JP2020523486A - Refractory metal or stainless steel having an electroplated layer on the surface, and electroplating process of refractory metal or stainless steel surface - Google Patents

Abstract

The present invention provides a refractory metal or stainless steel having an electroplated layer on its surface, which comprises a substrate and an electroplated layer formed on the surface of the substrate, wherein the substrate is a refractory metal substrate or Including a stainless steel substrate, the refractory metal substrate is titanium, tantalum, niobium, or an alloy thereof, and the electroplated layer includes a rhodium ruthenium alloy layer. The electroplated layer has good adhesive strength, corrosion resistance, solderability, and is advantageous for industrial applications by improving the welding strength of refractory metal products, and the present invention further provides refractory metal or stainless steel. Provide a surface electroplating process. [Selection diagram] None

Description

The present invention relates to the field of metal surface electroplating technology, and more particularly to refractory metal or stainless steel having an electroplated layer on the surface, and the plating process for refractory metal or stainless steel surfaces.

Refractory metals such as titanium, tantalum, and niobium are excellent high-temperature strength, corrosion resistance, and process plasticity, and are important high-temperature structural materials in industry. For electronic applications, the properties of the material are excellent, but the poor solderability of such metal makes it possible to achieve the advantages of high strength, corrosion resistance, light weight, solderability, etc. in the final product at the same time. It is necessary to plate another metal layer on.

However, the characteristics of refractory metal are very active, and the surface easily forms a dense passivation film in air and water. In order to obtain a plating layer with good adhesion, it is necessary to destroy the passivation film before electroplating, but since the passivation speed of such metal is too fast, a passivation film is newly formed immediately after removal. , It is very difficult to perform electroplating on it.

To solve the above problems, some people first strip the titanium material by electrolysis and then electroplate to form a gold layer, but the effect is not very satisfactory. Also, some people heat the niobium material to 1900° C. in a vacuum and then electroplate the gold layer after cooling, but the equipment and energy consumption required for this technique is high, making it difficult to apply in actual production. is there.

In summary, it is necessary to find an electroplating process that is effective and safe for electroplating refractory metals and obtains a plating layer with good adhesion, corrosion resistance and welding strength.

Thereby, the present invention provides a refractory metal or stainless steel having an electroplated layer on the surface, and a plating process on the refractory metal or stainless steel surface. The electroplated layer has good adhesive strength, corrosion resistance, and solderability, and is advantageous for industrial applications by improving the welding strength of refractory metal products.

According to a first aspect, the present invention provides a refractory metal or stainless steel having an electroplated layer on its surface, which comprises a substrate and an electroplated layer formed on the surface of said substrate, The base material includes a refractory metal base material or a stainless steel base material, the refractory metal base material is titanium, tantalum, niobium, or an alloy thereof, and the electroplating layer includes a rhodium ruthenium alloy layer.

In an embodiment of the present invention, the rhodium ruthenium alloy layer has a thickness of 0.01-10 μm, preferably 0.1-2 μm. In the rhodium ruthenium alloy layer, the mass content of ruthenium is 20% or less, preferably the mass content of ruthenium is 0.5%-10%, more preferably the mass content of ruthenium is 3%-5. %. In the present invention, the rhodium ruthenium alloy layer has good adhesion and anticorrosion performance and solderability, which is advantageous for a wide range of industrial applications of refractory metals. Controlling the amount of ruthenium in the alloy to a small amount further improves the adhesion and corrosion resistance of the plating layer.

In an embodiment of the present invention, the electroplating layer is formed from the base material and the rhodium in order to secure a specific thickness of the electroplating layer and improve certain properties of the base material, depending on the use of the base material. It further includes a gold layer, a copper layer, a nickel layer, or a palladium layer disposed between the ruthenium alloy layer and the ruthenium alloy layer. Here, the thickness of the gold layer or the palladium layer is 0.01-10 μm, preferably 0.1-2 μm, and the thickness of the copper layer and the nickel layer is 0.01-200 μm. It is preferably 1-100 μm. Here, the arrangement of the gold layer and the palladium layer can further improve the corrosion resistance of the base material, and the arrangement of the copper layer and the nickel layer can improve the conductivity of the base material.

In an embodiment of the present invention, the electroplating layer further comprises a gold layer, or a copper layer, or a nickel layer, or a palladium layer, and the gold layer, or a copper layer, or a gold layer arranged on the surface of the rhodium ruthenium alloy layer. It includes a second rhodium ruthenium alloy layer disposed on the surface of the nickel layer or the palladium layer. Here, the thickness of the gold layer, the palladium layer, and the second rhodium ruthenium alloy layer is 0.01-10 μm, preferably 0.1-2 μm, and the thickness of the copper layer and the nickel layer. Is 0.01-200 μm, preferably 1-100 μm, and in the second rhodium ruthenium alloy layer, the mass content of ruthenium is 20% or less, preferably the mass content of ruthenium is 0.5. %-10%, more preferably the ruthenium mass content is 3%-5%.

According to an embodiment of the present invention, the electroplating layer may further be a PVD plating layer, a decoration, according to actual demand, for example, functional demand such as conductivity, abrasion resistance, fingerprint resistance, and decorative demand such as appearance and color. A decorative metal plating layer or a decorative non-metal plating layer.

The refractory metal or stainless steel having an electroplated layer on the surface provided by the first aspect of the present invention, the electroplated layer has good adhesion, corrosion resistance and solderability, and in the prior art, To solve the problem that it is difficult to obtain safe and effective electroplating on a refractory metal base material and to obtain an electroplating layer having good adhesive strength, strong corrosion resistance, and high solderability.

According to a second aspect, the present invention provides an electroplating process for refractory metal or stainless steel surfaces, which comprises the following steps.

A refractory metal base material or a stainless steel base material is pretreated, and the refractory metal base material is titanium, tantalum, niobium, or an alloy thereof.

The surface of the refractory metal base material or stainless steel base material is electroplated with a rhodium ruthenium alloy layer, followed by heat treatment to obtain a refractory metal or stainless steel having an electroplated layer on the surface, The plating layer includes a rhodium ruthenium alloy layer.

In an embodiment of the present invention, according to the application of the substrate, a gold layer, or a copper layer is further formed on the surface of the rhodium ruthenium alloy layer in order to secure a certain thickness of the electroplating layer and improve certain performance of the substrate. Electroplating a layer, a nickel layer, or a palladium layer, and then electroplating a second rhodium ruthenium alloy layer on the surface of the gold layer, the copper layer, the nickel layer, or the palladium layer, and forming the electroplating layer on the surface. Obtain a refractory metal or stainless steel having. After electroplating the second rhodium ruthenium alloy layer, heat treatment may or may not be performed as necessary.

The present invention also provides an electroplating process for refractory metal or stainless steel surfaces, which comprises the following steps.

A refractory metal base material or a stainless steel base material is pretreated, and the refractory metal base material is titanium, tantalum, niobium, or an alloy thereof.

First, a gold layer, or a copper layer, or a nickel layer, or a palladium layer is electroplated on the surface of the refractory metal substrate or the stainless steel substrate, followed by heat treatment, and after cooling, the gold layer, or copper. A rhodium ruthenium alloy layer is electroplated on the surface of the layer, the nickel layer, or the palladium layer to obtain a refractory metal or stainless steel having an electroplated layer on the surface.

In this case, that is, when the electroplating layer has the two-layer structure, after the electroplating of the rhodium-ruthenium alloy layer, the heat treatment may or may not be performed as necessary.

In the above-mentioned electroplating process of the present invention, the pretreatment is such that the refractory metal base material or the stainless steel base material is first subjected to ultrasonic immersion treatment using a phosphorus-containing detergent, and then subjected to alkaline electrolytic degreasing. , Next, the loose structural layer on the surface of the substrate is removed by electrolytic removal in an acid solution or an alkaline solution, followed by immersion in a fluorine-containing acid solution for activation, and finally electrolytic activation in a fluorine-containing alkaline solution. Including that. Here, the dipping treatment is used to wash the surface of the base material, and the surface of the base material is slightly corroded, whereby the adhesion of the electroplated layer is improved. Further, the electric degreasing operation is for removing grease/dirt on the surface of the base material, and in the operation process, the base material sample is placed on the cathode, and the subsequent electrolytic or alkaline solution electrolytic removal is performed by electrolysis. Helps to strip loose parts of the surface of the material (ie remove loose structural layers) and improve the adhesion of the electroplated layer, placing the substrate sample on the anode in the operating process and Peel off the metal on the surface of the material. Further, the operation of activating the acid solution is to bring the surface of the base material into an activated state, and the activation of the alkali solution forms a very thin protective layer on the surface of the base material. It is prevented from being oxidized again and the adhesive strength of the next electroplating layer is reduced.

In an embodiment of the present invention, the immersion treatment temperature is 40-80° C., the time is 1-10 minutes, the electric degreasing temperature is 40-80° C., the current density is 5-20 ASD (ampere/square decimeter), The time is 1-10 minutes. The temperature of the acid solution electrolysis removal is 20-35° C., the current density is 1-10 ASD, the time is 20 seconds-10 minutes, the temperature of the alkaline solution electrolysis removal is 40-80° C., the current density is 0.5-10 ASD, The time is 20 seconds-10 minutes, the acid solution immersion activation temperature is 20-35°C, the time is 30 seconds-5 minutes, the alkaline solution electrolysis activation temperature is 20-35°C, and the current density is 1-10 ASD. , The time is 30 seconds-10 minutes.

The specific operation of the heat treatment relating to the electroplating process is as follows: heat treatment at 50-300° C. for 1-60 minutes, followed by heat treatment at 300-1300° C. for 1-60 minutes. Further, specifically, the heat treatment is first heat treatment at 80 to 150° C. for 5 to 30 minutes, and then at 300 to 900° C. for 5 to 30 minutes. By the heat treatment operation, the adhesive strength of the plating layer can be better improved.

Here, the electroplating gold layer is acidic gold plating, the operating temperature is 30-50° C., and the current density is 0.2-5 ASD. The electroplated copper layer is acidic copper plating, the operating temperature is 20-35°C, and the current density is 0.2-5 ASD. The palladium layer is acidic palladium plating and the operating temperature is 16-35°C and 0.2-5 ASD. The electroplated nickel layer is acidic nickel plated and its operating temperature is 50-70°C and 0.2-5 ASD. The electroplated rhodium ruthenium alloy layer is acidic rhodium ruthenium plating, the operating temperature is 25-45° C., and the current density is 0.2-5 ASD.

After the above electroplating process is completed, according to the actual demand, a new plating layer is further disposed on the electroplating layer, which may be PVD (physical vapor deposition) layer, decorative metal plating layer or decorative non-plating layer. It includes a metal plating layer, etc., which allows the substrate to meet functional needs such as conductivity, abrasion resistance, fingerprint resistance, and decorative needs such as various color and appearance effects.

The electroplating process of refractory metal or stainless steel surface provided by the above invention is a simple process and has low requirement for equipment, so it has excellent industrial production, good adhesion, corrosion resistance and solderability. An electroplated layer can be obtained.

The advantages of the invention will be set forth in the description part that follows, some of which may be apparent from the specification or through practice of the embodiments of the invention.

The following description is of preferred embodiments of the present invention, and those skilled in the art can make certain improvements and improvements without departing from the principles of the embodiments of the present invention. It should be pointed out that improvements and improvements are also considered to be within the protection scope of the embodiments of the present invention.

Example 1
The process of electroplating the surface of refractory titanium metal comprises the following steps.
(1) Using a titanium sheet as a base material, the titanium sheet is subjected to the following pretreatment, and first, an ultrasonic immersion treatment is performed using a phosphorus-containing detergent, the temperature of which is 70° C., and the time is 5 minutes. By placing a titanium sheet on the cathode and performing alkaline electrolytic degreasing, the temperature is 70° C., the current density is 10 ASD, the time is 1 minute, and then the titanium sheet is placed on the anode to perform electrolytic removal in an alkaline solution. The loose structural layer on the surface of the base material was removed, the temperature was 70° C., the current density was 1 ASD, the time was 1 minute, and the substrate was then immersed in a fluorine-containing acid solution for 1 minute for activation, and the temperature was 25. C., and finally activated by cathodic electrolysis in a fluorine-containing alkaline solution for 2 minutes at a temperature of 25.degree. C. and a current density of 5 ASD.

(2) After the pretreatment is completed, the operation of electroplating a gold layer having a thickness of 0.8 μm on the surface of the titanium sheet and electroplating the gold layer is acidic gold plating, and the operation temperature is 40° C. The current density is 0.5 ASD. Then, the sample is placed in an oven to be heat-treated under the conditions of first baking at 100° C. for 10 minutes, then baking at 400° C. for 20 minutes, and cooling the sample to a thickness on the surface of the gold layer. A 0.8 μm rhodium ruthenium alloy layer (ratio of the alloy is rhodium:ruthenium is 95%:5%) is electroplated, and after electroplating, the sample is placed in an oven and heat-treated under the following conditions: Baking at 100° C. for 10 minutes and then at 300° C. for 10 minutes to obtain a titanium sheet having an electroplating layer on the surface, the electroplating layer being a gold layer sequentially formed on the surface of the titanium sheet. And a rhodium ruthenium alloy layer, the electroplating rhodium ruthenium alloy layer is acidic rhodium ruthenium plating, the operating temperature is 35° C., and the current density is 1 ASD.

Example 2
The electroplating process of the surface of refractory metal tantalum includes the following steps.
(1) Using the tantalum sheet as a base material, the tantalum sheet is subjected to the following pretreatment, and is first subjected to ultrasonic immersion treatment using a phosphorus-containing cleaning agent, the temperature of which is 70° C., and the time is 10 minutes. By placing the tantalum sheet on the cathode and performing alkaline electrolytic degreasing, the temperature is 70° C., the current density is 10 ASD, the time is 5 minutes, and then the tantalum sheet is placed on the anode to perform electrolytic removal in the alkaline solution. The loose structural layer on the surface of the substrate was removed, the temperature was 70° C., the current density was 5 ASD, the time was 5 minutes, and then the substrate was immersed in a fluorine-containing acid solution for 1 minute for activation, and the temperature was 25. C., and finally activated by cathodic electrolysis in a fluorine-containing alkaline solution for 2 minutes at a temperature of 25.degree. C. and a current density of 5 ASD.

(2) After completion of the pretreatment, a rhodium ruthenium alloy layer having a thickness of 0.8 μm is electroplated on the surface of the tantalum sheet, and the ratio of the rhodium ruthenium alloy (Rh:Ru) is set to 95%:5%. The tantalum sheet sample was put in an oven to be heat-treated, firstly baked at 100° C. for 10 minutes and then at 300° C. for 20 minutes, and after the sample was cooled, the surface of the rhodium ruthenium alloy layer had a thickness of 0. Electroplating a 5 μm gold layer and finally electroplating a 0.2 μm thick second rhodium ruthenium alloy layer (rhodium:ruthenium is 95%:5% alloy ratio) on the gold layer, A tantalum sheet having an electroplated layer on a surface thereof is obtained, the electroplated layer including a rhodium ruthenium alloy layer, a gold layer and a second rhodium ruthenium alloy layer sequentially formed on the surface of the tantalum sheet, wherein: The operation of the electroplated gold layer is acid gold plating, the operation temperature is 40° C., the current density is 0.5 ASD, the electroplated rhodium ruthenium alloy layer is acid rhodium ruthenium plating, and the operation temperature is 35° C. , The current density is 1 ASD.

Example 3
The electroplating process on the surface of refractory niobium metal includes the following steps.
(1) Using the niobium sheet as a base material, the niobium sheet is subjected to the following pretreatment, and is first subjected to ultrasonic immersion treatment using a phosphorus-containing detergent, and the temperature is 70° C. and the time is 10 minutes, and then, By placing the niobium sheet on the cathode and performing alkaline electrolytic degreasing, the temperature is 70° C., the current density is 10 ASD, the time is 5 minutes, and then the niobium sheet is placed on the anode to perform electrolytic removal in the alkaline solution. The loose structural layer on the surface of the base material was removed, the temperature was 70° C., the current density was 1 ASD, the time was 1 minute, and the substrate was then immersed in a fluorine-containing acid solution for 1 minute for activation, and the temperature was 25. C., and finally activated by cathodic electrolysis in a fluorine-containing alkaline solution for 2 minutes at a temperature of 25.degree. C. and a current density of 5 ASD.

(2) After the pretreatment is completed, a rhodium ruthenium alloy layer having a thickness of 0.5 μm is electroplated on the surface of the niobium sheet so that the ratio of rhodium ruthenium alloy (Rh:Ru) is 97%:3%. The niobium sheet sample was placed in an oven to be heat-treated, firstly baked at 100° C. for 10 minutes, and then at 500° C. for 10 minutes to obtain a niobium sheet having an electroplated layer on the surface after the sample was cooled. Thus, the electroplating layer includes a rhodium ruthenium alloy layer formed on the surface of the niobium sheet, wherein the electroplating rhodium ruthenium alloy layer is acidic rhodium ruthenium plating, and its operating temperature is 35° C. The density is 1 ASD.

Example 4
The electroplating process on the surface of stainless steel includes the following steps.
(1) Using stainless steel as a base material, the following pretreatment is performed on the stainless steel, and then ultrasonic immersion treatment is first performed using a phosphorus-containing cleaning agent at a temperature of 70° C. for a time of 2 minutes, and thereafter. By placing stainless steel on the cathode and performing alkaline electrolytic degreasing, the temperature is 70° C., the current density is 5 ASD, the time is 2 minutes, and then the stainless steel is placed on the anode to perform electrolytic removal in the alkaline solution. The loose structural layer on the surface of the base material was removed, the temperature was 70° C., the current density was 1 ASD, the time was 1 minute, and the substrate was then immersed in a fluorine-containing acid solution for 1 minute for activation, and the temperature was 25. C., and finally activated by cathodic electrolysis in a fluorine-containing alkaline solution for 2 minutes at a temperature of 25.degree. C. and a current density of 5 ASD.

(2) After the pretreatment is completed, a rhodium ruthenium alloy layer having a thickness of 0.8 μm is electroplated on the surface of the stainless steel, and the ratio of the rhodium ruthenium alloy (Rh:Ru) is set to 95%:5%. , The stainless steel sample was placed in an oven to be heat treated, firstly baked at 100° C. for 10 minutes, then at 300° C. for 20 minutes, and after the sample was cooled, the surface of the rhodium ruthenium alloy layer had a thickness of 0. An 8 μm gold layer is electroplated, and finally a 1 μm thick second rhodium ruthenium alloy layer (alloy ratio is rhodium:ruthenium 97%:3%) is electroplated on the gold layer. Obtaining a stainless steel having an electroplated layer, the electroplated layer comprising a rhodium ruthenium alloy layer, a gold layer and a second rhodium ruthenium alloy layer sequentially formed on the surface of the stainless steel, wherein The operation of the plated gold layer is acidic gold plating, the operating temperature is 40° C., the current density is 0.5 ASD, the electroplating rhodium ruthenium alloy layer is acidic rhodium ruthenium plating, the operating temperature is 35° C., current The density is 1 ASD.

Example 5
The electroplating process of the surface of refractory metal tantalum includes the following steps.
(1) Using the tantalum sheet as a base material, the tantalum sheet is subjected to the following pretreatment, and is first subjected to ultrasonic immersion treatment using a phosphorus-containing cleaning agent, the temperature of which is 70° C., and the time is 10 minutes. By placing the tantalum sheet on the cathode and performing alkaline electrolytic degreasing, the temperature is 70° C., the current density is 10 ASD, the time is 5 minutes, and then the tantalum sheet is placed on the anode to perform electrolytic removal in the alkaline solution. The loose structural layer on the surface of the substrate was removed, the temperature was 70° C., the current density was 5 ASD, the time was 5 minutes, and then the substrate was immersed in a fluorine-containing acid solution for 1 minute for activation, and the temperature was 25. C., and finally activated by cathodic electrolysis in a fluorine-containing alkaline solution for 2 minutes at a temperature of 25.degree. C. and a current density of 5 ASD.

(2) After the pretreatment is completed, the operation of electroplating a nickel layer having a thickness of 1 μm on the surface of the tantalum sheet and electroplating the nickel layer is acidic nickel plating, the operating temperature is 60° C., current density Is 0.5 ASD. After that, the sample is placed in an oven to be heat-treated under the conditions of first baking at 100° C. for 10 minutes, then baking at 300° C. for 20 minutes, and then cooling the sample to a thickness on the surface of the nickel layer. A 1 μm rhodium ruthenium alloy layer (ratio of alloy is rhodium:ruthenium is 95%:5%) is electroplated to obtain a tantalum sheet having an electroplating layer on the surface, the electroplating layer being the tantalum sheet. Including a nickel layer and a rhodium ruthenium alloy layer, which are sequentially formed on the surface of, the electroplating rhodium ruthenium alloy layer is acidic rhodium ruthenium plating, the operating temperature is 35° C., and the current density is 1 ASD.

Example 6
The electroplating process on the surface of refractory niobium metal includes the following steps.
(1) Using the niobium sheet as a base material, the niobium sheet is subjected to the following pretreatment, and is first subjected to ultrasonic immersion treatment using a phosphorus-containing detergent, and the temperature is 70° C. and the time is 5 minutes. By placing the niobium sheet on the cathode and performing alkaline electrolytic degreasing, the temperature is 70° C., the current density is 10 ASD, the time is 1 minute, and then the niobium sheet is placed on the anode to perform electrolytic removal in an alkaline solution. The loose structural layer on the surface of the substrate was removed, the temperature was 70° C., the current density was 1 ASD, the time was 1 minute, and then the substrate was immersed in a fluorine-containing acid solution for 1 minute for activation, and the temperature was 25. C., and finally activated by cathodic electrolysis in a fluorine-containing alkaline solution for 2 minutes at a temperature of 25.degree. C. and a current density of 5 ASD.

(2) After the pretreatment is completed, the operation of electroplating a copper layer having a thickness of 2 μm on the surface of the niobium sheet and electroplating the gold layer is acidic gold plating, the operating temperature is 25° C., and the current density is Is 0.5 ASD. After that, the sample is placed in an oven to be heat-treated under the conditions of first baking at 100° C. for 10 minutes, then baking at 300° C. for 20 minutes, and then cooling the sample to a thickness on the surface of the copper layer. A 1 μm rhodium ruthenium alloy layer (ratio of the alloy is rhodium:ruthenium is 95%:5%) is electroplated to obtain a niobium sheet having an electroplating layer on the surface, and the electroplating layer is the niobium sheet. Including a copper layer and a rhodium ruthenium alloy layer which are sequentially formed on the surface thereof, the electroplating rhodium ruthenium alloy layer is acidic rhodium ruthenium plating, the operating temperature is 35° C., and the current density is 1 ASD.

Example 7
The electroplating process on the surface of stainless steel includes the following steps.
(1) Using stainless steel as a base material, the following pretreatment is performed on the stainless steel, and then ultrasonic immersion treatment is first performed using a phosphorus-containing cleaning agent at a temperature of 70° C. for a time of 2 minutes, and thereafter. By placing stainless steel on the cathode and performing alkaline electrolytic degreasing, the temperature is 70° C., the current density is 5 ASD, the time is 2 minutes, and then the stainless steel is placed on the anode to perform electrolytic removal in the alkaline solution. The loose structural layer on the surface of the base material was removed, the temperature was 70° C., the current density was 1 ASD, the time was 1 minute, and the substrate was then immersed in a fluorine-containing acid solution for 1 minute for activation, and the temperature was 25. C., and finally activated by cathodic electrolysis in a fluorine-containing alkaline solution for 2 minutes at a temperature of 25.degree. C. and a current density of 5 ASD.

(2) After the pretreatment is completed, the operation of electroplating a 0.5 μm-thick palladium layer on the surface of the stainless steel and electroplating the palladium layer is acidic palladium plating, and the operation temperature is 25° C. The current density is 0.5 ASD. Then, the sample is placed in an oven to be heat-treated under the conditions of first baking at 100° C. for 10 minutes, then baking at 300° C. for 20 minutes, and then cooling the sample to a thickness on the surface of the palladium layer. A 2 μm rhodium ruthenium alloy layer (ratio of the alloy is rhodium:ruthenium is 95%:5%) is electroplated to obtain a stainless steel having an electroplated layer on the surface, and the electroplated layer is the stainless steel. Including a palladium layer and a rhodium ruthenium alloy layer which are sequentially formed on the surface thereof, the electroplating rhodium ruthenium alloy layer is acidic rhodium ruthenium plating, the operating temperature is 35° C., and the current density is 1 ASD.

Effects Examples In order to strongly support the beneficial effects provided by the technical solutions of the embodiments of the present invention, the following performance tests are provided in particular.

(1) Grid test: A grid test was performed on the samples obtained in Examples 1-7, and specifically, a 10×10 (1 mm×1 mm) grid was carved with a grid knife and a brush was used to test the test area. The debris was swept, and No. 3 manufactured by 3M Company was used. The 600 tape is firmly glued to the grid, one end of the tape is grasped by hand and quickly pulled out of the vertical direction and two similar tests are done in the same position. If the edges of the slit are perfectly smooth and no edges of the grid are peeled off, then it passes. The results show that the samples of Examples 1-7 of the invention passed the grid test.

(2) 180° bending test: A 180° bending test was performed on the samples obtained in Examples 1-7. Specifically, No. 3 manufactured by 3M Company was used. The 600 tape is firmly adhered to the sample, the sample is bent 90° clockwise, then the sample is bent 180° in the opposite direction, and then the tape is quickly pulled out from the vertical direction.

The tape passes if no plating layer remains on the tape. The results show that the samples of Examples 1-7 of the invention passed the 180° bend test.

(3) Artificial perspiration electrolysis test: The samples obtained in Examples 1-7 are subjected to an artificial perspiration electrolysis test, and an artificial perspiration solution is first prepared in the following manner: sodium chloride 0.5% by weight, lactic acid 0.1. Mass%, urea 0.1% by weight, and balance are pure water. The solution is electrolyzed in an inverted fashion and the difference between the samples before and after electrolysis is observed. In the artificial sweat solution, the sample is placed in the anode position, the platinum titanium mesh is placed in the cathode position, the anode area:cathode area ratio is about 2:1 and the distance between the anode and the cathode is about 5 mm. The test is performed at a constant voltage of 5 V, and the difference in the appearance of the sample after electrolysis is observed for 10 minutes. As a result, after 10 minutes of electrolysis, there was no significant difference in the appearance of the samples of Examples 1-7, therefore it was found that the result of the electrolysis test was acceptable.

The above test results show that the surfaces of the samples of the examples of the present invention have good adhesion and corrosion resistance by disposing the electroplating layer containing the rhodium ruthenium alloy.

Claims (12)

A substrate and an electroplating layer formed on the surface of the substrate, the substrate comprises a refractory metal substrate or a stainless steel substrate, the refractory metal substrate is titanium, tantalum, niobium, or A refractory metal or stainless steel having an electroplated layer on the surface thereof, which is an alloy thereof, wherein the electroplated layer includes a rhodium ruthenium alloy layer. The electroplating layer further includes a gold layer, a copper layer, a nickel layer, or a palladium layer arranged between the base material and the rhodium ruthenium alloy layer, and the thickness of the gold layer or the palladium layer. Is 0.01-10 μm, and the thickness of the copper layer or the nickel layer is 0.01-200 μm. The refractory metal or stainless steel having an electroplated layer on the surface according to claim 1, wherein steel. The electroplating layer further comprises a gold layer, or a copper layer, or a nickel layer, or a palladium layer, which is disposed on the surface of the rhodium ruthenium alloy layer, and a gold layer, a copper layer, a nickel layer, or a palladium layer. A second rhodium ruthenium alloy layer disposed on the surface, wherein the gold layer, the palladium layer, and the second rhodium ruthenium alloy layer have a thickness of 0.01-10 μm, and the copper layer and the nickel layer. Has a thickness of 0.01-200 μm, and the mass content of ruthenium in the second rhodium ruthenium alloy layer is 20% or less. Having refractory metal or stainless steel. The thickness of the rhodium ruthenium alloy layer is 0.01-10 μm, and the mass content of ruthenium in the rhodium ruthenium alloy layer is 20% or less. Refractory metal or stainless steel with plating layer. A PVD plating layer, a decorative metal plating layer, or a decorative non-metal plating layer is further arranged on the electroplating layer, wherein the surface has an electroplating layer. Molten metal or stainless steel. An electroplating process for refractory metal or stainless steel surfaces, comprising:
Pretreating the refractory metal substrate or stainless steel substrate, which is titanium, tantalum, niobium, or an alloy thereof,
Electroless plating of a rhodium ruthenium alloy layer on the surface of the refractory metal base material or stainless steel base material, followed by heat treatment, and a refractory metal or stainless steel having an electroplating layer containing a rhodium ruthenium alloy layer on the surface. And a step of obtaining a refractory metal or stainless steel surface electroplating process. A gold layer, a copper layer, a nickel layer, or a palladium layer is further electroplated on the surface of the rhodium ruthenium alloy layer, and then a second rhodium layer is formed on the surface of the gold layer, the copper layer, the nickel layer, or the palladium layer. The electroplating process for a surface of a refractory metal or stainless steel according to claim 6, wherein the ruthenium alloy layer is electroplated to obtain a refractory metal or stainless steel having an electroplated layer on the surface. In the pretreatment, the refractory metal base material or the stainless steel base material is first subjected to ultrasonic immersion treatment using a phosphorus-containing detergent, and then subjected to alkaline electrolytic degreasing, and then an acid solution or an alkali solution. And removing the loose structural layer on the surface of the substrate by electrolytic removal in step 1, then immersing in a fluorine-containing acid solution for activation, and finally performing electrolytic activation in a fluorine-containing alkaline solution. The electroplating process for the surface of the refractory metal or stainless steel according to 6 or 7. The specific operation of the heat treatment is to perform heat treatment at 50-300°C for 1-60 minutes, and then heat treatment at 300-1300°C for 1-60 minutes. An electroplating process for the surface of refractory metal or stainless steel according to any of the above. An electroplating process for refractory metal or stainless steel surfaces, comprising:
Pretreating the refractory metal substrate or stainless steel substrate, which is titanium, tantalum, niobium, or an alloy thereof,
First, a gold layer, or a copper layer, or a nickel layer, or a palladium layer is electroplated on the surface of the refractory metal substrate or the stainless steel substrate, followed by heat treatment, and after cooling, the gold layer or the copper layer. , Or a nickel layer, or a palladium layer is electroplated with a rhodium-ruthenium alloy layer on the surface to obtain a refractory metal or stainless steel having an electroplated layer on the surface. Surface electroplating process. The pretreatment is performed on the refractory metal base material or the stainless steel base material by ultrasonic immersion treatment using a phosphorus-containing detergent, followed by alkaline electrolytic degreasing, and then using an acid solution or an alkaline solution. 11. The method comprises removing the loose structural layer on the surface of the substrate by electrolytic removal, subsequently immersing the substrate in a fluorine-containing acid solution for activation, and finally performing electrolytic activation in a fluorine-containing alkaline solution. Electroplating process of refractory metal or stainless steel surface as described in. The specific operation of the heat treatment is to perform heat treatment at 50-300° C. for 1-60 minutes, and subsequently heat treatment at 300-1300° C. for 1-60 minutes, according to claim 10 or 11. Electroplating process for surfaces of refractory metals or stainless steels described.