CN112376098A - Method for electroplating molybdenum-copper alloy surface - Google Patents
Method for electroplating molybdenum-copper alloy surface Download PDFInfo
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- CN112376098A CN112376098A CN202011156483.6A CN202011156483A CN112376098A CN 112376098 A CN112376098 A CN 112376098A CN 202011156483 A CN202011156483 A CN 202011156483A CN 112376098 A CN112376098 A CN 112376098A
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- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
- C25D5/38—Pretreatment of metallic surfaces to be electroplated of refractory metals or nickel
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- 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
- C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
- C23C18/36—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents using hypophosphites
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- 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
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- 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
- C23C28/023—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 only coatings of metal elements only
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- 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
- C23G1/10—Other heavy metals
- C23G1/106—Other heavy metals refractory metals
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- 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
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/20—Other heavy metals
- C23G1/205—Other heavy metals refractory metals
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- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
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- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
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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
- C25D5/10—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
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Abstract
The invention discloses a method for electroplating a molybdenum-copper alloy surface, which comprises oil removal, acid pickling, activation, special nickel plating, acidic chemical nickel plating and subsequent electroplating. The oil stain on the surface of the molybdenum-copper alloy is completely removed through the oil removing process, the oxidation film on the surface of the molybdenum-copper alloy is completely removed through the acid washing and activating processes, and the over-corrosion of copper is avoided while the oxidation film of molybdenum is removed; plating a very thin complete nickel layer with good binding force on the surface of the molybdenum-copper alloy through a special nickel plating process, and then increasing the thickness of the nickel layer through an acid chemical nickel plating process to prevent the atomic diffusion of molybdenum-copper materials and ensure the binding force of subsequent gold plating and silver plating; after the molybdenum-copper alloy is plated with gold or silver, the binding force can meet the requirement, and the gold-plated layer or the silver-plated layer has no bubbling or stripping phenomenon, thereby solving the problem that the metal layer on the molybdenum-copper alloy is difficult to plate. The method is not only suitable for parts with simple shapes and larger volumes, but also suitable for parts with complex shapes and smaller volumes.
Description
Technical Field
The invention belongs to the field of surface treatment, and relates to a method for electroplating a molybdenum-copper alloy surface.
Background
The molybdenum-copper alloy is a powder metallurgy material and has the excellent properties of high electric conductivity, high heat conductivity, small expansion coefficient, good corrosion resistance, no magnetism, good processability and the like. Particularly, the coefficient of thermal expansion, the heat conduction and the electric conduction of the molybdenum-copper material can be designed by adjusting the components of the material, thereby bringing great convenience to the application of the material. The molybdenum-copper alloy is widely applied to the fields of metallurgy, machinery, petrochemical industry, national defense, aerospace, electronics and the like, is particularly used as a package of a microwave device or an integrated circuit in microelectronic and power electronic devices, plays a role in supporting and radiating, and is widely applied to the field of military microelectronics. In practical use, the molybdenum-copper alloy used as a functional material is often subjected to surface treatment such as electroplating, coating and the like to meet some specific functional requirements of the surface, such as high-temperature brazing, contact resistance reduction and the like. The surface of the molybdenum-copper alloy is easy to be oxidized to form a complex oxide film, and the oxide film has stable chemical property and poor surface wettability, so that the surface treatment of the molybdenum-copper alloy is difficult. In order to prevent the formation of an oxide film on the surface of the molybdenum-copper alloy, a series of treatments are generally performed on the surface of the molybdenum-copper alloy, followed by gold plating and silver plating.
The existing electroplating method comprises the following steps: deoiling → sand blasting (uniform sand blasting with 100 mesh brown corundum under 0.4-0.6 MPa pressure) → anodic etching (sulfuric acid (98%): 80-150 ml/L, anodic current density: 3-5A/dm2And time: 1-3 min) → acid washing → activation → chromium plating (chromic anhydride: 110-150 g/L, sulfuric acid (98%): 1-1.5 g/L temperature: 50-55 ℃, current density: 15 to 25A/dm2And time: 2-5 min), impact nickel plating (nickel chloride: 220-260 g/L hydrochloric acid (3)6 percent of: 100-120 g/L, temperature: 20-30 ℃ and current density: 5 to 10A/dm2And time: 2-5 min) → vacuum heat treatment (the temperature is 900-980 ℃ in a vacuum environment, and the heat treatment is 20-30 min) → oil removal → activation → impact nickel plating → chemical nickel plating (bright nickel plating) → post-plating (gold plating or silver plating) according to the product requirements. The method comprises the steps of degreasing, sand blasting, anodic etching, acid washing and activating to completely remove an oxide film on the surface of the molybdenum-copper alloy, electroplating a thin layer of nickel on the surface of the molybdenum-copper alloy through chromium plating and nickel impact plating, then carrying out vacuum heat treatment to enable a nickel plating layer and a base material to form a diffusion layer with good bonding force, and then activating and nickel plating the diffusion layer to continuously electroplate a required plating layer. According to the adhesive tape test and the thermal shock test method in the GJB1290515290 'test method for the bonding strength of gold and gold alloy electroplated layers', the bonding force of the electroplated layers is respectively tested, and the qualification rate is only 70-80%.
The prior electroplating process of molybdenum-copper alloy mainly has the following problems: 1. an oxide film is easily formed on the surface of the molybdenum-copper alloy and is difficult to remove, and the base material cannot be effectively activated before electroplating, so that the binding force of a plating layer is influenced; 2. the existing oxide film removing method mainly comprises a sand blasting method, an anode etching method, a chromic acid treatment method and the like, but the sand blasting method is only suitable for parts with simple shapes and large volumes, and is not suitable for parts with complex shapes and small volumes; the anodic etching method is easy to cause over-corrosion of copper when the molybdenum-copper alloy is treated; the chromic acid treatment method needs high-content chromic acid, has complex process flow, is easy to cause environmental pollution and personal injury, and has low yield. The molybdenum-copper alloy is a powder metallurgy material, but not a true alloy, and the chemical properties of molybdenum and copper are very different, so a reliable oxide film removing process is to be found, and the over-corrosion of copper can not be caused while the oxide film of molybdenum is removed. Long-term process practice proves that the direct gold and silver plating on the molybdenum-copper alloy substrate cannot obtain a plating layer with good bonding force.
Disclosure of Invention
The invention aims to provide a novel molybdenum-copper alloy surface electroplating method aiming at the defects of the existing molybdenum-copper alloy surface electroplating method, and a coating with good bonding force can be obtained on the surface of the molybdenum-copper alloy by the novel molybdenum-copper alloy surface electroplating method.
The purpose of the invention is realized by the following technical scheme:
a method for electroplating the surface of Mo-Cu alloy includes such steps as removing oil, acid washing, activating, plating special Ni, acidic chemical Ni, and electroplating; the method specifically comprises the following steps:
step (1), deoiling: under the action of ultrasonic waves, soaking the molybdenum-copper alloy part in degreasing liquid for 20-30 min to remove oil stains on the surface of the molybdenum-copper alloy part; wherein the deoiling liquid contains 30-40 g/L of sodium carbonate, 40-50 g/L of trisodium phosphate and 5-10 g/L of water glass, and the temperature of the solution is 70-80 ℃;
step (2), acid washing: soaking the molybdenum-copper alloy part into a pickling solution, shaking for 10-15S, and washing off an oxide film and stains on the surface of the part to obtain a uniform and clean metal surface; after acid washing, immediately putting the molybdenum-copper alloy part into tap water for cleaning; wherein, every 1L of pickling solution is prepared by 80-100 mL of nitric acid, 400-420 mL of sulfuric acid and 5mL of hydrochloric acid, the concentration of the nitric acid is 63%, the concentration of the sulfuric acid is 98% and the concentration of the hydrochloric acid is 36%; the temperature of the pickling solution is 10-25 ℃; the acid washing process can quickly wash off oxide films and stains on the surfaces of the parts to obtain uniform and clean metal surfaces;
step (3), activation: immersing the molybdenum-copper alloy part into the activating solution for 1-2 min, further thoroughly removing an oxidation film on the surface of the molybdenum-copper alloy part after bubbles are uniformly separated from the surface of the part, taking out the part, and quickly putting the part into tap water for cleaning; wherein, each 1L of the activating solution is prepared from 40-60 mL of nitric acid and 400-420 mL of sulfuric acid, the concentration of the nitric acid is 63 percent, and the concentration of the sulfuric acid is 98 percent; the temperature of the activating solution is 20-30 ℃;
step (4), plating special nickel: immersing the molybdenum-copper alloy part into a nickel plating solution, wherein the nickel plating solution contains 8-15 g/L of nickel chloride, 80-90 g/L of sodium citrate, 40-60 g/L of ammonium chloride and 60-80 g/L of potassium nitrate, the pH value of the solution is 8-9.5, and the cathode current density is 0.5-1A/dm2The temperature of the solution is 25-35 ℃, an electrolytic nickel plate with the purity of 99.99% is adopted as an anode, and the nickel plating time is 1-4 min; a layer of thin and compact combination is rapidly generated on the surface of the molybdenum-copper alloyA nickel layer with excellent strength as a transitional coating of the subsequent acid chemical nickel plating;
step (5), acid chemical nickel plating: immersing the molybdenum-copper alloy part into an acidic chemical nickel plating solution, wherein the acidic chemical nickel plating solution contains 30-40 g/L nickel sulfate, 70-90 g/L citric acid, 7-10 g/L sodium acetate and 15-20 g/L sodium hypophosphite, the pH value is 4.5-5.5, the solution temperature is 85-95 ℃, the time is determined according to the product thickness requirement, the thickness of a chemical nickel layer is ensured to be more than 3 micrometers, so that the diffusion of copper and molybdenum atoms is thoroughly prevented, and the quality of a plating layer for subsequent gold and silver plating is ensured;
step (6) and subsequent electroplating: gold or silver plating.
The degreasing solution, the pickling solution, the activating solution, the nickel plating solution and the acidic chemical nickel plating solution are all aqueous solutions.
The invention has the beneficial effects that:
the oil stain on the surface of the molybdenum-copper alloy is completely removed through the oil removing process, the oxidation film on the surface of the molybdenum-copper alloy is completely removed through the acid washing and activating processes, and the over-corrosion of copper is avoided while the oxidation film of molybdenum is removed; plating a very thin complete nickel layer with good binding force on the surface of the molybdenum-copper alloy through a special nickel plating process, and then increasing the thickness of the nickel layer through an acid chemical nickel plating process to prevent the atomic diffusion of molybdenum-copper materials and ensure the binding force of subsequent gold plating and silver plating; after the molybdenum-copper alloy is plated with gold or silver, the binding force can meet the requirement, and the gold-plated layer or the silver-plated layer has no bubbling or stripping phenomenon, thereby solving the problem that the metal layer on the molybdenum-copper alloy is difficult to plate. If the special nickel plating process is omitted, the bonding force of the plating layer obtained by gold plating or silver plating cannot meet the requirement, and the failure rate reaches 100 percent.
The method is not only suitable for parts with simple shapes and larger volumes, but also suitable for parts with complex shapes and smaller volumes.
The invention simplifies the prior 13 steps of molybdenum-copper alloy electroplating into 6 steps, thereby greatly improving the production efficiency. The invention omits the chromium plating process, and reduces the pollution of hexavalent chromium; and vacuum heat treatment is omitted, so that the energy consumption is greatly reduced. The invention greatly reduces the cost, protects the environment, is a good technology and a good process for clean production, and is worthy of popularization and application.
Drawings
FIG. 1 is a graph showing the results of the tape test of the gold-plated Mo-Cu alloy support of example 1.
FIG. 2 is a graph showing the results of the thermal shock test method for the gold-plated Mo-Cu alloy support of example 1.
FIG. 3 is a graph showing the results of the tape test of the gold-plated Mo-Cu alloy carrier of example 2.
FIG. 4 is a graph showing the results of the thermal shock test method for the gold-plated Mo-Cu alloy support of example 2.
FIG. 5 is a graph showing the results of the thermal shock test method for the gold-plated Mo-Cu alloy support of example 3.
Detailed Description
And (3) testing and analyzing the performance of the plating layer:
the binding force of the plating layer is respectively tested according to a tape test and a thermal shock test method in GJB1290515290 'test method for the binding strength of gold and gold alloy electroplated layers'.
Tape test method: the surface of the test piece is scribed with square grids with the side length of 2mm, the pressure used during scribing is capable of cutting through the coating once to reach the base metal, then the test piece is adhered to the test surface by an adhesive tape, the test piece is pressed and pressed flat by a finger, after 10 seconds, the adhesive tape is quickly pulled up in the vertical direction of the surface of the sample, and whether the coating is peeled off or not is checked under an illumination observation system with the magnification of 8 times.
Thermal shock test method: and (3) putting the test piece into an oven at 200-300 ℃ (the temperature of the thermal shock test is 380-400 ℃ because the brazing temperature of the planting body is 350 ℃), heating for 30 minutes, taking out, immediately immersing into water at room temperature, taking out, and drying. The coating was examined for blistering and separation under an 8-fold magnification lighting observation system.
Example 1
A method for electroplating a molybdenum-copper alloy surface comprises the following steps:
step (1), deoiling: putting 500 pieces of molybdenum-copper alloy carriers (70 percent of molybdenum and 30 percent of copper; the specification is 14mm multiplied by 10mm multiplied by 1mm) into degreasing fluid, wherein the degreasing fluid is an aqueous solution containing 35g/L of sodium carbonate, 46g/L of trisodium phosphate and 8g/L of water glass, the temperature of the aqueous solution is 72-76 ℃, and the aqueous solution is soaked for 30 minutes under the ultrasonic action of ultrasonic frequency 25HZ and ultrasonic current 2A so as to completely remove oil stains on the surfaces of the carriers;
the carrier was taken out and washed in running tap water for 5 seconds while shaking the carrier left and right, up and down.
Step (2), acid washing: the pickling solution comprises the following components: 90mL/L nitric acid (63%), 420mL/L sulfuric acid (98%), and 5mL/L hydrochloric acid (36%); putting the carrier into a pickling solution, wherein the temperature of the solution is 22 ℃, and shaking the carrier in the pickling solution for 15 seconds to remove an oxide film on the surface of the carrier and obtain a uniform and clean metal surface;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (3), activation: the components of the activating solution are as follows: 50mL/L of nitric acid (63%) and 420mL/L of sulfuric acid (98%); putting a carrier into an activating solution, enabling the solution temperature to be 22 ℃, shaking the activating solution for 80 seconds, taking out the carrier when bubbles are uniformly separated out from the surface of the carrier, quickly putting the carrier into tap water, and shaking and cleaning the carrier for 2 seconds to further thoroughly remove an oxide film on the surface of the carrier and obtain a metal surface meeting the electroplating requirement;
step (4), plating special nickel: the nickel plating solution comprises the following components: 15g/L of nickel chloride, 90g/L of trisodium citrate, 50g/L of ammonium chloride, 80g/L of potassium nitrate and the pH value of 9.2; quickly putting the carrier into a nickel plating solution, wherein the solution temperature is 25-30 ℃, the anode is an electrolytic nickel plate with the concentration of 99.99 percent, and the cathode current density is 1A/dm2Electroplating for 3 minutes to form a thin and compact nickel layer with excellent binding force on the surface of the carrier;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (5), acid chemical nickel plating: quickly putting the carrier into the acidic chemical nickel plating solution, wherein the acidic chemical nickel plating solution comprises the following components in percentage by weight: 35g/L of nickel sulfate, 80g/L of citric acid, 10g/L of sodium acetate, 20g/L of sodium hypophosphite, 5.2 of pH value, 85-90 ℃ of solution temperature and 15 minutes to obtain a nickel layer of 3 microns;
the carrier was taken out and washed in running tap water for 5 seconds while shaking the carrier left and right, up and down.
Step (6), gold plating: the gold plating solution comprises the following components: 8g/L of potassium aurous cyanide, 130g/L of ammonium citrate and 5.5 of pH value; quickly putting the carrier into a gold plating solution, wherein the solution temperature is 35-40 ℃, the anode is a 316 stainless steel plate, and the cathode current density is 0.1A/dm2Electroplating for 40 minutes by using the current to obtain a 2-micron gold layer;
and taking out the carrier, shaking and cleaning the carrier in flowing tap water for 5 seconds, shaking and cleaning the carrier in deionized boiling water for 5 minutes, taking out the carrier, and drying the carrier by using an electric blower.
The 20 gold-plated molybdenum-copper alloy carriers are taken, the front and back surfaces of each carrier are respectively tested according to a tape test (shown in figure 1) and a thermal shock test (the thermal shock temperature is determined to be 400 ℃ according to the welding temperature requirement of the carriers) in a GJB1290515290 (gold and gold alloy electroplated layer bonding strength test method) (shown in figure 2), the electroplated layers are free of stripping and foaming phenomena, and the qualification rate is 100%.
Example 2
A method for electroplating a molybdenum-copper alloy surface comprises the following steps:
step (1), deoiling: 100 pieces of molybdenum-copper alloy carriers (molybdenum 85 percent, copper 15 percent, specification: 24mm multiplied by 18mm multiplied by 1mm) are put into degreasing liquid (the composition of the degreasing liquid is 33g/L of sodium carbonate, 50g/L of trisodium phosphate and 9g/L of water glass), the temperature of the solution is 71-78 ℃, and the carrier is soaked for 30 minutes under the ultrasonic action of ultrasonic frequency 25HZ and ultrasonic current 2A to thoroughly remove oil stains on the surface of the carrier;
the carrier was taken out and washed in running tap water for 5 seconds while shaking the carrier left and right, up and down.
Step (2), acid washing: the pickling solution comprises the following components: 90mL/L of nitric acid (63%), 415mL/L of sulfuric acid (98%), and 5mL/L of hydrochloric acid (36%); putting the carrier into a pickling solution, wherein the temperature of the solution is 24 ℃, and shaking the carrier in the pickling solution for 15 seconds to remove an oxide film on the surface of the carrier and obtain a uniform and clean metal surface;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (3), activation: the components of the activating solution are as follows: 50mL/L nitric acid (63%) and 415mL/L sulfuric acid (98%); putting the carrier into an activating solution, enabling the solution temperature to be 24 ℃, shaking the activating solution for 90 seconds, taking out the carrier when bubbles are uniformly separated out from the surface of the carrier, quickly putting the carrier into tap water, and shaking and cleaning the carrier for 2 seconds to further thoroughly remove an oxide film on the surface of the carrier and obtain a metal surface meeting the electroplating requirement;
step (4), plating special nickel: the nickel plating solution comprises the following components: 15g/L of nickel chloride, 85g/L of trisodium citrate, 50g/L of ammonium chloride, 75g/L of potassium nitrate and 9.0 of pH value; quickly putting the carrier into a nickel plating solution, wherein the solution temperature is 25-30 ℃, the anode is an electrolytic nickel plate with the concentration of 99.99 percent, and the cathode current density is 1A/dm2Electroplating for 3 minutes to form a thin and compact nickel layer with excellent binding force on the surface of the carrier;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (5), acid chemical nickel plating: the components of the acidic chemical nickel plating solution are as follows: 30g/L of nickel sulfate, 80g/L of citric acid, 10g/L of sodium acetate, 20g/L of sodium hypophosphite and a pH value of 5.0; and (3) quickly putting the carrier into the acidic chemical nickel plating solution, wherein the solution temperature is 85-90 ℃, and the nickel layer with the thickness of 4 microns is obtained after 20 minutes.
Taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (6), gold plating: the gold plating solution comprises the following components: 8.5g/L of potassium aurous cyanide, 125g/L of ammonium citrate and 5.4 of pH value; quickly putting the carrier into a gold plating solution, wherein the solution temperature is 35-40 ℃, the anode is a 316 stainless steel plate, and the cathode current density is 0.1A/dm2The current was electroplated for 40 minutes to obtain a 2 micron gold layer.
And taking out the carrier, shaking and cleaning the carrier in flowing tap water for 5 seconds, shaking and cleaning the carrier in deionized boiling water for 5 minutes, taking out the carrier, and drying the carrier by using an electric blower.
20 pieces of the gold-plated molybdenum-copper alloy support were subjected to the bonding strength test method of example 1. The adhesive tape test is shown in figure 3, the thermal shock test is shown in figure 4, the coating does not peel and bubble, and the qualification rate is 100%.
Example 3
A method for electroplating a molybdenum-copper alloy surface comprises the following steps:
step (1), deoiling: putting 1000 pieces of molybdenum-copper alloy carrier (70% of molybdenum and 30% of copper; the specification is 4.1mm multiplied by 2.3mm multiplied by 0.2mm) into degreasing liquid (the components of the degreasing liquid are 30g/L of sodium carbonate, 50g/L of trisodium phosphate and 8g/L of water glass), soaking for 30 minutes at the temperature of 72-76 ℃ under the ultrasonic action of ultrasonic frequency 25HZ and ultrasonic current 2A to thoroughly remove oil stains on the surface of the carrier;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (2), acid washing: the pickling solution comprises the following components: 90mL/L nitric acid (63%), 420mL/L sulfuric acid (98%), and 5mL/L hydrochloric acid (36%); putting the carrier into a pickling solution, wherein the temperature of the solution is 22 ℃, and shaking the carrier in the pickling solution for 15 seconds to remove an oxide film on the surface of the carrier and obtain a uniform and clean metal surface;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (3), activation: the components of the activating solution are as follows: 50mL/L of nitric acid (63%) and 420mL/L of sulfuric acid (98%); putting a carrier into an activating solution, enabling the solution temperature to be 22 ℃, shaking the carrier in the activating solution for 70 seconds, taking out the carrier when bubbles are uniformly separated out from the surface of the carrier, quickly putting the carrier into tap water, and shaking and cleaning the carrier for 2 seconds to further thoroughly remove an oxide film on the surface of the carrier and obtain a metal surface meeting the electroplating requirement;
step (4), plating special nickel: the nickel plating solution comprises the following components: 15g/L of nickel chloride, 90g/L of trisodium citrate, 50g/L of ammonium chloride, 80g/L of potassium nitrate and the pH value of 9.0; quickly putting the carrier into a nickel plating solution, wherein the solution temperature is 25-30 ℃, the anode is an electrolytic nickel plate with the concentration of 99.99 percent, and the cathode current density is 1A/dm2Electroplating for 4 minutes to form a thin and compact nickel layer with excellent binding force on the surface of the carrier;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (5), acid chemical nickel plating: the components of the acidic chemical nickel plating solution are as follows: 30g/L of nickel sulfate, 90g/L of citric acid, 10g/L of sodium acetate, 20g/L of sodium hypophosphite and a pH value of 5.1; quickly putting the carrier into an acidic chemical nickel plating solution, wherein the solution temperature is 85-90 ℃, and the nickel layer with the thickness of 3 microns is obtained after 15 minutes;
taking out the carrier, washing the carrier in flowing tap water for 5 seconds, and shaking the carrier left and right and up and down during washing;
step (6), gold plating: the gold plating solution comprises the following components: 7g/L of potassium aurous cyanide, 120g/L of ammonium citrate and 5.0 of pH value; quickly putting the carrier into a gold plating solution, wherein the solution temperature is 35-40 ℃, the anode is a 316 stainless steel plate, and the cathode current density is 0.1A/dm2Electroplating for 40 minutes by using the current to obtain a 2-micron gold layer;
and taking out the carrier, shaking and cleaning the carrier in flowing tap water for 5 seconds, shaking and cleaning the carrier in deionized boiling water for 5 minutes, taking out the carrier, and drying the carrier by using an electric blower.
The 20 pieces of gold-plated molybdenum-copper alloy carriers were tested according to the bonding strength test method of example 1 (only thermal shock test was performed because the carrier size was too small to perform tape test), the thermal shock test is shown in fig. 5, the plating layer did not foam and peel, and the yield was 100%.
Claims (6)
1. A method for electroplating the surface of a molybdenum-copper alloy is characterized by comprising the steps of oil removal, acid pickling, activation, special nickel plating, acidic chemical nickel plating and subsequent electroplating; the method specifically comprises the following steps:
step (1), deoiling: under the action of ultrasonic waves, soaking the molybdenum-copper alloy part in degreasing fluid to remove oil stains on the surface of the molybdenum-copper alloy part;
step (2), acid washing: soaking the molybdenum-copper alloy part into a pickling solution, shaking for 10-15S, and washing off an oxide film and stains on the surface of the part to obtain a uniform and clean metal surface;
step (3), activation: immersing the molybdenum-copper alloy part into the activating solution for 1-2 min, taking out the part after bubbles are uniformly separated from the surface of the part, and putting the part into water for cleaning;
step (4), plating special nickel: immersing the molybdenum-copper alloy part into a nickel plating solution containing 8-15 g/L of chlorideNickel, 80-90 g/L sodium citrate, 40-60 g/L ammonium chloride and 60-80 g/L potassium nitrate, the pH value of the solution is 8-9.5, and the cathode current density is 0.5-1A/dm2The temperature of the solution is 25-35 ℃, an electrolytic nickel plate with the purity of 99.99% is adopted as an anode, and the nickel plating time is 1-4 min; generating a transitional coating on the surface of the molybdenum-copper alloy;
step (5), acid chemical nickel plating: immersing the molybdenum-copper alloy part into an acidic chemical nickel plating solution to obtain a chemical nickel layer with the thickness of more than 3 microns;
step (6) and subsequent electroplating: gold or silver plating.
2. The method for electroplating the surface of the molybdenum-copper alloy according to claim 1, wherein in the step (1), the degreasing fluid contains 30-40 g/L sodium carbonate, 40-50 g/L trisodium phosphate and 5-10 g/L water glass, and the temperature of the solution is 70-80 ℃.
3. The method for electroplating the surface of the molybdenum-copper alloy as claimed in claim 1, wherein in the step (2), the molybdenum-copper alloy part is immediately put into water for cleaning after being acid-washed.
4. The method for electroplating the surface of the molybdenum-copper alloy according to claim 1, wherein in the step (2), each 1L of the pickling solution is prepared from 80-100 mL of nitric acid, 400-420 mL of sulfuric acid and 5mL of hydrochloric acid, wherein the concentration of the nitric acid is 63%, the concentration of the sulfuric acid is 98% and the concentration of the hydrochloric acid is 36%; the temperature of the pickling solution is 10-25 ℃.
5. The method for electroplating the surface of the molybdenum-copper alloy according to claim 1, wherein in the step (3), each 1L of the activating solution is prepared from 40-60 mL of nitric acid and 400-420 mL of sulfuric acid, the concentration of the nitric acid is 63% and the concentration of the sulfuric acid is 98%; the temperature of the activating solution is 20-30 ℃.
6. The method for electroplating the surface of the molybdenum-copper alloy according to claim 1, wherein in the step (3), the acidic electroless nickel plating solution contains 30-40 g/L nickel sulfate, 70-90 g/L citric acid, 7-10 g/L sodium acetate, and 15-20 g/L sodium hypophosphite, has a pH of 4.5-5.5, and has a solution temperature of 85-95 ℃.
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| CN115449769A (en) * | 2022-10-28 | 2022-12-09 | 西安稀有金属材料研究院有限公司 | High-temperature-resistant low-diffusion alloy film for copper substrate and preparation method thereof |
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| CN115449769B (en) * | 2022-10-28 | 2023-11-21 | 西安稀有金属材料研究院有限公司 | High-temperature-resistant low-diffusion alloy film for copper matrix and preparation method thereof |
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