CN113445092B - Copper plating method for 0Cr15Ni25Ti2MoAlVB stainless steel surface - Google Patents

Copper plating method for 0Cr15Ni25Ti2MoAlVB stainless steel surface Download PDF

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CN113445092B
CN113445092B CN202110730116.0A CN202110730116A CN113445092B CN 113445092 B CN113445092 B CN 113445092B CN 202110730116 A CN202110730116 A CN 202110730116A CN 113445092 B CN113445092 B CN 113445092B
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stainless steel
copper plating
copper
acid washing
activation
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CN113445092A (en
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孙永庆
齐超
刘振宝
杨玉军
王长军
杨志勇
梁剑雄
于腾
杨亮
丑英玉
侯少林
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FUSHUN SPECIAL STEEL SHARES CO LTD
Central Iron and Steel Research Institute
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FUSHUN SPECIAL STEEL SHARES CO LTD
Central Iron and Steel Research Institute
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/34—Pretreatment of metallic surfaces to be electroplated
    • C25D5/36—Pretreatment of metallic surfaces to be electroplated of iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • 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
    • C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
    • C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
    • C23G1/02—Cleaning or pickling metallic material with solutions or molten salts with acid solutions
    • C23G1/08—Iron or steel
    • C23G1/088—Iron or steel solutions containing organic acids
    • 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
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F1/00—Electrolytic cleaning, degreasing, pickling or descaling
    • C25F1/02—Pickling; Descaling
    • C25F1/04—Pickling; Descaling in solution
    • C25F1/06—Iron or steel

Abstract

The invention discloses a copper plating method for a 0Cr15Ni25Ti2MoAlVB stainless steel surface, belongs to the technical field of copper plating, and solves the problems that oxalate is adopted as a 0Cr15Ni25Ti2MoAlVB stainless steel coating in the prior art and is easy to fall off and lose lubrication effect, and an oxide film cannot be cleaned up before copper plating of the 0Cr15Ni25Ti2MoAlVB stainless steel surface, so that the quality of the coating is poor. The method comprises the following steps: sequentially carrying out electrolytic degreasing, primary pickling, secondary pickling, activation, pretreatment and copper plating on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel; the secondary acid washing comprises the following steps: carrying out secondary acid washing on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel subjected to the primary acid washing, wherein the components of a secondary acid washing solution comprise 100-150 ml/L of HCl and 0.5-1 g/L of urotropin; the activation comprises the following steps: activating the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel after the secondary acid washing, wherein the components of the activation solution comprise 80 to 120ml/L of HCl and 0.01 to 0.03g/L of polyethylene glycol. The method can be used for copper plating of the surface of 0Cr15Ni25Ti2MoAlVB stainless steel.

Description

Copper plating method for 0Cr15Ni25Ti2MoAlVB stainless steel surface
Technical Field
The invention belongs to the technical field of copper plating, and particularly relates to a copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel.
Background
In order to improve the workability of 0Cr15Ni25Ti2MoAlVB stainless steel, it is generally necessary to form a plating layer on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel.
For example, when 0Cr15Ni25Ti2MoAlVB wire rod is processed into a fastener, the surface of the wire rod is coated with oxalate, although the oxalate coating may also provide some protection and lubrication, however, oxalate is not firmly bonded to the surface of the wire rod and is not suitable for long-term storage because the oxalate coating is easily removed under damp, hot and humid conditions, thereby losing lubrication.
In addition, 0Cr15Ni25Ti2MoAlVB stainless steel is very susceptible to passivation in air, resulting in a dense oxide film that protects the substrate from corrosion. However, in the prior art, when the surface treatment is carried out on 0Cr15Ni25Ti2MoAlVB stainless steel, the oxide film generated spontaneously can not be cleaned, and the quality of the plating layer is affected.
Disclosure of Invention
In view of the above analysis, the present invention aims to provide a method for plating copper on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, which solves the problems in the prior art that oxalate is adopted as a plating layer of 0Cr15Ni25Ti2MoAlVB stainless steel, which is easy to fall off and loses lubrication effect, and an oxide film cannot be cleaned up before plating copper on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, so that the quality of the plating layer is poor.
The purpose of the invention is mainly realized by the following technical scheme:
the invention provides a copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, which comprises the following steps:
sequentially carrying out electrolytic degreasing, primary acid washing (general acid washing), secondary acid washing (weak acid washing), activation, pretreatment and copper plating on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel;
the secondary acid washing comprises the following steps: performing secondary acid washing on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel subjected to the primary acid washing, wherein the secondary acid washing solution comprises 100-150 ml/L of HCl and 0.5-1 g/L of urotropine, and the solvent is water;
the activation comprises the following steps: activating the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel subjected to secondary acid washing, wherein the activating solution comprises 80-120 ml/L of HCl and 0.01-0.03 g/L of polyethylene glycol, and the solvent is water.
Furthermore, the temperature of the secondary acid washing is 20-30 ℃, and the time of the secondary acid washing is 3-5 min.
Further, the relative molecular weight of polyethylene glycol is 400 to 600.
Furthermore, the activation temperature is 20-30 ℃, and the activation time is 3-5 min.
Further, the above copper plating method of the surface of 0Cr15Ni25Ti2MoAlVB stainless steel is applied to a 0Cr15Ni25Ti2MoAlVB stainless steel strip, a 0Cr15Ni25Ti2MoAlVB stainless steel wire rod or a 0Cr15Ni25Ti2MoAlVB stainless steel strip.
Further, the above-mentioned copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel was used for copper plating of a 0Cr15Ni25Ti2MoAlVB stainless steel wire rod.
Furthermore, 0.2 to 0.4ml/L of 30 percent hydrogen peroxide diluted by one time of deionized water or distilled water is added into the plating solution for copper plating every 24 to 48 hours.
Further, after the copper plating solution is used for 1-1.5 months, the plating solution is heated to 70-75 ℃, 1-2 ml/L of 30% hydrogen peroxide is added under continuous stirring, the mixture is fully stirred for 1-1.5 h, then 3-5 g/L of powdered activated carbon is slowly added, the mixture is continuously stirred for 0.5-1.0 h, the mixture is kept stand, and the plating solution is filtered after being clarified.
Further, in the above electrolytic degreasing, the electrolytic degreasing solution contains: naOH 20-40 g/L, na 3 PO 4 ·12H 2 O5～10g/L、Na 2 CO 3 20～30g/L、Na 2 SiO 3 5 to 15g/L, 0.5 to 1ml/L OP emulsifier, 0.3 to 0.5ml/L defoamer and water as solvent.
Furthermore, the temperature of electrolytic degreasing is 20-30 ℃, and the current density of electrolytic degreasing is 5-10A/dm 2 The time of electrolytic degreasing is 5-10 min.
Further, the primary pickling solution comprises the following components: HNO 3 50～90ml/L、NH 4 HF 2 1-2 g/L, 5-10 g/L of citric acid and 1-2 g/L of urotropine, and the solvent is water.
Furthermore, the temperature of the primary acid washing is 20-30 ℃, and the time of the primary acid washing is 10-15 min.
Further, the components of the pretreatment solution include: 100-150 ml/L of HCl and NiCl 2 200-300 g/L sodium dodecyl benzene sulfonate 0.01-0.03 g/L and water as solvent.
Furthermore, the temperature of the pretreatment is 20-30 ℃, and the time of the pretreatment is 5-10 min.
Further, the copper plating solution comprises the following components: 200-300 g/L of copper sulfate, 50-100 ml/L of sulfuric acid, 0.1-0.2 ml/L of cylinder opening agent, 1-2 ml/L of brightening agent, 0.5-1 ml/L of wetting agent and 0.2-5 ml/L of softening agent, and the solvent is water.
Further, the temperature of the copper plating is 20-30 ℃, and the current density of the copper plating is 3-4A/dm 2 The copper plating time is 10-15 min.
Further, the method also comprises the following steps after copper plating:
the copper-plated 0Cr15Ni25Ti2MoAlVB stainless steel is subjected to post-treatment.
Further, the post-treatment medium is an anti-discoloration solution.
Furthermore, the temperature of the post-treatment is 20-30 ℃, and the time of the post-treatment is 10-15 min.
Further, the method also comprises the following steps after post-processing:
and (3) washing the post-treated 0Cr15Ni25Ti2MoAlVB stainless steel with water (washing for multiple times) and drying (drying for one time) in sequence.
Furthermore, the drying temperature is 100-120 ℃, and the drying time is 2-3 min.
Compared with the prior art, the invention can realize at least one of the following beneficial effects:
a) According to the method for plating the copper on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel, the secondary pickling solution and the activating solution with specific components are adopted, so that an oxide film can be completely dissolved, the oxide film can be prevented from being generated again, a substrate can be protected from excessive corrosion, and the quality of a plating layer can be effectively improved.
b) The invention provides a copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, and the 0Cr15Ni25Ti2MoAlVB stainless steel belongs to Fe-25Ni-15 Cr-based high-temperature alloy. The material has high yield strength and creep resistance at the temperature of below 650 ℃, and has excellent processing plasticity and welding performance, so the material is widely used as a high-temperature bearing part material of an engine or an automobile turbine engine, such as a turbine disc, a pressure machine disc, a rotor blade, a fastener and the like.
c) The method for plating copper on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel provided by the invention immediately transfers the activated 0Cr15Ni25Ti2MoAlVB stainless steel to a pretreatment procedure, adopts the pretreatment solution and NiCl of the components 2 The surface of the 0Cr15Ni25Ti2MoAlVB stainless steel is chemically replaced by more active Fe ions to form Ni, and a protective layer can be rapidly deposited on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel. Although the thickness of the protective layer is thinner and less than 1 μm, the protective layer plays a key role in the binding force and the density of a surface copper layer, can realize stable and continuous copper plating process, and has controllable plating layer thickness and stable plating solution components.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objectives and other advantages of the invention will be realized and attained by the structure particularly pointed out in the written description and drawings.
Drawings
The drawings, in which like reference numerals refer to like parts throughout, are for the purpose of illustrating particular embodiments only and are not to be considered limiting of the invention.
FIG. 1 is a physical representation of a copper layer formed without secondary pickling, activation and pretreatment of the 0Cr15Ni25Ti2MoAlVB stainless steel surface;
FIG. 2 is an enlarged cross-sectional view of a copper layer formed without secondary pickling, activation and pretreatment of the surface of 0Cr15Ni25Ti2MoAlVB stainless steel;
FIG. 3 is a drawing showing a copper layer in accordance with the copper plating method for a 0Cr15Ni25Ti2MoAlVB stainless steel surface according to the first example;
FIG. 4 is an enlarged cross-sectional view of the copper layer using the copper plating method on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel of example one;
FIG. 5 is a schematic view of the line scanning direction of the 0Cr15Ni25Ti2MoAlVB stainless steel of the first embodiment, wherein the arrow direction is from the copper layer to the substrate;
FIG. 6 is a line scan graph of 0Cr15Ni25Ti2MoAlVB stainless steel of the first embodiment.
Detailed Description
The preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings, which form a part hereof, and which together with the embodiments of the invention serve to explain the principles of the invention.
The invention provides a copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, which comprises the following steps:
sequentially carrying out electrolytic degreasing, primary acid washing (general acid washing), secondary acid washing (weak acid washing), activation, pretreatment and copper plating on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel;
wherein, the secondary acid washing comprises the following steps:
carrying out secondary pickling on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel subjected to primary pickling, wherein the secondary pickling solution comprises 100-150 ml/L of HCl and 0.5-1 g/L of urotropine, the solvent is water, the temperature of the secondary pickling is 20-30 ℃, and the time of the secondary pickling is 3-5 min;
the activation comprises the following steps:
activating the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel subjected to secondary pickling, wherein the components of an activation solution comprise 80-120 ml/L of HCl and 0.01-0.03 g/L of polyethylene glycol, the solvent is water, the relative molecular weight of the polyethylene glycol is 400-600, the polyethylene glycol is ensured to be liquid, the uniform mixing and dispersion are facilitated, the activation temperature is 20-30 ℃, and the activation time is 3-5 min.
The electrochemical reaction occurring at the surface of the anode electrode during the copper plating process is represented as follows:
Cu→Cu 2+ +2e (1)
the electrochemical reaction occurring at the surface of the cathode electrode comprises Cu 2+ The reaction equation is as follows:
Cu 2+ +2e→Cu (2)
H 2+ +2e→H 2 ↑ (3)
the difficulty in pretreatment of 0Cr15Ni25Ti2MoAlVB stainless steel is how to thoroughly clean the oxide film on the surface of the stainless steel and ensure that the surface of a substrate is in an activated state before copper plating, namely the surface does not generate the oxide film again.
Compared with the prior art, the copper plating method for the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel, provided by the invention, has the advantages that the secondary pickling solution and the activating solution with specific components are adopted, so that the oxide film can be completely dissolved, the oxide film can be prevented from being generated again, meanwhile, the matrix can be protected from excessive corrosion, and the quality of a plating layer can be effectively improved.
The 0Cr15Ni25Ti2MoAlVB stainless steel is a Fe-25Ni-15 Cr-based superalloy. The material has high yield strength and creep resistance at the temperature of below 650 ℃, and has excellent processing plasticity and welding performance, so the material is widely used as a high-temperature bearing part material of an engine or an automobile turbine engine, such as a turbine disc, a pressure machine disc, a rotor blade, a fastener and the like.
Specifically, the functions of the respective steps are as follows:
electrolytic degreasing: the residual grease or other dirt on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel can be removed, and the electrolytic oil removing effect is superior to that of common oil removing.
Primary acid washing: slightly removing residual oxide films and other pollutants on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel.
Secondary acid washing: after the first acid washing, the second acid washing (weak acid washing) is carried out to remove the thin oxide film again so as to obtain 0CrThe surface of the 15Ni25Ti2MoAlVB stainless steel is thoroughly cleaned, so that the adhesion of a plating layer can be improved. Specifically, HCl functions to remove a surface oxide film (mainly Cr component) 2 O 3 ) The urotropine acts as a corrosion inhibitor to prevent the HCl from excessively corroding the 0Cr15Ni25Ti2MoAlVB stainless steel matrix. Meanwhile, the temperature and time of secondary pickling are controlled, so that the oxide film can be completely removed, and the substrate cannot be seriously corroded.
And (3) activation: before 0Cr15Ni25Ti2MoAlVB stainless steel enters a copper plating solution, the activation is carried out, so that an oxide film can be effectively removed, the surface of a matrix is in an activated state before copper plating, and the oxide film cannot be generated again. Wherein HCl is used for removing the oxide film (main component Cr) possibly generated on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel at any time 2 O 3 ) The polyethylene glycol acts as a dispersant to prevent excessive concentration of HCl somewhere and thereby excessive corrosion of the 0Cr15Ni25Ti2MoAlVB stainless steel matrix.
Pretreatment: before the 0Cr15Ni25Ti2MoAlVB stainless steel enters the plating solution for copper plating, pretreatment is carried out, an oxide film can be removed again, and the adhesive force of the plating layer is improved.
Illustratively, the above-described copper plating method of the surface of 0Cr15Ni25Ti2MoAlVB stainless steel is used for a strip of 0Cr15Ni25Ti2MoAlVB stainless steel, or the like.
It should be noted that the above-mentioned copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel is particularly suitable for copper plating of 0Cr15Ni25Ti2MoAlVB stainless steel wire rods, because the plating layer deposition speed is fast for the continuous plating process of the wire rods, and in order to prevent concentration polarization from occurring and affecting the quality of the plating layer, the concentration of copper sulfate in the copper plating solution has to be increased, however, once the concentration of copper sulfate is increased, the cathode polarization will be weakened and a compact plating layer is not easily obtained, therefore, the surface of 0Cr15Ni25Ti2MoAlVB stainless steel should be activated to increase the cathode polarization, and the plating layer deposition speed is appropriately decreased to increase the bonding force and density of the plating layer.
It is worth noting that the Cr content in the 0Cr15Ni25Ti2MoAlVB high-temperature resistant alloy is high, and the quality of a coating layer is seriously influenced by the continuous increase of the Cr content in the plating solution in the batch production process. Therefore, impurity ions such as Cr and Fe in the plating solution need to be removed in time, and the following two methods can be specifically adopted:
daily purification: in daily production, 0.2-0.4 ml/L of 30% hydrogen peroxide diluted by one time of deionized water or distilled water is added into the plating solution every 24-48 hours, so that the cuprous copper can be oxidized into cupric copper.
Periodic purification: after the plating solution is used for 1-1.5 months, the plating solution is heated to 70-75 ℃, 1-2 ml/L of 30% hydrogen peroxide is added under continuous stirring, the mixture is fully stirred for 1-1.5 h, then 3-5 g/L of powdered activated carbon is slowly added, the mixture is continuously stirred for 0.5-1.0 h, the mixture is kept stand, and the plating solution is filtered after being clarified.
In order to further remove residual grease or other dirt on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel, in the electrolytic degreasing, the electrolytic degreasing solution comprises the following components: naOH 20-40 g/L, na 3 PO 4 ·12H 2 O5～10g/L、Na 2 CO 3 20～30g/L、Na 2 SiO 3 5-15 g/L, OP emulsifier 0.5-1 ml/L and defoaming agent 0.3-0.5 ml/L, the solvent is water, the temperature for electrolytic degreasing is 20-30 ℃, and the current density for electrolytic degreasing is 5-10A/dm 2 The time of electrolytic degreasing is 5-10 min. Thus, through NaOH and Na 3 PO 4 、Na 2 CO 3 And (3) removing the grease dirt on the surface of the material by using an alkaline solvent. Because the physical stirring effect and the chemical effect are achieved in the electrolytic degreasing process, the electrolytic degreasing effect is superior to that of common immersion degreasing.
In order to further remove the residual oxides and other pollutants on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel, in the primary pickling, the composition of the primary pickling solution comprises: HNO 3 50～90ml/L、NH 4 HF 2 1-2 g/L, 5-10 g/L of citric acid and 1-2 g/L of urotropine, wherein the solvent is water, the temperature of one-time acid washing is 20-30 ℃, and the time of one-time acid washing is 10-15 min. Wherein, HNO 3 The main function is to remove the refractory oxide and NH on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel 4 HF 2 Has strong corrosivity, and can remove refractory oxides. LemonThe citric acid and the urotropine are used as corrosion inhibitors, and can avoid serious corrosion on a 0Cr15Ni25Ti2MoAlVB stainless steel matrix.
In order to further remove the oxide film and improve the adhesion of the plating layer, the pretreatment solution comprises the following components: 100-150 ml/L of HCl and NiCl 2 200 to 300g/L, 0.01 to 0.03g/L of sodium dodecyl benzene sulfonate and water as solvent, the temperature of the pretreatment is between 20 and 30 ℃, and the time of the pretreatment is between 5 and 10min. Thus, the activated 0Cr15Ni25Ti2MoAlVB stainless steel was immediately transferred to the pretreatment step using the pretreatment solution of the above composition, niCl 2 The surface of the 0Cr15Ni25Ti2MoAlVB stainless steel is chemically replaced by the active Fe ions to form Ni, and a protective layer can be rapidly deposited on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel. Although the thickness of the protective layer is thinner and less than 1 μm, the protective layer plays a key role in the binding force and the density of a surface copper layer, can realize stable and continuous copper plating process, and has controllable plating layer thickness and stable plating solution components.
In order to further improve the copper plating quality, in the copper plating, the copper plating solution comprises the following components: 200 to 300g/L of copper sulfate, 50 to 100ml/L of sulfuric acid, 0.1 to 0.2ml/L of cylinder opening agent, 1 to 2ml/L of brightening agent, 0.5 to 1ml/L of wetting agent and 0.2 to 5ml/L of softening agent, wherein the solvent is water, the temperature of copper plating is between 20 and 30 ℃, and the current density of the copper plating is between 3 and 4A/dm 2 The copper plating time is 10-15 min. Wherein, copper sulfate is a main reagent, and Cu is electrodeposited; the sulfuric acid provides mainly an acidic environment, maintaining sufficient H + Ions; the cylinder opening agent, the brightening agent, the wetting agent and the softening agent are mainly used for filling micropores, removing burrs on the surface of a plating layer, reducing surface tension and the like.
In order to protect the surface of the formed copper layer, improve the corrosion resistance of the copper layer and prevent the surface of the copper layer from discoloring or rusting, the method for plating the copper on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel further comprises the following steps after the copper plating:
the copper-plated 0Cr15Ni25Ti2MoAlVB stainless steel is subjected to post-treatment.
Specifically, in the post-treatment, the post-treatment medium is an anti-discoloration solution, the post-treatment temperature is 20-30 ℃, and the post-treatment time is 10-15 min. The anti-discoloration solution can prevent discoloration and oxidation after copper plating and keep brightness.
Similarly, the surface of the formed copper layer is subjected to a protective treatment to improve the corrosion resistance of the copper layer and prevent the surface of the copper layer from being discolored or rusted, and the following method may be adopted:
the copper plating method for the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel further comprises the following steps after post-treatment:
and (3) washing the post-treated 0Cr15Ni25Ti2MoAlVB stainless steel with water (washing for multiple times) and drying (drying for one time) in sequence.
Specifically, in the post-treatment, the drying temperature is 100-120 ℃, and the drying time is 2-3 min. The purpose of drying is to remove surface moisture and prevent rusting during storage. The drying temperature should not be too high, so that the copper layer can be prevented from being oxidized.
Example one
The embodiment provides a copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, which comprises the following steps:
the method comprises the following steps of sequentially carrying out electrolytic degreasing, primary acid washing, secondary acid washing, activation, pretreatment, copper plating, post-treatment and water washing drying on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel.
The reagents and process parameters used were as follows:
electrolytic degreasing:
NaOH：40g/L
Na 3 PO 4 .12H 2 O：5g/L
Na 2 CO 3 ：30g/L
Na 2 SiO 3 ：5g/L
OP emulsifier: 1ml/L
Defoaming agent (silicone emulsion): 0.3ml/L
Temperature: 30 deg.C
Current density: 5A/dm 2
Time: for 10min
Primary acid washing:
HNO 3 ：50ml/L
NH 4 HF 2 ：2g/L
citric acid: 5g/L
Urotropin: 2g/L
Temperature: room temperature (20 ℃ C.)
Time: 15min
Secondary acid washing (weak acid washing):
HCl：100ml/L
urotropin: 1g/L
Temperature: room temperature (20 ℃ C.)
Time: 5min
Activation:
HCl：80ml/L
polyethylene glycol (relative molecular weight 400 to 600): 0.03g/L
Temperature: room temperature (20 ℃ C.)
Time: 5min
Pretreatment:
HCl：100ml/L
NiCl 2 ：300g/L
sodium dodecylbenzenesulfonate: 0.01g/L
Temperature: room temperature (20 ℃ C.)
Time: for 10min
Copper plating:
copper sulfate: 200g/L
Sulfuric acid: 100ml/L
Cylinder opening agent (copper sulfate CuSO) 4 ·5H 2 O200g·L -1 Sulfuric acid H 2 SO 4 (d＝1.84)60g·L -1 0.0008 g.L of 2-thiazolidinethione -1 0.015 g/L sodium phenyl polydithio-propane sulfonate -1 Polyethylene glycol (relative molecular mass 6000) 0.04 g.L -1 And chloride ion Cl - 60mg·L -1 Sodium lauryl sulfate (or AEO emulsifier) 0.06 g.L -1 )：0.1ml/L
Brightener (N (1, 2-ethylenethiourea)): 2ml/L
Wetting agent (polyethylene glycol formal): 0.5ml/L
Softener (sodium phenyl polydithio propane sulfonate): 5ml/L
Temperature: room temperature (20 ℃ C.)
Current density: 4A/dm 2
Time: for 10min
And (3) post-treatment:
medium: anti-tarnishing solution (benzotriazole)
Temperature: room temperature (20 ℃ C.)
Time: and (5) 10min.
Washing and drying:
temperature: 120 deg.C
Time: and 2min.
In contrast, the copper layer of the copper-plated steel surface gave relatively satisfactory results. As can be seen from FIGS. 2 to 3, a clear copper layer was formed on the surface of the substrate, and the copper layer had a uniform thickness and good adhesion, and had a thickness of about 10 μm. Meanwhile, the SEM appearance of the cross section of the copper-plated steel shown in FIG. 4 can clearly show that the copper layer is completely covered on the surface of the substrate and is firmly combined, which means that the copper plating layer can play a better protection role.
Fig. 1 to 2 are a schematic diagram and an enlarged sectional view of a copper layer without secondary pickling, activation and pretreatment of a 0Cr15Ni25Ti2MoAlVB stainless steel surface, and fig. 3 to 4 are a schematic diagram and an enlarged sectional view of a copper layer using the copper plating method of a 0Cr15Ni25Ti2MoAlVB stainless steel surface according to the first embodiment, and it can be seen from fig. 1 to 4 that a plated layer formed without secondary pickling, activation and pretreatment of a 0Cr15Ni25Ti2MoAlVB stainless steel surface is inferior in quality, and is peeled off and poor in plating. The coating of the first embodiment is compact and compact in bonding, and does not fall off.
FIG. 5 is a schematic view of the line scanning direction of the 0Cr15Ni25Ti2MoAlVB stainless steel of the first embodiment, wherein the arrow direction is from the copper layer to the substrate; FIG. 6 is a line scan graph of 0Cr15Ni25Ti2MoAlVB stainless steel of the first embodiment, and it can be seen from FIGS. 5 to 6 that a plating layer with a thickness of about 7 μm is formed on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel substrate of the first embodiment.
Example two
The embodiment provides a copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, which comprises the following steps:
the method comprises the following steps of sequentially carrying out electrolytic degreasing, primary pickling, secondary pickling, activation, pretreatment, copper plating, post-treatment and washing and drying on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel.
The reagents and process parameters used were as follows:
electrolytic degreasing:
NaOH：20g/L
Na 3 PO 4 .12H 2 O：10g/L
Na 2 CO 3 ：20g/L
Na 2 SiO 3 ：15g/L
OP emulsifier: 0.5ml/L
Defoaming agent (silicone emulsion): 0.5ml/L
Temperature: 20 deg.C
Current density: 10A/dm 2
Time: 5min
Primary acid washing:
HNO 3 ：90ml/L
NH 4 HF 2 ：1g/L
and (3) citric acid: 10g/L
Urotropin: 12g/L
Temperature: room temperature (20 ℃ C.)
Time: 15min
Secondary acid washing (weak acid washing):
HCl：100ml/L
urotropin: 1g/L
Temperature: room temperature (20 ℃ C.)
Time: 3min
Activation:
HCl：120ml/L
polyethylene glycol (relative molecular weight 400-600): 0.01g/L
Temperature: room temperature (20 ℃ C.)
Time: 5min
Pretreatment:
HCl：150ml/L
NiCl 2 ：200g/L
sodium dodecylbenzenesulfonate: 0.03g/L
Temperature: room temperature (20 ℃ C.)
Time: 5min
Copper plating:
copper sulfate: 300g/L
Sulfuric acid: 50ml/L
Cylinder opening agent (copper sulfate CuSO) 4 ·5H 2 O200g·L -1 Sulfuric acid H 2 SO 4 (d＝1.84)60g·L -1 0.0008 g.L of 2-thiazolidinethione -1 0.015 g.L of sodium phenyl polydithio-propane sulfonate -1 Polyethylene glycol (relative molecular mass 6000) 0.04 g.L -1 Chloride ion Cl - 60mg·L -1 Sodium lauryl sulfate (or AEO emulsifier) 0.06 g.L -1 )：0.2ml/L
Brightener (M (2-mercaptobenzimidazole)): 1ml/L
Wetting agent (polyethylene glycol formal): 1ml/L
Softener (sodium phenyl-polydithio-propane sulfonate): 0.2ml/L
Temperature: room temperature (20 ℃ C.)
Current density: 3A/dm 2
Time: 15min
And (3) post-treatment:
medium: anti-tarnishing solution (benzotriazole)
Temperature: room temperature (20 ℃ C.)
Time: and (5) 15min.
Washing and drying:
temperature: 100 deg.C
Time: 3min.
EXAMPLE III
The embodiment provides a copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel, which comprises the following steps:
the method comprises the following steps of sequentially carrying out electrolytic degreasing, primary pickling, secondary pickling, activation, pretreatment, copper plating, post-treatment and washing and drying on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel.
The reagents and process parameters used were as follows:
electrolytic degreasing:
NaOH：30g/L
Na 3 PO 4 .12H 2 O：8g/L
Na 2 CO 3 ：25g/L
Na 2 SiO 3 ：10g/L
OP emulsifier: 0.8ml/L
Defoaming agent (silicone emulsion): 0.4ml/L
Temperature: 30 deg.C
Current density: 8A/dm 2
Time: 7min
Primary acid washing:
HNO 3 ：70ml/L
NH 4 HF 2 ：1.5g/L
citric acid: 8g/L
Urotropin: 1.5g/L
Temperature: room temperature (25 ℃ C.)
Time: 13min
Secondary acid washing (weak acid washing):
HCl：130ml/L
urotropin: 0.8g/L
Temperature: room temperature (30 ℃ C.)
Time: 4min
Activation:
HCl：100ml/L
polyethylene glycol (relative molecular weight 400-600): 0.02g/L
Temperature: room temperature (30 ℃ C.)
Time: 4min
Pretreatment:
HCl：130ml/L
NiCl 2 ：250g/L
sodium dodecylbenzenesulfonate: 0.02g/L
Temperature: room temperature (30 ℃ C.)
Time: 8min
Copper plating:
copper sulfate: 250g/L
Sulfuric acid: 80ml/L
Cylinder opening agent (copper sulfate CuSO) 4 ·5H 2 O200g·L -1 Sulfuric acid H 2 SO 4 (d＝1.84)60g·L -1 0.0008 g.L of 2-thiazolidinethione -1 0.015 g.L of sodium phenyl polydithio-propane sulfonate -1 Polyethylene glycol (relative molecular mass 6000) 0.04 g.L -1 Chloride ion Cl - 60mg·L -1 Sodium lauryl sulfate (or AEO emulsifier) 0.06 g.L -1 )：0.15ml/L
Brightener (SP sodium polydithio dipropanesulfonate): 1.5ml/L
Wetting agent (polyethylene glycol formal): 0.8ml/L
Softener (sodium phenyl-polydithio-propane sulfonate): 3.5ml/L
Temperature: room temperature (30 ℃ C.)
Current density: 3.5A/dm 2
Time: 12min
And (3) post-treatment:
medium: anti-tarnishing solution (benzotriazole)
Temperature: room temperature (30 ℃ C.)
Time: and 13min.
Washing and drying:
temperature: 110 deg.C
Time: 2.5min.
In the above copper plating process, the reagents used are commercially available.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.

Claims (7)

1. A copper plating method for the surface of 0Cr15Ni25Ti2MoAlVB stainless steel is characterized by comprising the following steps:
sequentially carrying out electrolytic degreasing, primary pickling, secondary pickling, activation, pretreatment and copper plating on the surface of 0Cr15Ni25Ti2MoAlVB stainless steel;
the secondary acid washing comprises the following steps: performing secondary acid washing on the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel subjected to the primary acid washing, wherein the components of a secondary acid washing solution comprise 100-150 ml/L of HCl and 0.5-1 g/L of urotropine;
the activation comprises the following steps: activating the surface of the 0Cr15Ni25Ti2MoAlVB stainless steel subjected to secondary pickling, wherein the components of an activation solution comprise 80-120 ml/L of HCl and 0.01-0.03 g/L of polyethylene glycol; the relative molecular weight of the polyethylene glycol is 400-600;
the electrolytic degreasing solution comprises the following components: naOH 20-40 g/L, na 3 PO 4 ·12H 2 O 5～10g/L、Na 2 CO 3 20～30g/L、Na 2 SiO 3 5 to 15g/L, 0.5 to 1ml/L OP emulsifier and 0.3 to 0.5ml/L defoamer; the temperature for electrolytic oil removal is 20-30 ℃;
the primary pickling solution comprises the following components: HNO 3 50～90ml/L、NH 4 HF 2 1-2 g/L, 5-10 g/L citric acid and 1-2 g/L urotropine;
the components of the pretreatment solution include: 100-150 ml/L of HCl and NiCl 2 200-300 g/L and 0.01-0.03 g/L of sodium dodecyl benzene sulfonate.
2. The method for copper plating of 0Cr15Ni25Ti2MoAlVB stainless steel surface according to claim 1, wherein the temperature of the secondary pickling is 20-30 ℃, and the time of the secondary pickling is 3-5 min.
3. The method for copper plating of 0Cr15Ni25Ti2MoAlVB stainless steel surface according to claim 1, wherein the activation temperature is 20-30 ℃ and the activation time is 3-5 min.
4. The method of copper plating a surface of 0Cr15Ni25Ti2MoAlVB stainless steel according to claim 1, wherein the composition of the copper plating solution comprises: 200 to 300g/L of copper sulfate, 50 to 100ml/L of sulfuric acid, 0.1 to 0.2ml/L of cylinder opening agent, 1 to 2ml/L of brightening agent, 0.5 to 1ml/L of wetting agent and 0.2 to 5ml/L of softening agent.
5. The method for copper plating of 0Cr15Ni25Ti2MoAlVB stainless steel surface according to any one of claims 1 to 4, further comprising the following steps after copper plating:
the copper-plated 0Cr15Ni25Ti2MoAlVB stainless steel is subjected to post-treatment.
6. The method of copper plating a surface of 0Cr15Ni25Ti2MoAlVB stainless steel according to claim 5, further comprising the steps after post-treatment of:
and (3) washing and drying the post-treated 0Cr15Ni25Ti2MoAlVB stainless steel in sequence.
7. The method for copper plating of a surface of 0Cr15Ni25Ti2MoAlVB stainless steel according to any one of claims 1 to 4, characterized in that the method for copper plating of a surface of 0Cr15Ni25Ti2MoAlVB stainless steel is used for a strip of 0Cr15Ni25Ti2MoAlVB stainless steel, a wire of 0Cr15Ni25Ti2MoAlVB stainless steel or a strip of 0Cr15Ni25Ti2MoAlVB stainless steel.
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