CN111962117B - Multilayer nickel plating process for ceramic-metal shell - Google Patents
Multilayer nickel plating process for ceramic-metal shell Download PDFInfo
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- CN111962117B CN111962117B CN202010638974.8A CN202010638974A CN111962117B CN 111962117 B CN111962117 B CN 111962117B CN 202010638974 A CN202010638974 A CN 202010638974A CN 111962117 B CN111962117 B CN 111962117B
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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
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
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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
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
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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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1646—Characteristics of the product obtained
- C23C18/165—Multilayered product
- C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
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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
- 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
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1689—After-treatment
- C23C18/1692—Heat-treatment
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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
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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
- 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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/007—Current directing devices
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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
- C25D3/12—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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- 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
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- 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
- C25D5/54—Electroplating of non-metallic surfaces
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Abstract
The invention discloses a multilayer nickel plating process of a ceramic-metal shell, which comprises a shell plating pretreatment process, a shell nickel plating process and a dehydrogenation process, wherein the shell plating pretreatment process comprises the following steps: grinding and polishing, oil removal and acid cleaning, wherein in the oil removal treatment, the ceramic-metal shell is placed in an oil removal agent, and ultrasonic waves are introduced into the oil removal agent; the shell nickel plating process comprises the following steps: electroplating impact nickel → deionized water → electroplating high phosphorus nickel → cleaning, drying → annealing → dry spraying → hydrochloric acid → deionized water → putting in protective liquid → reducing liquid → deionized water → small current electroplating nickel → deionized water → chemical plating middle phosphorus nickel → deionized water → gold plating → deionized water drying and drying; the dehydrogenation treatment process is to carry out annealing treatment at the temperature of 470-500 ℃; the stress among the plating layer, the shell and the plating layer is effectively reduced, the hydrogen embrittlement phenomenon of the lead and the penetration of a plating layer pinhole are prevented, and the problems of peeling, cracks and the like in the plating layer of the ceramic-metal shell are effectively solved.
Description
Technical Field
The invention relates to the technical field of ceramic-metal shell manufacturing, in particular to a multilayer nickel plating process of a ceramic-metal shell.
Background
Electroplating is a process of plating a thin layer of other metals or alloys on the surface of some metals by using the principle of electrolysis, and is a process of attaching a layer of metal film on the surface of a metal or other material product by using the action of electrolysis, thereby having the effects of preventing metal oxidation (such as corrosion), improving wear resistance, conductivity, light reflection, corrosion resistance (such as copper sulfate and the like), enhancing the appearance and the like.
At present, the ceramic-metal shell for packaging electronic components has the following problems in the aspects of plating process and pre-plating treatment: at high temperature, the defects such as stripping, cracks and the like are easy to appear in the coating of the ceramic-metal shell, and the air tightness and reliability of the ceramic-metal shell are seriously influenced, because internal stress exists between the coating and a base material and between the coating and the coating, and when the temperature rises, the defects such as stripping, cracks and the like of the coating can be caused by the stress; the ceramic-metal shell is stained by animal and vegetable oil and mineral oil simultaneously in the manufacturing process, a good effect cannot be achieved by only using the degreasing agent, the ceramic-metal shell is complex in structure, and the degreasing agent is only used for degreasing and is difficult to completely degrease at a dead angle of the structure, so that the surface of a matrix is excessively polluted, and the plating performance is unstable due to incomplete pre-plating treatment; moreover, the high-temperature and high-low temperature circulating environment is more unfavorable for the adhesion of the coating; in addition, the existing nickel plating process can cause the nickel plating layer to be uneven under the influence of various factors, and the unevenness of the plating layer can also cause the occurrence of larger stress, thereby causing the phenomena of stripping, cracking and the like of the plating layer; in the prior art, a nickel plating layer generates pinholes which are difficult to solve through the process, and the pinholes can penetrate through the metal surface to seriously affect the salt spray resistance of the shell. Therefore, in order to make the ceramic-metal case normally usable in a high temperature environment, it is necessary to reduce the stress between the plating layer and the base material, and between the plating layers, to increase the adhesion, and to prevent the hydrogen embrittlement phenomenon.
Disclosure of Invention
In order to solve the problems, the invention provides a multilayer nickel plating process for a ceramic-metal shell, the ceramic-metal shell electroplated by the process has uniform plating, effectively improves the phenomena of stripping, cracking and the like of the plating, and can stably work at the high temperature of 250 ℃.
The technical scheme adopted by the invention is as follows:
a multilayer nickel plating process of a ceramic-metal shell comprises a shell plating pretreatment process, a shell nickel plating process and a dehydrogenation process, wherein the shell plating pretreatment process comprises the following steps: and sequentially carrying out grinding and polishing, oil removal and acid pickling on the ceramic-metal shell, wherein in the oil removal treatment, the ceramic-metal shell is placed in an oil removal agent, and ultrasonic waves are introduced into the oil removal agent.
The shell nickel plating process comprises the following steps:
electroplating impact nickel → deionized water → electroplating high phosphorus nickel → cleaning, drying → annealing → dry spraying → hydrochloric acid → deionized water → putting in protective liquid → reducing liquid → deionized water → small current electroplating nickel → deionized water → chemical plating medium phosphorus nickel → deionized water → gold plating → deionized water drying and drying.
The dehydrogenation treatment process comprises the steps of performing dehydrogenation treatment at the temperature of 470-500 ℃ and under the pressure of less than or equal to 5 multiplied by 10-3Annealing treatment is carried out under the condition of Pa.
In the process of pretreatment of plating on the ceramic-metal shell, the ceramic-metal shell is degreased by a process combining chemical degreasing agent degreasing and ultrasonic cleaning, an ultrasonic field is introduced into a chemical degreasing solvent, mechanical energy generated by ultrasonic oscillation can generate a large number of vacuum cavities in the solution, and the cavities promote the solution to oscillate, so that oil stains on all parts of the ceramic-metal shell are impacted, and the combination of the chemical degreasing and the ultrasonic degreasing can remove animal and vegetable oil and mineral oil simultaneously, and the oil stains on the dead corners of the structure can be removed completely, thereby ensuring the cleanness of the surface of the ceramic-metal shell before electroplating, and effectively reducing the stress between a plating layer and a base material caused by incomplete pretreatment of plating.
In the shell nickel plating process, the ceramic-metal shell is subjected to multilayer nickel plating, annealing and dry spraying treatment are carried out after high-phosphorus nickel is electroplated, and then electroplating of low-current nickel electroplating is carried out, so that pinholes among the coatings can be staggered, the penetration of the coating pinholes is prevented, and the salt spray resistance of the ceramic-metal shell is effectively improved.
In the dehydrogenation treatment process, the ceramic-metal shell is annealed at the temperature of 470-500 ℃, so that hydrogen generated by the grain boundary of the lead material of the ceramic-metal shell in the electroplating process is eliminated, and the hydrogen embrittlement phenomenon that the lead is easily embrittled is prevented.
Preferably, the electroplating process of the shell nickel plating process is carried out in an electroplating bath, a U-shaped copper wire is arranged in the electroplating bath, two ends of the U-shaped copper wire are respectively hung on the upper edges of two opposite sides of the electroplating bath, and the bottom of the U-shaped copper wire extends into the bottom of the electroplating bath; in the electroplating process, the current at the bottom of the electroplating bath is large, and the current at the bottom of the electroplating bath is upwards transmitted along the U-shaped copper wire by arranging the U-shaped copper wire, so that the current in the electroplating bath is uniformly distributed, and the problems of uneven plating layer and brittle lead caused by large local current density in the electroplating bath are solved.
Preferably, the electroplating current density adopted by the low-current nickel electroplating is 0.3A/dm2Adjusting the plating current density prevents the problem of lead embrittlement caused by excessive current density.
Preferably, the formulation of the solution for electroplating the strike nickel is: 180-240 g/L of nickel chloride, 80-120 g/L of hydrochloric acid and the balance of water; the formula of the solution for electroplating high phosphorus nickel is as follows: 300g/L of nickel sulfate, 40g/L of boric acid and the balance of water.
The formula of the solution for low-current nickel electroplating is as follows: 180g/L of nickel sulfate 160-180g/L, 30-40g/L of sodium chloride, 35-40g/L of boric acid, 30-35g/L of magnesium sulfate and the balance of water; the pH value of the solution is 3-4, and the electroplating temperature is 45-55 ℃; in order to meet the condition of low-current nickel electroplating, the formula is optimized for low-current nickel electroplating, the concentration of nickel sulfate in the conventional nickel electroplating formula is reduced to 160-180g/L, and the lead is prevented from becoming brittle due to high current and the uniformity of a plating layer is ensured.
The formula of the solution for chemically plating the phosphorus and the nickel comprises the following components: 45ml/L of nickel sulfamate solution, 100ml/L of sodium hydroxide solution and the balance of water.
Preferably, in the annealing treatment in the dehydrogenation treatment process, the annealing treatment is carried out at 470-500 ℃ for 30-40min, and then the annealing treatment is cooled to room temperature.
Preferably, the gold plating solution formulation is: 5-12g/L of gold potassium citrate, 150g/L of potassium citrate 140-; the pH of the gold plating solution is 3.5-5.8, and the plating temperature is 40-50 ℃.
Preferably, in the grinding and polishing treatment, the ceramic-metal shell is ground and polished by using an abrasive material with the particle size of 300-250 μm; the frequency of ultrasonic wave adopted by ultrasonic treatment is 16 KHz; the pickling solution adopted in the pickling treatment is a hydrochloric acid solution with the volume ratio of hydrochloric acid to water being 1: 1.
Preferably, the multilayer nickel structure of the ceramic-metal shell obtained by the multilayer nickel plating process of the ceramic-metal shell comprises a ceramic-metal shell, an impact nickel layer, a high-phosphorus nickel layer, a low-current electroplated nickel layer, a medium-phosphorus nickel layer and a gold plating layer which are sequentially connected from bottom to top; the multilayer nickel plating effectively prevents the pinhole from penetrating, and improves the salt spray resistance of the ceramic-metal shell; the ceramic-metal shell is electroplated with impact nickel in a reduction state, so that the binding force between the plating layer and the ceramic-metal shell is enhanced, and the stress between the ceramic-metal shell and the plating layer is reduced; the phosphorus element accounts for 10-12% of the high-phosphorus nickel layer by mass, the phosphorus element accounts for 7-9% of the medium-phosphorus nickel layer by mass, and the high-phosphorus nickel can be diffused among the plating layers, so that the bonding force among the plating layers is further enhanced, and the stress among the plating layers is reduced; the outermost layer is plated with the gold layer, so that the antirust performance is better, and the ceramic-metal shell is effectively protected.
Compared with the prior art, the multilayer nickel plating process of the ceramic-metal shell provided by the invention,
1. the ceramic-metal shell is annealed at 470-500 ℃ for dehydrogenation treatment, so that the hydrogen embrittlement phenomenon that the lead is easily embrittled is effectively prevented.
2. The U-shaped copper wire is arranged in the electroplating bath, so that the current at the bottom of the electroplating bath is transmitted upwards along the U-shaped copper wire, and the problems of uneven plating and fragile lead caused by high local current density in the electroplating bath are solved.
3. The ceramic-metal shell is degreased by adopting a process combining chemical degreasing agent degreasing and ultrasonic cleaning, so that the stress between a plating layer and a base material, which is generated by incomplete plating pretreatment, is effectively reduced.
4. The ceramic-metal shell is plated with multilayer nickel, so that the penetration of a coating pinhole is prevented, and the salt spray resistance of the ceramic-metal shell is effectively improved; the ceramic-metal shell is electroplated with impact nickel in a reduction state, so that the stress between the ceramic-metal shell and the coating is reduced; the high-phosphorus nickel can be diffused among the coating layers, so that the stress among the coating layers is further reduced; the outermost layer is plated with the gold layer, so that the antirust performance is better, and the ceramic-metal shell is effectively protected.
Drawings
FIG. 1 is a schematic structural view of a U-shaped copper wire placed in an electroplating bath;
FIG. 2 is a schematic structural view of a multilayer nickel of a ceramic-metal housing;
reference numerals: 1. plating a gold layer; 2. a medium phosphorus nickel layer; 3. electroplating a nickel layer at a low current; 4. a high phosphorus nickel layer; 5. impacting the nickel layer;
6. a ceramic-metal housing; 7. an electroplating bath; 8. a U-shaped copper wire; 9. and (4) electroplating solution.
Detailed Description
In order that those skilled in the art will be better able to understand the present invention, the following detailed description of the invention is given in conjunction with the accompanying drawings.
A multilayer nickel plating process for ceramic-metal shells comprises a shell plating pretreatment process, a shell nickel plating process and a dehydrogenation process,
the shell plating pretreatment process comprises the following steps: sequentially carrying out grinding polishing, oil removal and acid pickling treatment on the ceramic-metal shell; in the grinding and polishing treatment, the ceramic-metal shell is ground and polished by adopting an abrasive material with the particle size of 300-250 mu m; in the oil removal treatment, the ceramic-metal shell is placed in an alkaline oil removal agent, and ultrasonic waves are introduced into the alkaline oil removal agent; the frequency of ultrasonic wave adopted by ultrasonic treatment is 16 KHz; the pickling solution adopted in the pickling treatment is a hydrochloric acid solution with the volume ratio of hydrochloric acid to water being 1: 1.
The shell nickel plating process comprises the following steps:
electroplating impact nickel → deionized water → electroplating high phosphorus nickel → cleaning, drying → annealing → dry spraying → hydrochloric acid → deionized water → putting in protective liquid → reducing liquid → deionized water → small current electroplating nickel → deionized water → chemical plating medium phosphorus nickel → deionized water → gold plating → deionized water drying and drying.
In the shell nickel plating process, the electroplating processes of impact nickel electroplating, high-phosphorus nickel electroplating and low-current nickel electroplating are respectively carried out in an electroplating bath, as shown in fig. 1, an electroplating solution 9 is contained in the electroplating bath 7, a U-shaped copper wire 8 is arranged in the electroplating bath 7, two ends of the U-shaped copper wire 8 are respectively hung on the upper edges of two opposite sides of the electroplating bath 7, and the bottom of the U-shaped copper wire 8 extends into the bottom of the electroplating bath 7; in the electroplating process, the current at the bottom of the electroplating bath 7 is large, and the current at the bottom of the electroplating bath 7 is upwards transmitted along the U-shaped copper wire 8 by arranging the U-shaped copper wire 8, so that the current in the electroplating bath 7 is uniformly distributed, and the problems of uneven plating and fragile lead caused by large local current density in the electroplating bath are solved.
The electroplating current density adopted by the low-current nickel electroplating is 0.3A/dm2In order to meet the condition of low-current nickel electroplating, the formula of the low-current nickel electroplating solution is optimized, and the formula of the low-current nickel electroplating solution is as follows: 180g/L of nickel sulfate 160-180g/L, 30-40g/L of sodium chloride, 35-40g/L of boric acid, 30-35g/L of magnesium sulfate and the balance of water; the pH value of the solution is 3-4, and the electroplating temperature is 45-55 ℃; in order to meet the condition of low-current nickel electroplating, the formula is optimized for low-current nickel electroplating, the concentration of nickel sulfate in the conventional nickel electroplating formula is reduced to 160-180g/L, and the lead is prevented from becoming brittle due to high current and the uniformity of a plating layer is ensured.
The formula of the solution for electroplating impact nickel is as follows: 180-240 g/L of nickel chloride, 80-120 g/L of hydrochloric acid and the balance of water; the formula of the solution for electroplating high phosphorus nickel is as follows: 300g/L of nickel sulfate, 40g/L of boric acid and the balance of water; the formula of the solution for chemically plating the phosphorus and the nickel comprises the following components: 45ml/L of nickel sulfamate solution, 100ml/L of sodium hydroxide solution and the balance of water.
The formula of the gold plating solution is as follows: 5-12g/L of gold potassium citrate, 150g/L of potassium citrate 140-; the pH of the gold plating solution is 3.5-5.8, and the plating temperature is 40-50 ℃.
The dehydrogenation treatment process comprises the steps of performing dehydrogenation treatment at the temperature of 470-500 ℃ and under the pressure of less than or equal to 5 multiplied by 10-3Annealing treatment is carried out under the condition of Pa, the temperature is kept at 470-500 ℃ for 30-40min, and then the temperature is cooled to room temperature, so that hydrogen generated by the grain boundary of the lead material of the ceramic-metal shell in the electroplating process is eliminated, and the phenomenon of hydrogen embrittlement of the lead is prevented.
As shown in fig. 2, the multilayer nickel structure of the ceramic-metal case obtained by the multilayer nickel plating process of the ceramic-metal case comprises a ceramic-metal case 6, an impact nickel layer 5, a high-phosphorus nickel layer 4, a low-current electroplated nickel layer 3, a medium-phosphorus nickel layer 2 and a gold-plated layer 1 which are sequentially connected from bottom to top; pinholes among the plating layers are staggered, so that the penetration of the plating layer pinholes is prevented, and the salt spray resistance of the ceramic-metal shell is effectively improved; the ceramic-metal shell is electroplated with impact nickel in a reduction state, so that the stress between the ceramic-metal shell and the coating is reduced; the phosphorus element accounts for 10-12% of the high-phosphorus nickel layer by mass, the phosphorus element accounts for 7-9% of the medium-phosphorus nickel layer by mass, and the high-phosphorus nickel can be diffused among the plating layers, so that the stress among the plating layers is further reduced; the outermost layer is plated with the gold layer, so that the antirust performance is better, and the ceramic-metal shell is effectively protected.
In a temperature cycle test, the ceramic-metal shell treated by the multilayer nickel plating process of the ceramic-metal shell provided by the embodiment is subjected to tightening examination after being cycled for 100 times within the temperature range of-65 ℃ to +175 ℃, and is cycled for 10 times within the temperature range of-65 ℃ to +300 ℃, so that the plating layer has no air bubbles, no peeling and no color change at the external lead under a 10-time magnifier. After 24 hours of salt spray test, the surface of the shell meets the requirement of the salt spray test in GJB 548B-2005.
The multi-layer nickel plating process for the ceramic-metal shell provided by the invention is described in detail above. The principles and embodiments of the present invention are explained herein using specific examples, which are presented only to assist in understanding the method and central concepts of the present invention. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (6)
1. A multilayer nickel plating process for a ceramic-metal shell is characterized by comprising a shell plating pretreatment process, a shell nickel plating process and a dehydrogenation process,
the shell plating pretreatment process comprises the following steps: sequentially carrying out grinding polishing, oil removal and acid pickling on the ceramic-metal shell, wherein in the oil removal treatment, the ceramic-metal shell is placed in an oil removal agent, and ultrasonic waves are introduced into the oil removal agent;
the shell nickel plating process comprises the following steps:
electroplating impact nickel → deionized water → electroplating high phosphorus nickel → cleaning, drying → annealing → dry spraying → hydrochloric acid → deionized water → putting in protective liquid → reducing liquid → deionized water → small current electroplating nickel → deionized water → chemical plating middle phosphorus nickel → deionized water → gold plating → deionized water drying and drying;
the dehydrogenation treatment process comprises the steps of performing dehydrogenation treatment at the temperature of 470-500 ℃ and under the pressure of less than or equal to 5 multiplied by 10-3Annealing treatment is carried out under the condition of Pa;
the formula of the solution for electroplating high phosphorus nickel is as follows: 300g/L of nickel sulfate, 40g/L of boric acid and the balance of water;
the formula of the solution for low-current nickel electroplating is as follows: 180g/L of nickel sulfate 160-180g/L, 30-40g/L of sodium chloride, 35-40g/L of boric acid, 30-35g/L of magnesium sulfate and the balance of water; the pH value of the solution is 3-4, and the electroplating temperature is 45-55 ℃; the electroplating current density adopted by the low-current nickel electroplating is 0.3A/dm2；
The formula of the solution for chemically plating the phosphorus and the nickel comprises the following components: 45ml/L of nickel sulfamate solution, 100ml/L of sodium hydroxide solution and the balance of water;
the multilayer nickel structure of the ceramic-metal shell obtained by the multilayer nickel plating process of the ceramic-metal shell comprises the ceramic-metal shell, an impact nickel layer, a high-phosphorus nickel layer, a low-current electroplated nickel layer, a medium-phosphorus nickel layer and a gold plating layer which are sequentially connected from bottom to top, wherein the phosphorus element accounts for 10-12% of the high-phosphorus nickel layer by mass, and the phosphorus element accounts for 7-9% of the medium-phosphorus nickel layer by mass.
2. A multi-layer nickel plating process for a ceramic-metal shell according to claim 1, wherein the plating process in the shell nickel plating process is carried out in a plating bath, a U-shaped copper wire is arranged in the plating bath, two ends of the U-shaped copper wire are respectively hung on two opposite upper edges of the plating bath, and the bottom of the U-shaped copper wire extends into the bottom of the plating bath.
3. A process of multilayer nickel plating of ceramic-metal enclosures as claimed in claim 1 wherein the solution formulation of the electroplated strike nickel is: 180-240 g/L of nickel chloride, 80-120 g/L of hydrochloric acid and the balance of water.
4. The process of claim 1, wherein the annealing step is performed at 470-500 ℃ for 30-40min, and then the temperature is cooled to room temperature.
5. A process of multilayer nickel plating of ceramic-metal housing as claimed in claim 1 wherein the gold plating solution formulation is: 5-12g/L of gold potassium citrate, 150g/L of potassium citrate 140-; the pH of the gold plating solution is 3.5-5.8, and the plating temperature is 40-50 ℃.
6. A multi-layer nickel plating process for ceramic-metal shell according to claim 1, wherein in the grinding and polishing process, the ceramic-metal shell is ground and polished by using an abrasive material with a particle size of 300-250 μm; the frequency of ultrasonic wave adopted by ultrasonic treatment is 16 KHz; the pickling solution adopted in the pickling treatment is a hydrochloric acid solution with the volume ratio of hydrochloric acid to water being 1: 1.
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