CN114150318A - Pre-plating treatment method for copper-nickel-silicon alloy and method for electroplating silver on surface of copper-nickel-silicon alloy - Google Patents
Pre-plating treatment method for copper-nickel-silicon alloy and method for electroplating silver on surface of copper-nickel-silicon alloy Download PDFInfo
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- 238000007747 plating Methods 0.000 title claims abstract description 79
- ZUPBPXNOBDEWQT-UHFFFAOYSA-N [Si].[Ni].[Cu] Chemical compound [Si].[Ni].[Cu] ZUPBPXNOBDEWQT-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 64
- 239000004332 silver Substances 0.000 title claims abstract description 64
- 229910021484 silicon-nickel alloy Inorganic materials 0.000 title claims abstract description 57
- 238000000034 method Methods 0.000 title claims abstract description 46
- 238000009713 electroplating Methods 0.000 title claims abstract description 23
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 63
- 238000005498 polishing Methods 0.000 claims abstract description 60
- 239000002253 acid Substances 0.000 claims abstract description 45
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 27
- 238000004140 cleaning Methods 0.000 claims abstract description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000000203 mixture Substances 0.000 claims abstract description 21
- 239000010949 copper Substances 0.000 claims abstract description 19
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052802 copper Inorganic materials 0.000 claims abstract description 18
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 13
- 239000010703 silicon Substances 0.000 claims abstract description 13
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 11
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 239000000463 material Substances 0.000 claims abstract description 11
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 claims abstract description 11
- 229910000342 sodium bisulfate Inorganic materials 0.000 claims abstract description 11
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 11
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 11
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- LFAGQMCIGQNPJG-UHFFFAOYSA-N silver cyanide Chemical compound [Ag+].N#[C-] LFAGQMCIGQNPJG-UHFFFAOYSA-N 0.000 claims description 12
- 229940098221 silver cyanide Drugs 0.000 claims description 12
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 claims description 10
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 7
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 claims description 6
- 238000005554 pickling Methods 0.000 claims description 4
- 239000011777 magnesium Substances 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 18
- 229910000676 Si alloy Inorganic materials 0.000 abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000006243 chemical reaction Methods 0.000 abstract description 6
- 230000036632 reaction speed Effects 0.000 abstract description 6
- 238000005406 washing Methods 0.000 abstract description 5
- 230000005587 bubbling Effects 0.000 abstract description 3
- 239000011247 coating layer Substances 0.000 abstract description 3
- 238000004090 dissolution Methods 0.000 abstract description 3
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 abstract description 2
- 238000002203 pretreatment Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 28
- 239000012266 salt solution Substances 0.000 description 7
- 238000005238 degreasing Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007517 polishing process Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Images
Classifications
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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
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B1/00—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes
- B24B1/005—Processes of grinding or polishing; Use of auxiliary equipment in connection with such processes using a magnetic polishing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24B—MACHINES, DEVICES, OR PROCESSES FOR GRINDING OR POLISHING; DRESSING OR CONDITIONING OF ABRADING SURFACES; FEEDING OF GRINDING, POLISHING, OR LAPPING AGENTS
- B24B27/00—Other grinding machines or devices
- B24B27/033—Other grinding machines or devices for grinding a surface for cleaning purposes, e.g. for descaling or for grinding off flaws in the surface
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C9/00—Alloys based on copper
- C22C9/06—Alloys based on copper with nickel or cobalt as the next major constituent
-
- 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
- C25D3/40—Electroplating: Baths therefor from solutions of copper from cyanide baths, e.g. with Cu+
-
- 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- 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
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention belongs to the technical field of electroplating of copper alloys, and particularly relates to a pre-plating treatment method of a copper nickel silicon alloy and a method for electroplating silver on the surface of the copper nickel silicon alloy. The plating pretreatment method comprises the following steps: and carrying out magnetic polishing on the copper-nickel-silicon alloy substrate subjected to acid cleaning and descaling, wherein the polishing solution used for the magnetic polishing consists of water and a polishing composition, and the polishing composition consists of glucose, sodium bicarbonate, sodium bisulfate and sodium fluoride. When the oxide skin is removed by acid washing, the reaction speed of copper element and acid is high, the reaction speed of nickel element and acid is low, silicon element hardly reacts with acid, metal nickel and silicon are gradually precipitated and accumulated on the surface of a part along with the reaction and dissolution of copper element and acid, the surface of the part is gradually covered by a black film layer, and the combination of a subsequent coating layer is influenced. The magnetic polishing is adopted to mainly remove nickel and silicon accumulated on the surface and expose clean and active base materials, thereby avoiding the phenomena of poor binding force such as bubbling, peeling, silver layer stripping and the like during later silver plating.
Description
Technical Field
The invention belongs to the technical field of electroplating of copper alloys, and particularly relates to a pre-plating treatment method of a copper nickel silicon alloy and a method for electroplating silver on the surface of the copper nickel silicon alloy.
Background
The copper-nickel-silicon alloy material has the characteristics of high strength, high elasticity, medium conductivity, excellent stress relaxation resistance and the like, and is widely applied to the fields of precision relays, high-grade switches and the like. During the use process, a method of plating a metal covering layer, such as a silver plating layer, on the surface of the copper-nickel-silicon alloy is generally adopted to further improve the performance.
In order to improve the bonding force between the coating and the copper nickel silicon alloy during coating, the copper nickel silicon alloy is usually subjected to pre-coating treatment such as degreasing, pickling to remove surface scale, and the like. When the copper-nickel-silicon alloy is subjected to acid cleaning, the used acid is usually an environment-friendly acid, sulfuric acid and other acids, the reaction speed of copper elements and the acid is high, the reaction speed of nickel elements and the acid is low, and silicon elements hardly react with the acid. Along with the reaction and dissolution of the copper element and the acid, the metal nickel and the silicon are gradually precipitated and accumulated on the surface of the part, and the alloy surface is gradually covered by the black film layer. Therefore, in order to remove the black film layer on the surface, mixed acid mainly consisting of nitric acid and hydrofluoric acid is required to be adopted for cleaning after acid cleaning. During the cleaning process, the reaction is vigorous and produces a large amount of yellow, dense smoke exhaust. If the waste gas is not properly treated, the health of operating personnel is directly harmed, and the atmospheric environment is polluted; and the violent reaction directly influences the processing size of parts.
Disclosure of Invention
The invention aims to provide a method for treating a copper-nickel-silicon alloy before plating, which is pollution-free and does not influence the processing size of parts.
The second purpose of the invention is to provide a method for electroplating silver on the surface of the copper-nickel-silicon alloy, which can effectively improve the binding force between the copper-nickel-silicon alloy and the silver plating layer.
In order to achieve the purpose, the invention adopts the technical scheme that:
a pre-plating treatment method of a copper-nickel-silicon alloy comprises the following steps: performing magnetic polishing on the copper-nickel-silicon alloy substrate subjected to acid cleaning and descaling, wherein a polishing solution used for the magnetic polishing consists of water and a polishing composition, and the polishing composition consists of the following components in percentage by mass: 8-10% of glucose, 30-35% of sodium bicarbonate, 35-40% of sodium bisulfate and 15-20% of sodium fluoride.
When the oxide skin is removed by acid washing, the reaction speed of copper element and acid is high, the reaction speed of nickel element and acid is low, silicon element hardly reacts with acid, metal nickel and silicon are gradually precipitated and accumulated on the surface of a part along with the reaction and dissolution of copper element and acid, the surface of the part is gradually covered by a black film layer, and the combination of a subsequent coating layer is influenced. The magnetic polishing in the polishing solution removes nickel and silicon accumulated on the surface to expose a clean and active substrate, thereby avoiding the phenomena of poor binding force such as bubbling, peeling, silver layer stripping and the like during later silver plating.
The magnetic polishing is adopted to remove a large amount of impurity particles (metal nickel and silicon) on the surface by physical friction. The components such as sodium bicarbonate and sodium bisulfate in the polishing solution play roles in reducing acidity and stabilizing pH value, so that the weak acidity of the solution can be maintained, and impurity molecules can be prevented from being continuously separated out; the components such as sodium fluoride and glucose in the polishing solution remove residual impurity molecules of the matrix through chemical reaction and complexation.
When the oxide skin is removed by acid washing, strong acid such as nitric acid and sulfuric acid or environment-friendly acid can be used, and preferably, the environment-friendly acid is used, so that copper oxide and basic copper carbonate can be effectively removed. The preferred pickling time is 1-4 min.
As the surface of the copper nickel silicon alloy base material can be polluted by oil stains in the transferring and transporting process, the copper nickel silicon alloy base material can be optionally cleaned to remove the surface oil stains before the scale is removed by acid washing. The cleaning can be carried out by adopting normal-temperature degreasing powder or solution of degreasing and degreasing reagents (which can be used for emulsification and saponification) to clean the oil stains on the surface of the copper-nickel-silicon alloy base material, wherein the cleaning time can be determined according to the condition of the oil stains on the surface; and a degreasing reagent can be added into acid during acid cleaning, so that degreasing and scale removal are realized simultaneously.
Preferably, the polishing solution used has a total concentration of the polishing composition of 60 to 120 g/L.
The proper cleaning degree of the surface of the copper-nickel-silicon alloy is further ensured by adjusting the magnetic polishing process, the preferred polishing frequency of the magnetic polishing is 50-70 Hz, and the time is 5-10 min.
The copper nickel silicon alloy base material can be workpieces of various sizes processed by copper nickel silicon alloy, and can also be unprocessed copper nickel silicon alloy. The copper-nickel-silicon alloy base material is a commercially available copper-nickel-silicon alloy and consists of the following elements in percentage by mass: 2.2 to 4.2% of nickel, 0.25 to 1.2% of silicon, 0.05 to 0.3% of magnesium, and the balance of copper and inevitable impurities.
The invention adopts the technical scheme that the method for electroplating silver on the surface of the copper-nickel-silicon alloy comprises the following steps:
a method for electroplating silver on the surface of a copper-nickel-silicon alloy comprises the following steps:
(1) pre-plating treatment: performing magnetic polishing on the copper-nickel-silicon alloy substrate subjected to acid cleaning and scale removal; the polishing solution for magnetic polishing consists of water and a polishing composition, wherein the polishing composition consists of the following components in percentage by mass: 8-10% of glucose, 30-35% of sodium bicarbonate, 35-40% of sodium bisulfate and 15-20% of sodium fluoride;
(2) silver electroplating: copper plating is performed first, and then silver plating is performed.
Based on the pre-plating treatment method, the surface of the copper nickel silicon alloy base material is cleaned before silver plating, and a plating layer (pre-plating copper layer) is pre-plated before silver plating, so that the binding force between the silver plating layer and the copper nickel silicon alloy base material is effectively improved, and the silver plating quality is ensured.
Preferably, in the step (1), the total concentration of the polishing composition in the polishing solution is 60 to 120 g/L.
Since an oxide film may be generated again on the surface of the copper nickel silicon alloy substrate between processes before the subsequent plating treatment is performed after the magnetic polishing, it is preferable that the oxide film generated between processes is removed by acid washing after the magnetic polishing in step (1). More preferably, the acid for pickling is hydrochloric acid, the concentration of the hydrochloric acid is 580-600 mL/L, and the cleaning time is 30 s-1 min.
The electroplating process and thickness of the pre-copper plating and silver plating can be adjusted according to the actual situation. Preferably, the electroplating process adopted by the invention is as follows: the current density during copper plating is 0.8-1.5A/dm2The time is 10-20 min; the concentration of copper cyanide in the plating solution is 35-42 g/L, and the concentration of sodium cyanide is 46-60 g/L.
The silver plating comprises pre-silver plating and silver plating, wherein the time for pre-silver plating is 5-15 s, and the time for silver plating is 20-30 min; the current density during pre-silver plating is 1.2-2.0A/dm2The concentration of silver cyanide in the plating solution is 2-6 g/L, and the concentration of sodium cyanide is 46-60 g/L; the current density during silver plating is 0.8-1.5A/dm2The concentration of silver cyanide in the plating solution is 30-40 g/L, and the concentration of potassium cyanide is 120-150 g/L. And the copper-nickel-silicon alloy substrate is electrified and enters the tank during pre-silver plating. The silver pre-plating can prevent the silver layer with rough crystallization and poor adhesion from being replaced on the surface of the copper-nickel-silicon alloy base material.
The pre-copper plating is carried out at room temperature, the temperature of the pre-silver plating is 20-40 ℃, and the temperature of the silver plating is 20-30 ℃.
Drawings
Fig. 1 is a flow chart of a silver plating process of a copper-nickel-silicon alloy according to embodiment 2 of the present invention.
Detailed Description
The invention is further explained below with reference to examples and figures.
The copper-nickel-silicon alloy used in the following examples is a C70250 alloy, and is composed of the following components in percentage by mass: 96.2% of Cu, 3% of Ni, 0.65% of Si and 0.15% of Mg.
First, the embodiment of the method for pre-plating treatment of copper-nickel-silicon alloy
Example 1
The method for the pre-plating treatment of the copper-nickel-silicon alloy comprises the following steps of:
(1) cleaning the copper-nickel-silicon alloy part in a water solution for removing oil powder at normal temperature, and swinging the part up and down for 2-3 times during cleaning so as to effectively clean the inner cavity or blind hole of the copper-nickel-silicon alloy part;
(2) cleaning the cleaned copper-nickel-silicon alloy part in an environment-friendly acid solution for 1-4 min; and then, carrying out magnetic polishing on the copper-nickel-silicon alloy part in an acid salt solution to remove metal impurities of nickel and silicon on the surface of the part, wherein the acid salt solution consists of water and a polishing composition, and the polishing composition consists of the following components in percentage by mass: 8% of glucose, 34% of sodium bicarbonate, 39% of sodium bisulfate, 19% of sodium fluoride, and the total concentration of the polishing composition in the acid salt solution is 100 g/L; the frequency of magnetic polishing was 60Hz and the time was 8 min.
After the pretreatment, the copper-nickel-silicon alloy part is cleaned in hydrochloric acid with the concentration of 580-600 mL/L for 30 s-1 min according to the circumstances so as to remove an oxidation film generated in the process, and then a required metal covering layer is plated on the surface of the copper-nickel-silicon alloy part by adopting the conventional process.
Second, example of the method for electroplating silver on the surface of copper-nickel-silicon alloy
Example 2
The process of the method for electroplating silver on the surface of copper-nickel-silicon alloy of the embodiment is shown in fig. 1, and specifically includes the following steps:
(1) cleaning the copper-nickel-silicon alloy part in a water solution for removing oil powder at normal temperature, and swinging the part up and down for 2-3 times during cleaning so as to effectively clean the inner cavity or blind hole of the copper-nickel-silicon alloy part;
(2) cleaning the cleaned copper-nickel-silicon alloy part in an environment-friendly acid solution for 1-4 min; and then, carrying out magnetic polishing on the copper-nickel-silicon total part in an acid salt solution to remove metal impurities of nickel and silicon on the surface of the part, wherein the acid salt solution of the acid salt solution consists of water and a polishing composition, and the polishing composition consists of the following components in percentage by mass: : 8% of glucose, 35% of sodium bicarbonate, 40% of sodium bisulfate, 17% of sodium fluoride, and the total concentration of the polishing composition in the acid salt solution is 90 g/L; the frequency of magnetic polishing is 60Hz, and the time is 8 min;
in other implementations, the total concentration can be adjusted to 80, 120g/L, etc. The magnetic polishing adjustment can be adjusted to 70Hz for 5 min; or 50Hz, 10min, etc.
(3) Then, cleaning the copper-nickel-silicon alloy part in hydrochloric acid solution with the concentration of 590mL/L for 30 s-1 min to remove the oxide film on the surface;
(4) then, pre-copper plating treatment is carried out on the copper-nickel-silicon alloy parts at room temperature, and the current density is 1.0A/dm2The time is 15 min; the plating solution is a mixed solution of copper cyanide and sodium cyanide, wherein the concentration of the copper cyanide is 38g/L, and the concentration of the sodium cyanide is 52 g/L;
(5) then carrying out pre-silvering treatment on the copper-nickel-silicon alloy part at room temperature, wherein the current density is 1.5A/dm2The time is 10s, and the temperature is 30 ℃; the plating solution is a mixed solution of silver cyanide and potassium cyanide, wherein the concentration of the silver cyanide is 4g/L, and the concentration of the potassium cyanide is 130 g/L; the copper-nickel-silicon alloy base material is electrified and put into a groove during pre-silver plating;
(6) finally, silver plating is carried out, and the current density is 1.0A/dm2The time is 25min and the temperature is 25 ℃; the plating solution is a mixed solution of silver cyanide and potassium cyanide, wherein the concentration of the silver cyanide is 35g/L, and the concentration of the potassium cyanide is 140 g/L.
Example 3
The process of the method for electroplating silver on the surface of the copper-nickel-silicon alloy is basically the same as that of the example 2, and the difference is only that:
the current density used in the copper preplating in the step (4) is 1.2A/dm2The time is 14 min; the concentration of copper cyanide in the plating solution is 37g/L, and the concentration of sodium cyanide is 55 g/L;
the current density used in the pre-silver plating in the step (5) is 1.6A/dm2The time is 8 s; the concentration of silver cyanide in the plating solution is 3g/L, and the concentration of potassium cyanide is 125 g/L;
the current density used in the silver plating in the step (6) is 0.9A/dm2The time is 26 min; the concentration of silver cyanide in the plating solution used was 36g/L and the concentration of potassium cyanide was 135 g/L.
Example 4
The process of the method for electroplating silver on the surface of the copper-nickel-silicon alloy is basically the same as that of the example 2, and the difference is only that:
the current density used in the copper preplating in the step (4) is 0.9A/dm2The time is 16 min; the concentration of copper cyanide in the plating solution used is 38g/L, and the concentration of sodium cyanide isThe concentration is 56 g/L;
the current density used in the pre-silver plating in the step (5) is 1.7A/dm2The time is 6 s; the concentration of silver cyanide in the plating solution is 5g/L, and the concentration of sodium cyanide is 129 g/L;
the current density used in the silver plating in the step (6) is 1.2A/dm2The time is 22 min; the concentration of silver cyanide in the plating solution was 38g/L and the concentration of potassium cyanide was 137 g/L.
In another embodiment of the method for electroplating silver on the surface of copper-nickel-silicon alloy of the present invention, the following composition for magnetic polishing can be selected, and the effects substantially equivalent to those of embodiments 2 to 4 can be obtained.
Formula 1: 9% glucose, 33% sodium bicarbonate, 39% sodium bisulfate, 19% sodium fluoride.
And (2) formula: 8% glucose, 34% sodium bicarbonate, 38% sodium bisulfate, 20% sodium fluoride.
And (3) formula: 10% glucose, 34% sodium bicarbonate, 40% sodium bisulfate, 16% sodium fluoride.
Third, comparative example section
The silver plating process of the copper-nickel-silicon alloy of the comparative example is basically the same as that of example 2, except that the polishing solution used in the magnetic polishing in step (2) is a 5% nitric acid solution.
Fourth, test example section
In the test example, the bonding performance between the silver coating layer and the part of the parts in examples 2 to 4 and comparative example 1 was tested, and the test method was: and heating the part to 250 ℃ by using an oven, preserving heat for 2 hours, then cooling the part at room temperature, and observing whether the silver layer on the surface of the part has the phenomena of bubbling, peeling, silver layer stripping and the like.
The test result shows that the silver-plated parts in the examples 2-4 have no phenomena of foaming, peeling, silver layer stripping and the like, and the silver layer has good bonding force; the silver-plated parts of the comparative examples have the phenomenon of dense pinhole size foaming and have unqualified binding force.
Claims (10)
1. A pre-plating treatment method of a copper-nickel-silicon alloy is characterized by comprising the following steps: performing magnetic polishing on the copper-nickel-silicon alloy substrate subjected to acid cleaning and descaling, wherein a polishing solution used for the magnetic polishing consists of water and a polishing composition, and the polishing composition consists of the following components in percentage by mass: 8-10% of glucose, 30-35% of sodium bicarbonate, 35-40% of sodium bisulfate and 15-20% of sodium fluoride.
2. The method for treating a copper-nickel-silicon alloy before plating according to claim 1, wherein the total concentration of the polishing composition in the polishing solution is 60 to 120 g/L.
3. The method for the pre-plating treatment of the copper-nickel-silicon alloy as claimed in claim 1, wherein the polishing frequency of the magnetic polishing is 50 to 70Hz, and the time is 5 to 10 min.
4. The method for treating the copper-nickel-silicon alloy before plating according to any one of claims 1 to 3, wherein the copper-nickel-silicon alloy base material is composed of the following elements in percentage by mass: 2.2 to 4.2% of nickel, 0.25 to 1.2% of silicon, 0.05 to 0.3% of magnesium, and the balance of copper and inevitable impurities.
5. The method for electroplating silver on the surface of the copper-nickel-silicon alloy is characterized by comprising the following steps of:
(1) pre-plating treatment: performing magnetic polishing on the copper-nickel-silicon alloy substrate subjected to acid cleaning and scale removal; the polishing solution for magnetic polishing consists of water and a polishing composition, wherein the polishing composition consists of the following components in percentage by mass: 8-10% of glucose, 30-35% of sodium bicarbonate, 35-40% of sodium bisulfate and 15-20% of sodium fluoride;
(2) silver electroplating: copper plating is performed first, and then silver plating is performed.
6. The method for electroplating silver on the surface of the copper-nickel-silicon alloy according to claim 5, wherein in the step (1), the total concentration of the polishing composition in the polishing solution is 60-120 g/L.
7. The method for electroplating silver on the surface of copper-nickel-silicon alloy according to claim 5, wherein in the step (1), the oxide film generated in the step of removing is washed away by acid after magnetic polishing.
8. The method for electroplating silver on the surface of copper-nickel-silicon alloy according to claim 7, wherein the acid used for pickling is hydrochloric acid, the concentration of the hydrochloric acid used is 580-600 mL/L, and the cleaning time is 30 s-1 min.
9. The method of claim 5, wherein the current density during copper plating is 0.8-1.5A/dm2The time is 10-20 min; the concentration of copper cyanide in the plating solution is 35-42 g/L, and the concentration of sodium cyanide is 46-60 g/L.
10. The method for electroplating silver on the surface of the copper-nickel-silicon alloy according to claim 5 or 9, wherein the silver plating comprises pre-silver plating and silver plating, the time for pre-silver plating is 5-15 s, and the time for silver plating is 20-30 min; the current density during pre-silver plating is 1.2-2.0A/dm2The concentration of silver cyanide in the plating solution is 2-6 g/L, and the concentration of potassium cyanide is 120-140 g/L; the current density during silver plating is 0.8-1.5A/dm2The concentration of silver cyanide in the plating solution is 30-40 g/L, and the concentration of potassium cyanide is 120-150 g/L.
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