate 200.
As shown in fig. 2, in the illustrated embodiment, the foregoing composite plating structure includes three nickel-phosphorus binary alloy plating layers 210, 220, 230, and the three nickel-phosphorus binary alloy plating layers 210, 220, 230 include: a first nickel-phosphorus binary alloy plating layer 210 formed on the surface of the substrate 200; a second nickel-phosphorus binary alloy plating layer 220 formed on a surface of the first nickel-phosphorus binary alloy plating layer 210; and a third nickel-phosphorus binary alloy plating layer 230 formed on a surface of the second nickel-phosphorus binary alloy plating layer 220.
As shown in fig. 2, in the illustrated embodiment, the first nickel-phosphorous binary alloy coating 210 has a phosphorous content of 2-4 wt%, the second nickel-phosphorous binary alloy coating 220 has a phosphorous content of greater than 10wt%, and the third nickel-phosphorous binary alloy coating 230 has a phosphorous content of 5-9 wt%.
As shown in fig. 2, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy plating layer 210 and the second nickel phosphorus binary alloy plating layer 220 are different; the second nickel-phosphorus binary alloy plating layer 220 and the third nickel-phosphorus binary alloy plating layer 230 differ in the phosphorus content. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 2, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy coating may exhibit different corrosion potential differences, and thus, electrochemical corrosion tendencies preferentially occur between the multi-layered nickel-phosphorus binary alloy coatings 210, 220, 230 or on the outermost nickel-phosphorus binary alloy coating 230 having a smaller potential. Thus, electrochemical corrosion does not occur on the substrate 200, and thus the substrate 200 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is generally 480-700 HV, and can reach 800HV after heat hardening, which is very similar to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 2, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 210 having a phosphorus content of 2 to 4wt% is used as a bottom plating layer of the composite plating structure, the first nickel-phosphorus binary alloy plating layer 210 may be formed on the surface of the substrate 200 in an alkaline electroless plating manner at room temperature, and the thickness of the first nickel-phosphorus binary alloy plating layer 210 is about 0.5um for increasing the bonding force between the plating layer and the substrate.
As shown in fig. 2, in the illustrated embodiment, the second nickel-phosphorus binary alloy plating layer 220 with a phosphorus content greater than 10wt% is used as an intermediate plating layer of the composite plating layer structure, and is mainly used for improving stress and corrosion resistance, and the thickness depends on practical applications, for example, the thickness may be 2-4um when the application is generally performed indoors, the thickness may be 4-10um when the application is performed indoors, the thickness may be greater than 10um when the application is performed outdoors, the application is performed industrially, automobile, etc., and the thickness may be greater than 20um when the application is performed by navigation aviation military.
As shown in fig. 2, in the illustrated embodiment, a third nickel-phosphorus binary alloy plating layer 230 having a phosphorus content of 5 to 9wt% is used as an outermost plating layer of the composite plating structure for improving the wear resistance and solderability of the plating layer. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 2, in the illustrated embodiment, a nano-scale protective agent layer 240 may be selectively coated on the outer surface of the outermost plating layer (the third nickel-phosphorus binary alloy plating layer 230 in fig. 2) of the composite plating structure according to various applications, and the protective agent layer 240 may play roles of lubrication, high temperature resistance, oxidation resistance, soldering, etc.
As shown in fig. 2, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 210 having a phosphorus content of 2 to 4wt% and the third nickel-phosphorus binary alloy plating layer 230 having a phosphorus content of 5 to 9wt% have a low heat hardening temperature, and may be heat-treated at a low temperature of about 200 ℃ in a vacuum environment to further increase the hardness and bonding force with a substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Third embodiment
Fig. 3 shows a schematic view of a composite plating structure formed on a substrate according to a third embodiment of the present invention.
As shown in fig. 3, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 300 and a composite plating structure formed on a surface of the substrate 300.
As shown in fig. 3, in the illustrated embodiment, the foregoing composite plating structure includes three nickel-phosphorus binary alloy plating layers 310, 320, 330, the three nickel-phosphorus binary alloy plating layers 310, 320, 330 including: a first nickel-phosphorus binary alloy plating layer 310 formed on the surface of the substrate 300; a second nickel-phosphorus binary alloy plating layer 320 formed on a surface of the first nickel-phosphorus binary alloy plating layer 310; and a third nickel-phosphorus binary alloy plating layer 330 formed on a surface of the second nickel-phosphorus binary alloy plating layer 320.
As shown in fig. 3, in the illustrated embodiment, the content of phosphorus in the first nickel-phosphorus binary alloy coating 310 is 2 to 4wt%, the content of phosphorus in the second nickel-phosphorus binary alloy coating 320 is 5 to 9wt%, and the content of phosphorus in the third nickel-phosphorus binary alloy coating 330 is 2 to 5wt%.
As shown in fig. 3, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy plating layer 310 and the second nickel phosphorus binary alloy plating layer 320 are different; the second nickel-phosphorus binary alloy plating layer 320 and the third nickel-phosphorus binary alloy plating layer 330 differ in the phosphorus content. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 3, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy coating may exhibit different corrosion potential differences, and thus, electrochemical corrosion tendencies preferentially occur between the multi-layered nickel-phosphorus binary alloy coatings 310, 320, 330 or on the outermost nickel-phosphorus binary alloy coating 330 having a smaller potential. Thus, electrochemical corrosion does not occur on the substrate 300, and thus the substrate 300 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is generally 480-700 HV, and can reach 800HV after heat hardening, which is very similar to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 3, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 310 having a phosphorus content of 2 to 4wt% is used as a bottom plating layer of the composite plating structure, the first nickel-phosphorus binary alloy plating layer 310 may be formed on the surface of the substrate 300 in an alkaline electroless plating manner at room temperature, and the thickness of the first nickel-phosphorus binary alloy plating layer 310 is about 0.5um for increasing the bonding force of the plating layer with the substrate.
As shown in fig. 3, in the illustrated embodiment, the second nickel-phosphorus binary alloy plating layer 320 with a phosphorus content of 5-9 wt% is used as an intermediate plating layer of the composite plating layer structure, and is mainly used for improving stress and corrosion resistance, and the thickness is determined according to practical applications, for example, the thickness can be 2-4um when the application is generally performed indoors, the thickness can be 4-10um when the application is performed indoors, the thickness can be more than 10um when the application is performed outdoors, the application is performed industrially, automobile, etc., and the thickness can be more than 20um when the application is performed by navigation aviation military.
As shown in fig. 3, in the illustrated embodiment, a third nickel-phosphorus binary alloy plating layer 330 having a phosphorus content of 2 to 5wt% is used as an outermost plating layer of the composite plating structure for improving the wear resistance and solderability of the plating layer. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 3, in the illustrated embodiment, a nano-scale protective agent layer 340 may be selectively coated on the outer surface of the outermost plating layer (the third nickel-phosphorus binary alloy plating layer 330 in fig. 3) of the composite plating structure according to various applications, and the protective agent layer 340 may play roles of lubrication, high temperature resistance, oxidation resistance, soldering, etc.
As shown in fig. 3, in the illustrated embodiment, the heat hardening temperature of the first nickel-phosphorous binary alloy coating 310 having a phosphorous content of 2 to 4wt%, the second nickel-phosphorous binary alloy coating 320 having a phosphorous content of 5 to 9wt% and the third nickel-phosphorous binary alloy coating 330 having a phosphorous content of 2 to 5wt% is low, and it is possible to heat treat it at a low temperature of about 200 ℃ in a vacuum environment to further increase the hardness and bonding force with a substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Fourth embodiment
Fig. 4 shows a schematic view of a composite plating structure formed on a substrate according to a fourth embodiment of the present invention.
As shown in fig. 4, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 400 and a composite plating structure formed on a surface of the substrate 400.
As shown in fig. 4, in the illustrated embodiment, the foregoing composite plating structure includes two nickel-phosphorus binary alloy plating layers 410, 420. The two nickel-phosphorus binary alloy plating layers 410, 420 include: a first nickel-phosphorus binary alloy plating layer 410 formed on the surface of the substrate 400; and a second nickel-phosphorus binary alloy plating layer 420 formed on a surface of the first nickel-phosphorus binary alloy plating layer 410.
As shown in fig. 4, in the illustrated embodiment, the phosphorus content of the first nickel-phosphorus binary alloy coating 410 is greater than 10wt% and the phosphorus content of the second nickel-phosphorus binary alloy coating 420 is 2-5 wt%.
As shown in fig. 4, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy coating 410 and the second nickel phosphorus binary alloy coating 420 are different. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 4, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy coating may exhibit different corrosion potential differences, and thus electrochemical corrosion tendencies preferentially occur between the multi-layered nickel-phosphorus binary alloy coatings 410, 420 or on the nickel-phosphorus binary alloy coating 420 having the outermost layer of smaller potential. Thus, electrochemical corrosion does not occur on the substrate 400, and thus the substrate 400 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is generally 480-700 HV, and can reach 800HV after heat hardening, which is very similar to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 4, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 410 with a phosphorus content greater than 10wt% is used as a bottom plating layer of the composite plating layer structure, and is mainly used for improving stress and corrosion resistance, and the thickness is determined according to practical applications, for example, the thickness can be 2-4um when the indoor electronic application is performed, the thickness can be 4-10um when the indoor electronic application is performed, the thickness can be greater than 10um when the outdoor electronic application is performed, the industrial application is performed, the automotive application is performed, and the thickness can be greater than 20um when the marine aviation military application is performed.
As shown in fig. 4, in the illustrated embodiment, a second nickel-phosphorus binary alloy plating layer 420 having a phosphorus content of 2 to 5wt% is used as the outermost plating layer of the composite plating structure for improving the wear resistance and solderability of the plating layer. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 4, in the illustrated embodiment, a nano-scale protective agent layer 430 may be selectively coated on the outer surface of the outermost plating layer (the second nickel-phosphorus binary alloy plating layer 420 in fig. 4) of the composite plating structure according to various applications, and the protective agent layer 430 may serve as lubrication, high temperature resistance, oxidation resistance, soldering aid, etc.
As shown in fig. 4, in the illustrated embodiment, the second nickel-phosphorus binary alloy plating layer 420 having a phosphorus content of 2-5 wt% has a low heat hardening temperature, and may be heat treated at a low temperature of about 200 ℃ in a vacuum environment to further increase its hardness and bonding force with a substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Fifth embodiment
Fig. 5 shows a schematic view of a composite plating structure formed on a substrate according to a fifth embodiment of the present invention.
As shown in fig. 5, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 500 and a composite plating structure formed on a surface of the substrate 500.
As shown in fig. 5, in the illustrated embodiment, the foregoing composite plating structure includes two nickel-phosphorus binary alloy plating layers 510, 520. The two nickel-phosphorus binary alloy coatings 510, 520 include: a first nickel-phosphorus binary alloy plating layer 510 formed on the surface of the substrate 500; and a second nickel-phosphorus binary alloy plating layer 520 formed on a surface of the first nickel-phosphorus binary alloy plating layer 510.
As shown in fig. 5, in the illustrated embodiment, the phosphorus content in the first nickel-phosphorus binary alloy coating 510 is greater than 10wt% and the phosphorus content in the second nickel-phosphorus binary alloy coating 520 is 5-9 wt%.
As shown in fig. 5, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy coating 510 and the second nickel phosphorus binary alloy coating 520 are different. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 5, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy coating may exhibit different corrosion potential differences, and thus electrochemical corrosion tendencies preferentially occur between the multi-layered nickel-phosphorus binary alloy coatings 510, 520 or on the outermost nickel-phosphorus binary alloy coating 520 having a smaller potential. In this way, electrochemical corrosion does not occur on the substrate 500 first, and thus the substrate 500 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is generally 480-700 HV, and can reach 800HV after heat hardening, which is very similar to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 5, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 510 with a phosphorus content greater than 10wt% is used as a bottom plating layer of the composite plating layer structure, and is mainly used for improving stress and corrosion resistance, and the thickness is determined according to practical applications, for example, the thickness can be 2-4um when the indoor electronic application is performed, the thickness can be 4-10um when the indoor electronic application is performed, the thickness can be greater than 10um when the outdoor electronic application is performed, the industrial application is performed, the automotive application is performed, and the thickness can be greater than 20um when the marine aviation military application is performed.
As shown in fig. 5, in the illustrated embodiment, a second nickel-phosphorus binary alloy coating 520 having a phosphorus content of 5 to 9wt% is used as the outermost coating of the composite coating structure for improving the wear resistance and solderability of the coating. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 5, in the illustrated embodiment, a nano-scale protective agent layer 530 may be selectively coated on the outer surface of the outermost plating layer (the second nickel-phosphorus binary alloy plating layer 520 in fig. 5) of the composite plating structure according to various applications, and the protective agent layer 530 may serve as lubrication, high temperature resistance, oxidation resistance, soldering aid, etc.
As shown in fig. 5, in the illustrated embodiment, the second nickel-phosphorus binary alloy coating 520 having a phosphorus content of 5 to 9wt% has a low heat hardening temperature, and may be heat treated at a low temperature of about 200 ℃ in a vacuum environment to further increase the hardness and bonding force with the substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Seventh embodiment
Fig. 7 shows a schematic view of a composite plating structure formed on a substrate according to a seventh embodiment of the present invention.
As shown in fig. 7, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 700 and a composite plating structure formed on a surface of the substrate 700.
As shown in fig. 7, in the illustrated embodiment, the aforementioned composite plating structure includes one nickel plating layer 710 and two nickel-phosphorus binary alloy plating layers 720, 730. A nickel plating layer 710 is formed on the surface of the substrate 400.
As shown in fig. 7, in the illustrated embodiment, the two nickel-phosphorus binary alloy plating layers 720, 730 include: a first nickel-phosphorus binary alloy plating layer 720 formed on the surface of the nickel plating layer 710; and a second nickel-phosphorus binary alloy plating layer 730 formed on a surface of the first nickel-phosphorus binary alloy plating layer 720.
As shown in fig. 7, in the illustrated embodiment, the content of phosphorus in the first nickel-phosphorus binary alloy coating 720 is greater than 10wt%, and the content of phosphorus in the second nickel-phosphorus binary alloy coating 730 is 2 to 5wt%.
As shown in fig. 7, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy coating 720 and the second nickel phosphorus binary alloy coating 730 are different. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 7, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy coating may exhibit different corrosion potential differences, and thus electrochemical corrosion tendencies preferentially occur between the multi-layered nickel-phosphorus binary alloy coatings 720, 730 or on the nickel-phosphorus binary alloy coating 730 having the outermost layer of smaller potential. In this way, electrochemical corrosion does not occur on the substrate 700 first, and thus the substrate 700 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is generally 480-700 HV, and can reach 800HV after heat hardening, which is very similar to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 7, in the illustrated embodiment, the nickel plating layer 710 is used as the bottom plating layer of the composite plating structure, and the thickness of the nickel plating layer 710 is about 0.5um for increasing the bonding force between the plating layer and the substrate.
As shown in fig. 7, in the illustrated embodiment, the first nickel-phosphorus binary alloy coating 720 with a phosphorus content greater than 10wt% is used as an intermediate coating of the composite coating structure, and is mainly used for improving stress and corrosion resistance, and the thickness is determined according to practical applications, for example, the thickness can be 2-4um when the indoor electronic application is performed, the thickness can be 4-10um when the indoor electronic application is performed, the thickness can be greater than 10um when the outdoor electronic application is performed, the industrial application is performed, the automotive application is performed, and the thickness can be greater than 20um when the marine aviation military application is performed.
As shown in fig. 7, in the illustrated embodiment, a second nickel-phosphorus binary alloy plating layer 730 having a phosphorus content of 2 to 5wt% is used as the outermost plating layer of the composite plating structure for improving the wear resistance and solderability of the plating layer. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 7, in the illustrated embodiment, a nano-scale protective agent layer 740 may be selectively coated on the outer surface of the outermost plating layer (the second nickel-phosphorus binary alloy plating layer 730 in fig. 7) of the composite plating structure according to various applications, and the protective agent layer 740 may serve as lubrication, high temperature resistance, oxidation resistance, soldering aid, etc.
As shown in fig. 7, in the illustrated embodiment, the second nickel-phosphorus binary alloy coating 730 having a phosphorus content of 2 to 5wt% has a low heat hardening temperature, and may be heat treated at a low temperature of about 200 ℃ in a vacuum environment to further increase its hardness and bonding force with a substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Eighth embodiment
Fig. 8 shows a schematic view of a composite plating structure formed on a substrate according to an eighth embodiment of the present invention.
As shown in fig. 8, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 800 and a composite plating structure formed on a surface of the substrate 800.
As shown in fig. 8, in the illustrated embodiment, the foregoing composite plating structure includes one nickel plating layer 810 and two nickel-phosphorus binary alloy plating layers 820, 830. A nickel plating layer 810 is formed on the surface of the substrate 400.
As shown in fig. 8, in the illustrated embodiment, the two nickel-phosphorus binary alloy plating layers 820, 830 include: a first nickel-phosphorus binary alloy plating layer 820 formed on the surface of the nickel plating layer 810; and a second nickel-phosphorus binary alloy plating layer 830 formed on a surface of the first nickel-phosphorus binary alloy plating layer 820.
As shown in FIG. 8, in the illustrated embodiment, the phosphorus content of the first nickel-phosphorus binary alloy coating 820 is greater than 10wt% and the phosphorus content of the second nickel-phosphorus binary alloy coating 830 is between 5 and 9wt%.
As shown in fig. 8, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy plating layer 820 and the second nickel phosphorus binary alloy plating layer 830 is different. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 8, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy coating may exhibit different corrosion potential differences, and thus electrochemical corrosion tendencies preferentially occur between the multi-layered nickel-phosphorus binary alloy coatings 820, 830 or on the outermost nickel-phosphorus binary alloy coating 830 having a smaller potential. Thus, electrochemical corrosion does not occur on the substrate 800, and the substrate 800 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is generally 480HV-800HV, and can reach 800HV after heat hardening, which is very similar to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 8, in the illustrated embodiment, the nickel plating layer 810 is used as the bottom plating layer of the composite plating layer structure, and the thickness of the nickel plating layer 810 is about 0.5um, so as to increase the bonding force between the plating layer and the substrate.
As shown in fig. 8, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 820 with a phosphorus content greater than 10wt% is used as an intermediate plating layer of the composite plating layer structure, and is mainly used for improving stress and corrosion resistance, and the thickness is determined according to practical applications, for example, the thickness can be 2-4um when the indoor electronic application is performed, the thickness can be 4-10um when the indoor electronic application is performed, the thickness can be greater than 10um when the outdoor electronic application is performed, the industrial application is performed, the automotive application is performed, and the thickness can be greater than 20um when the marine aviation military application is performed.
As shown in fig. 8, in the illustrated embodiment, a second nickel-phosphorus binary alloy plating layer 830 having a phosphorus content of 5 to 9wt% is used as the outermost plating layer of the composite plating structure for improving the wear resistance and solderability of the plating layer. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 8, in the illustrated embodiment, a nano-scale protective agent layer 840 may be selectively coated on the outer surface of the outermost plating layer (the second nickel-phosphorus binary alloy plating layer 830 in fig. 8) of the composite plating structure according to various applications, and the protective agent layer 840 may play roles of lubrication, high temperature resistance, oxidation resistance, soldering, etc.
As shown in fig. 8, in the illustrated embodiment, the second nickel-phosphorus binary alloy coating 830 having a phosphorus content of 5-9 wt% has a low heat hardening temperature, and may be heat treated at a low temperature of about 200 c in a vacuum environment to further increase its hardness and bonding force with a substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Ninth embodiment
Fig. 9 shows a schematic view of a composite plating structure formed on a substrate according to a ninth embodiment of the invention.
As shown in fig. 9, in the illustrated embodiment, a workpiece, e.g., a terminal member, is disclosed. The workpiece includes a substrate 900 and a composite plating structure formed on a surface of the substrate 900.
As shown in fig. 9, in the illustrated embodiment, the aforementioned composite plating structure includes one nickel plating layer 910 and two nickel-phosphorus binary alloy plating layers 920, 930. A nickel plating layer 910 is formed on the surface of the substrate 400.
As shown in fig. 9, in the illustrated embodiment, the two nickel-phosphorus binary alloy plating layers 920, 930 include: a first nickel-phosphorus binary alloy plating layer 920 formed on the surface of the nickel plating layer 910; and a second nickel-phosphorus binary alloy plating layer 930 formed on a surface of the first nickel-phosphorus binary alloy plating layer 920.
As shown in fig. 9, in the illustrated embodiment, the phosphorus content in the first nickel-phosphorus binary alloy plating layer 920 is 5-9 wt% and the phosphorus content in the second nickel-phosphorus binary alloy plating layer 930 is 2-5 wt%.
As shown in fig. 9, in the illustrated embodiment, the phosphorus content in the first nickel phosphorus binary alloy plating layer 920 and the second nickel phosphorus binary alloy plating layer 930 are different. That is, the phosphorus content in the adjacent two nickel-phosphorus binary alloy coatings is different.
As shown in fig. 9, in the illustrated embodiment, the different amounts of phosphorus in the nickel-phosphorus binary alloy plating layers may exhibit different corrosion potential differences, and thus electrochemical corrosion tendencies preferentially occur between the multi-layer nickel-phosphorus binary alloy plating layers 920, 930 or on the nickel-phosphorus binary alloy plating layer 930 having the outermost layer of smaller potential. In this way, electrochemical corrosion does not occur on the substrate 900 first, and the substrate 900 can be effectively protected.
The electrochemical corrosion potential of the nickel-phosphorus binary alloy plating layer in the invention is usually 0.6V-1.6V, while the electrochemical corrosion potential of the sulfur-nickel binary alloy plating layer in the prior art is usually 0.3V-0.5V. Therefore, the electrochemical corrosion potential of the nickel-phosphorus binary alloy coating is far higher than that of the sulfur-nickel binary alloy coating in the prior art, so that the composite coating structure has better corrosion resistance and does not need to add a chromium coating on the outermost surface.
The hardness of the nickel-phosphorus binary alloy plating layer in the invention is usually 480-900 HV, and can reach 900HV after heat hardening, which is very close to the hardness of chromium. Whereas the hardness of the prior art sulfur-nickel binary alloy plating is usually only 350HV-450HV, in order to increase the surface hardness, it is necessary to add a chromium plating on the outermost surface in the prior art. However, the welding performance of the chromium plating layer is not good, and the nickel-phosphorus binary alloy plating layer in the invention has good weldability.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has better wear resistance and corrosion resistance, higher heat conduction durability and better weldability. Although the production efficiency of the multi-layer nickel-phosphorus binary alloy coating is lower and the cost is high, the multi-layer sulfur-nickel binary alloy coating can only be prepared by electroplating, and the multi-layer nickel-phosphorus binary alloy coating can be prepared by electroplating or chemical plating. Therefore, the multi-layer nickel-phosphorus binary alloy plating layer can be electroplated on non-metal, magnesium-aluminum alloy and base materials with high dimensional accuracy requirements which are not easy to plate.
As shown in fig. 9, in the illustrated embodiment, the nickel plating layer 910 is used as the bottom plating layer of the composite plating structure, and the thickness of the nickel plating layer 910 is about 0.5um, so as to increase the bonding force between the plating layer and the substrate.
As shown in fig. 9, in the illustrated embodiment, the first nickel-phosphorus binary alloy plating layer 920 with a phosphorus content of 5-9 wt% is used as an intermediate plating layer of the composite plating layer structure, and is mainly used for improving stress and corrosion resistance, and the thickness is determined according to practical applications, for example, the thickness can be 2-4um when the indoor electronic application is performed, the thickness can be 4-10um when the indoor electronic application is performed, the thickness can be more than 10um when the outdoor electronic application is performed, the industrial application is performed, the automotive application is performed, and the thickness can be more than 20um when the marine aviation military application is performed.
As shown in fig. 9, in the illustrated embodiment, a second nickel-phosphorus binary alloy plating 930 having a phosphorus content of 2 to 5wt% is used as the outermost plating layer of the composite plating structure for improving the wear resistance and solderability of the plating. The thickness is practical, for example, the thickness can be greater than 4um for wear resistance and 1-2um for solderability.
As shown in fig. 9, in the illustrated embodiment, a nano-scale protective agent layer 940 may be selectively coated on the outer surface of the outermost plating layer (the second nickel-phosphorus binary alloy plating layer 930 in fig. 9) of the composite plating structure according to various applications, and the protective agent layer 940 may serve as lubrication, high temperature resistance, oxidation resistance, soldering assistance, and the like.
As shown in fig. 9, in the illustrated embodiment, the heat hardening temperature of the first nickel-phosphorus binary alloy plating layer 920 having a phosphorus content of 5 to 9wt% and the second nickel-phosphorus binary alloy plating layer 930 having a phosphorus content of 2 to 5wt% is low, and it is possible to heat treat them at a relatively low temperature of about 200 ℃ in a vacuum environment to further increase the hardness and bonding force with the substrate. In the present invention, since the temperature of the thermosetting is low, the base material is not adversely affected during the thermosetting.
Compared with the existing composite coating structure with the multi-layer sulfur-nickel binary alloy coating, the composite coating structure with the multi-layer nickel-phosphorus binary alloy coating has higher surface hardness and better corrosion resistance, and can be electroplated and chemically plated, so that the composite coating structure can be formed on a metal substrate (such as an iron substrate, an aluminum substrate, a copper substrate, a magnesium-aluminum alloy substrate and the like) in an electroplating manner or can be formed on a non-metal substrate (such as a plastic substrate and a ceramic substrate) in an electroless plating manner.
Those skilled in the art will appreciate that the embodiments described above are exemplary and that modifications may be made by those skilled in the art, and that the structures described in the various embodiments may be freely combined without conflict in terms of structure or principle.
Although the present invention has been described with reference to the accompanying drawings, the examples disclosed in the drawings are intended to illustrate preferred embodiments of the invention and are not to be construed as limiting the invention.
Although a few embodiments of the present general inventive concept have been shown and described, it would be appreciated by those skilled in the art that changes may be made in these embodiments without departing from the principles and spirit of the general inventive concept, the scope of which is defined in the claims and their equivalents.
It should be noted that the word "comprising" does not exclude other elements or steps, and the word "a" or "an" does not exclude a plurality. In addition, any reference signs in the claims shall not be construed as limiting the scope of the invention.

Claims (6)

1. A composite coating structure formed on a substrate, characterized by:
the composite coating structure comprises three nickel-phosphorus binary alloy coatings,
the three-layer nickel-phosphorus binary alloy coating comprises:
a first nickel-phosphorus binary alloy plating layer (110) for forming on a surface of the substrate (100) as an underlying plating layer of the composite plating layer structure;
a second nickel-phosphorus binary alloy plating layer (120) formed as an intermediate plating layer of the composite plating layer structure on a surface of the first nickel-phosphorus binary alloy plating layer (110); and
A third nickel-phosphorus binary alloy plating layer (130) formed on a surface of the second nickel-phosphorus binary alloy plating layer (120),
the phosphorus content in two adjacent nickel-phosphorus binary alloy coatings in the three layers of nickel-phosphorus binary alloy coatings is different, the phosphorus content of the first nickel-phosphorus binary alloy coating is smaller than that of the second nickel-phosphorus binary alloy coating,
the content of phosphorus in the first nickel-phosphorus binary alloy coating (110) is 2-4wt%, the content of phosphorus in the second nickel-phosphorus binary alloy coating (120) is more than 10wt%, the content of phosphorus in the third nickel-phosphorus binary alloy coating (130) is 2-5wt%, and
the first nickel-phosphorus binary alloy coating and the third nickel-phosphorus binary alloy coating are adapted to be heat treated in a vacuum environment at a temperature of around 200 ℃.
2. A composite coating structure formed on a substrate, characterized by:
the composite coating structure comprises three nickel-phosphorus binary alloy coatings,
the three-layer nickel-phosphorus binary alloy coating comprises:
a first nickel-phosphorus binary alloy coating layer for forming on the surface of the substrate as an underlying coating layer of the composite coating structure;
a second nickel-phosphorus binary alloy plating layer formed as an intermediate plating layer of the composite plating layer structure on a surface of the first nickel-phosphorus binary alloy plating layer; and
A third nickel-phosphorus binary alloy plating layer formed on a surface of the second nickel-phosphorus binary alloy plating layer,
the phosphorus content in two adjacent nickel-phosphorus binary alloy coatings in the three layers of nickel-phosphorus binary alloy coatings is different, the phosphorus content of the first nickel-phosphorus binary alloy coating is smaller than that of the second nickel-phosphorus binary alloy coating,
the content of phosphorus in the first nickel-phosphorus binary alloy coating is 2-4wt%, the content of phosphorus in the second nickel-phosphorus binary alloy coating is more than 10wt%, the content of phosphorus in the third nickel-phosphorus binary alloy coating is 5-9wt%,
the first nickel-phosphorus binary alloy coating and the third nickel-phosphorus binary alloy coating are adapted to be heat treated in a vacuum environment at a temperature of around 200 ℃.
3. A composite coating structure formed on a substrate, characterized by:
the composite coating structure comprises three nickel-phosphorus binary alloy coatings,
the three-layer nickel-phosphorus binary alloy coating comprises:
a first nickel-phosphorus binary alloy coating layer for forming on the surface of the substrate as an underlying coating layer of the composite coating structure;
a second nickel-phosphorus binary alloy plating layer formed as an intermediate plating layer of the composite plating layer structure on a surface of the first nickel-phosphorus binary alloy plating layer; and
A third nickel-phosphorus binary alloy plating layer formed on a surface of the second nickel-phosphorus binary alloy plating layer,
the phosphorus content in two adjacent nickel-phosphorus binary alloy coatings in the three layers of nickel-phosphorus binary alloy coatings is different, the phosphorus content of the first nickel-phosphorus binary alloy coating is smaller than that of the second nickel-phosphorus binary alloy coating,
the content of phosphorus in the first nickel-phosphorus binary alloy coating is 2-4wt%, the content of phosphorus in the second nickel-phosphorus binary alloy coating is 5-9wt%, the content of phosphorus in the third nickel-phosphorus binary alloy coating is 2-5wt%,
the first nickel-phosphorus binary alloy coating, the second nickel-phosphorus binary alloy coating, and the third nickel-phosphorus binary alloy coating are adapted to be heat treated in a vacuum environment at a temperature of about 200 ℃.
4. A workpiece, comprising:
a base material (100); and
a composite plating layer structure formed on the surface of the substrate (100),
the method is characterized in that:
the composite plating structure is a composite plating structure according to any one of claims 1 to 3, in which a first nickel-phosphorus binary alloy plating layer is formed on a surface of the substrate (100).
5. The workpiece according to claim 4, wherein:
The workpiece further includes a protective agent layer (140) formed on an outer surface of an outermost one of the plating layers of the composite plating structure.
6. The workpiece according to claim 5, characterized in that: the substrate (100) is a metal substrate or a non-metal substrate.
CN201910016063.9A 2019-01-08 2019-01-08 Composite coating structure formed on substrate and workpiece Active CN111411359B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201910016063.9A CN111411359B (en) 2019-01-08 2019-01-08 Composite coating structure formed on substrate and workpiece

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201910016063.9A CN111411359B (en) 2019-01-08 2019-01-08 Composite coating structure formed on substrate and workpiece

Publications (2)

Publication Number Publication Date
CN111411359A CN111411359A (en) 2020-07-14
CN111411359B true CN111411359B (en) 2023-10-24

Family

ID=71488786

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201910016063.9A Active CN111411359B (en) 2019-01-08 2019-01-08 Composite coating structure formed on substrate and workpiece

Country Status (1)

Country Link
CN (1) CN111411359B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111394716A (en) * 2019-01-03 2020-07-10 泰科电子(上海)有限公司 Multi-coating stacked structure, preparation method and application thereof

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104264091A (en) * 2014-09-25 2015-01-07 芜湖海成科技有限公司 Guide plate for charge and discharge system and preparation method of guide plate

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104264091A (en) * 2014-09-25 2015-01-07 芜湖海成科技有限公司 Guide plate for charge and discharge system and preparation method of guide plate

Also Published As

Publication number Publication date
CN111411359A (en) 2020-07-14

Similar Documents

Publication Publication Date Title
US6397896B2 (en) Heat and corrosion resistant steel pipe having multi-layered coating
MY151913A (en) Surface-treated copper foil, surface-treated copper foil with very thin primer resin layer, method for manufacturing the surface-treated copper foil, and method for manufacturing the surface-treated copper foil with very thin primer resin layer
MX2020005505A (en) Fe-Al PLATED HOT-STAMPED MEMBER AND METHOD FOR PRODUCING Fe-Al PLATED HOT-STAMPED MEMBER.
CN111411359B (en) Composite coating structure formed on substrate and workpiece
KR20130014507A (en) Fastening means and associated production method
EP1850031B1 (en) Corrosion resistant roller chain
CN101341273A (en) Steel pipe for automobile piping
WO2004009871A1 (en) Multilayer plated fuel line parts for automobile
WO2003029520A1 (en) Corrosion-resistant coating structure containing no 6-valent chromium which has resin layer and metal layer excellent in adhesion to resin layer
GB2173424A (en) Anticorrosive coated steel pipe
JPS6196279A (en) Metallic pipe to which corrosion-preventive coating is executed and manufacture thereof
KR20150009988A (en) Pipe having heat-resistant corrosion-resistant plating layer that has excellent processability
JP2008001930A (en) Metal surface treatment method
EP2119812A1 (en) Composite material for electric and electronic components, electric and electronic components, and method for manufacturing composite material for electric and electronic components
JPH0494928A (en) High corrosion resistant damping steel sheet
WO2002079535A3 (en) Coating powder based on chemically modified titanium suboxides
CN107532292B (en) Substrate with intermediate coating and carbon coating
JP2954555B2 (en) Heat and corrosion resistant multi-layer plated steel
JP4318633B2 (en) Hot-dip hot-dip galvanized steel sheet
JP4234038B2 (en) Anticorrosive chain
JPS6050195A (en) Plated layer concentration gradient type zinc alloy plated steel plate
JPH11310897A (en) Surface treated steel plate for fuel tank
JPS59116397A (en) Corrosion preventive steel sheet having high corrosion resistance
WO2008083683A1 (en) A combined object with corrosion resistant properties
CN205155405U (en) Petrochemical equipment uses corrosion -resistant flange

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