CN113186572A - Rhodium ruthenium alloy electroplating process - Google Patents
Rhodium ruthenium alloy electroplating process Download PDFInfo
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- CN113186572A CN113186572A CN202110478019.7A CN202110478019A CN113186572A CN 113186572 A CN113186572 A CN 113186572A CN 202110478019 A CN202110478019 A CN 202110478019A CN 113186572 A CN113186572 A CN 113186572A
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- plating
- rhodium
- washing
- metal product
- drying
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- YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 238000009713 electroplating Methods 0.000 title claims abstract description 19
- 230000008569 process Effects 0.000 title claims abstract description 17
- 229910000929 Ru alloy Inorganic materials 0.000 title claims abstract description 15
- 238000007747 plating Methods 0.000 claims abstract description 78
- 229910052751 metal Inorganic materials 0.000 claims abstract description 36
- 239000002184 metal Substances 0.000 claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 28
- 230000004913 activation Effects 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- 239000010949 copper Substances 0.000 claims abstract description 19
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052737 gold Inorganic materials 0.000 claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 18
- 238000005238 degreasing Methods 0.000 claims abstract description 17
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 24
- 238000007789 sealing Methods 0.000 claims description 19
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- CSJDJKUYRKSIDY-UHFFFAOYSA-N 1-sulfanylpropane-1-sulfonic acid Chemical compound CCC(S)S(O)(=O)=O CSJDJKUYRKSIDY-UHFFFAOYSA-N 0.000 claims description 5
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- FGRVOLIFQGXPCT-UHFFFAOYSA-L dipotassium;dioxido-oxo-sulfanylidene-$l^{6}-sulfane Chemical compound [K+].[K+].[O-]S([O-])(=O)=S FGRVOLIFQGXPCT-UHFFFAOYSA-L 0.000 claims description 5
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 5
- 235000019387 fatty acid methyl ester Nutrition 0.000 claims description 5
- LNOPIUAQISRISI-UHFFFAOYSA-N n'-hydroxy-2-propan-2-ylsulfonylethanimidamide Chemical compound CC(C)S(=O)(=O)CC(N)=NO LNOPIUAQISRISI-UHFFFAOYSA-N 0.000 claims description 5
- DAHPIMYBWVSMKQ-UHFFFAOYSA-N n-hydroxy-n-phenylnitrous amide Chemical compound O=NN(O)C1=CC=CC=C1 DAHPIMYBWVSMKQ-UHFFFAOYSA-N 0.000 claims description 5
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 5
- 239000001508 potassium citrate Substances 0.000 claims description 5
- 229960002635 potassium citrate Drugs 0.000 claims description 5
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 5
- 235000011082 potassium citrates Nutrition 0.000 claims description 5
- YWFDDXXMOPZFFM-UHFFFAOYSA-H rhodium(3+);trisulfate Chemical compound [Rh+3].[Rh+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YWFDDXXMOPZFFM-UHFFFAOYSA-H 0.000 claims description 5
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 5
- ZWZLRIBPAZENFK-UHFFFAOYSA-J sodium;gold(3+);disulfite Chemical compound [Na+].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O ZWZLRIBPAZENFK-UHFFFAOYSA-J 0.000 claims description 5
- MRGUSFYIQDLKNZ-UHFFFAOYSA-M sodium;prop-1-yne-1-sulfonate Chemical compound [Na+].CC#CS([O-])(=O)=O MRGUSFYIQDLKNZ-UHFFFAOYSA-M 0.000 claims description 5
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 5
- ICLYJLBTOGPLMC-KVVVOXFISA-N (z)-octadec-9-enoate;tris(2-hydroxyethyl)azanium Chemical compound OCCN(CCO)CCO.CCCCCCCC\C=C/CCCCCCCC(O)=O ICLYJLBTOGPLMC-KVVVOXFISA-N 0.000 claims description 3
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims description 3
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims description 3
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 239000000344 soap Substances 0.000 claims description 3
- 229940117013 triethanolamine oleate Drugs 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 229910052707 ruthenium Inorganic materials 0.000 abstract description 2
- 229910052703 rhodium Inorganic materials 0.000 abstract 1
- 239000010948 rhodium Substances 0.000 abstract 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 abstract 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- 239000002994 raw material Substances 0.000 description 8
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 description 3
- MDMNGFFWUZNOSO-UHFFFAOYSA-N 3-ethyl-1h-imidazole-2-thione Chemical compound CCN1C=CN=C1S MDMNGFFWUZNOSO-UHFFFAOYSA-N 0.000 description 3
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000004115 Sodium Silicate Substances 0.000 description 3
- OVQABVAKPIYHIG-UHFFFAOYSA-N n-(benzenesulfonyl)benzenesulfonamide Chemical compound C=1C=CC=CC=1S(=O)(=O)NS(=O)(=O)C1=CC=CC=C1 OVQABVAKPIYHIG-UHFFFAOYSA-N 0.000 description 3
- KVBGVZZKJNLNJU-UHFFFAOYSA-N naphthalene-2-sulfonic acid Chemical compound C1=CC=CC2=CC(S(=O)(=O)O)=CC=C21 KVBGVZZKJNLNJU-UHFFFAOYSA-N 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 description 3
- 229940074439 potassium sodium tartrate Drugs 0.000 description 3
- 239000000176 sodium gluconate Substances 0.000 description 3
- 229940005574 sodium gluconate Drugs 0.000 description 3
- 235000012207 sodium gluconate Nutrition 0.000 description 3
- 235000011006 sodium potassium tartrate Nutrition 0.000 description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 3
- 229910052911 sodium silicate Inorganic materials 0.000 description 3
- XHJZXCYPSJOWPV-UHFFFAOYSA-N sulfanyl ethanesulfonate Chemical compound CCS(=O)(=O)OS XHJZXCYPSJOWPV-UHFFFAOYSA-N 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- -1 dithio-terephthalic acid piperidine salt Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000037452 priming Effects 0.000 description 2
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229940069328 povidone Drugs 0.000 description 1
- 230000008439 repair process Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- 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
-
- 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group 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
-
- 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
- C25D5/48—After-treatment of electroplated surfaces
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention relates to the technical field of electroplating, in particular to a rhodium-ruthenium alloy electroplating process, which comprises the following steps: (1) ultrasonic degreasing; (2) primary activation; (3) copper plating; (4) secondary activation; (5) nickel plating; (6) gold plating; (7) plating rhodium and ruthenium; (8) and (4) protecting. The electroplating process can realize the simultaneous electroplating of various metals, has simple process steps, convenient operation and control, stable quality, high production efficiency and low production cost, and can realize large-scale industrial production.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a rhodium-ruthenium alloy electroplating process.
Background
The electroplated product has the advantages of light weight, good corrosion resistance and easy molding of plastics, and the advantages of organic solvent resistance, illumination resistance, metallic luster, thermal conductivity, electrical conductivity, electromagnetic shielding, easy welding and the like of metals, and is widely applied to industries such as hardware, electronics, communication and the like.
At present, the single electroplating can not meet the requirements of customers, and various metals need to be electroplated simultaneously on the existing plastic products so as to meet the requirements of products; however, due to the respective properties of the various metals, it is often difficult to simultaneously plate several metals on a workpiece.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a rhodium-ruthenium alloy electroplating process.
The purpose of the invention is realized by the following technical scheme: a rhodium ruthenium alloy electroplating process comprises the following steps:
(1) ultrasonic degreasing: carrying out ultrasonic thermal degreasing treatment on the metal product, and then washing and drying the metal product;
(2) primary activation: carrying out acid washing and activation on the metal product subjected to ultrasonic oil removal, and then washing and drying;
(3) copper plating: carrying out copper plating treatment on the metal product subjected to primary activation, and then washing and drying;
(4) and (3) secondary activation: carrying out acid washing and activation on the metal product after copper plating, and then washing and drying;
(5) nickel plating: carrying out nickel plating treatment on the metal product subjected to secondary activation, and then washing and drying;
(6) gold plating: carrying out gold plating treatment on the nickel-plated metal product, and then washing and drying;
(7) rhodium-ruthenium plating: carrying out rhodium-ruthenium plating treatment on the metal product after gold plating, and then washing and drying;
(8) protection: and (4) sealing holes of the electroplated metal product, and then washing and drying.
Preferably, in the step (1), the ultrasonic degreasing uses an alkaline solution, and the components are as follows: 2-6% of fatty acid methyl ester ethoxylate sulfonate, 15-25% of sodium hydroxide and the balance of water. The invention realizes the removal of the grease on the surface of the workpiece to be plated by adopting ultrasonic degreasing.
Preferably, in the step (2) and the step (4), a sulfuric acid solution with a mass fraction of 10% -20% is used for acid washing activation. The invention can activate the surface of the piece to be plated by adopting acid washing activation, thereby improving the efficiency of subsequent electroplating.
Preferably, in the step (3), the solution composition of the copper plating solution is: 80-120g/L of copper sulfate, 180g/L of sulfuric acid 140-. The copper plating solution adopts the raw materials, strictly controls the weight ratio of the raw materials, adopts the copper plating layer for priming, can repair the worn part, prevents local carburization and improves the conductivity, and has the advantages of soft and bright copper plating layer, excellent leveling property, strong deep plating capability and high electroplating efficiency.
Preferably, in the step (5), the solution composition of the nickel plating solution is: 250g/L of nickel chloride 150-. The nickel plating solution of the invention can improve the oxidation resistance, corrosion resistance and wear resistance of the plating layer by adopting the raw materials and strictly controlling the weight ratio of the raw materials, can also be used as a barrier layer between a copper plating layer and a gold plating layer to prevent metals from mutually diffusing to influence the weldability and service life of a cooked product, and simultaneously, the mechanical strength of the gold plating layer is greatly increased by priming the nickel plating layer, and the corrosion resistance and the wear resistance are improved.
Preferably, in the step (6), the gold plating solution has the following solution components: 5-15g/L of gold sodium sulfite, 20-40g/L of potassium citrate, 30-50g/L of potassium thiosulfate, 5-15g/L of citric acid, 1-5g/L of sodium ethylene diamine tetracetate, 2-6mg/L of sodium propynyl sulfonate, 0.5-1.5g/L of mercaptopropane sulfonic acid and 0.1-0.3g/L of N-nitrosophenylhydroxylamine. The gold plating solution of the invention can form a gold-dipping plating layer with good adhesiveness and uniform thickness distribution on the surface of a plating piece matrix by adopting the raw materials and strictly controlling the weight ratio of the raw materials, and the plating layer has an excellent crystal structure, high hardness, and better conductivity, corrosion resistance and weldability.
Preferably, in the step (7), the rhodium ruthenium plating solution comprises the following components: 1-5g/L rhodium sulfate, 20-60mL/L sulfuric acid, 0.5-1.5g/L ruthenium trichloride and 40-80g/L sulfamic acid. By adopting the raw materials and strictly controlling the weight ratio of the raw materials, the rhodium-plated ruthenium solution can improve the hardness of the surface of a plating layer, improve the wear resistance and the plugging resistance, and prolong the service life of hardware products.
Preferably, in the step (8), the hole sealing is performed by using a water-based hole sealing agent hydroxypropyl cellulose or povidone; or, an oily hole sealing agent of triethanolamine oleate soap is used for hole sealing. By adopting hole sealing treatment, the invention can carry out hole sealing operation on small holes of the plating layer so as to improve the anti-rust capability of the plating layer.
The invention has the beneficial effects that: the electroplating process can realize the simultaneous electroplating of various metals, has simple process steps, convenient operation and control, stable quality, high production efficiency and low production cost, and can realize large-scale industrial production.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
In the following examples, the temperature of ultrasonic degreasing is 60 ℃ and the degreasing time is 3 min; the electrolytic degreasing temperature is 60 deg.C, the degreasing time is 3min, the workpiece to be plated is used as anode, andthe stainless steel plate is used as a cathode, and the cathode current density is 10A/dm2(ii) a The temperature of acid washing activation is 40 ℃, and the time is 20 s; the current density adopted by electroplating is 10A/dm2The temperature is 45 ℃ and the electroplating time is 5 min.
Example 1
A rhodium ruthenium alloy electroplating process comprises the following steps:
(1) ultrasonic degreasing: carrying out ultrasonic thermal degreasing treatment on the metal product, and then washing and drying the metal product;
(2) primary activation: carrying out acid washing and activation on the metal product subjected to ultrasonic oil removal, and then washing and drying;
(3) copper plating: carrying out copper plating treatment on the metal product subjected to primary activation, and then washing and drying;
(4) and (3) secondary activation: carrying out acid washing and activation on the metal product after copper plating, and then washing and drying;
(5) nickel plating: carrying out nickel plating treatment on the metal product subjected to secondary activation, and then washing and drying;
(6) gold plating: carrying out gold plating treatment on the nickel-plated metal product, and then washing and drying;
(7) rhodium-ruthenium plating: carrying out rhodium-ruthenium plating treatment on the metal product after gold plating, and then washing and drying;
(8) protection: and (4) sealing holes of the electroplated metal product, and then washing and drying.
In the step (1), the ultrasonic degreasing uses an alkaline solution, and the components are as follows: the mass fraction of the fatty acid methyl ester ethoxylate sulfonate is 2%, the mass fraction of the sodium hydroxide is 15%, and the balance is water.
In the step (2) and the step (4), a sulfuric acid solution with the mass fraction of 10% is adopted for acid washing activation.
In the step (3), the solution components of the copper plating solution are as follows: 80-120g/L of copper sulfate, 140g/L of sulfuric acid, 0.1g/L of hydrochloric acid, 0.1g/L of polyethylene glycol, 0.2g/L of sodium silicate, 0.4g/L of sodium gluconate, 0.04g/L of mercaptoethane sulfonate, 0.02g/L of dithio-terephthalic acid piperidine salt and 0.1g/L of 1-ethyl-1H-imidazole-2-thiol.
In the step (5), the solution components of the nickel plating solution are as follows: 150g/L of nickel chloride, 20g/L of potassium sodium tartrate, 0.5g/L of diphenylsulfonimide, 0.1g/L of beta-naphthalenesulfonic acid and 80mL/L of hydrochloric acid.
In the step (6), the gold plating solution comprises the following components: 5g/L of sodium gold sulfite, 20g/L of potassium citrate, 30g/L of potassium thiosulfate, 5g/L of citric acid, 1g/L of sodium ethylene diamine tetracetate, 2mg/L of sodium propynyl sulfonate, 0.5g/L of mercaptopropanesulfonic acid and 0.1g/L of N-nitrosophenylhydroxylamine.
In the step (7), the rhodium ruthenium plating solution comprises the following components: 1g/L rhodium sulfate, 20mL/L sulfuric acid, 0.5g/L ruthenium trichloride and 40g/L sulfamic acid.
In the step (8), the hole sealing is performed by using a water-based hole sealing agent hydroxypropyl cellulose.
Example 2
This embodiment is different from embodiment 1 described above in that:
in the step (1), the ultrasonic degreasing uses an alkaline solution, and the components are as follows: 4% of fatty acid methyl ester ethoxylate sulfonate, 20% of sodium hydroxide and the balance of water.
In the step (2) and the step (4), a sulfuric acid solution with the mass fraction of 15% is adopted for acid washing activation.
In the step (3), the solution components of the copper plating solution are as follows: 100g/L of copper sulfate, 160g/L of sulfuric acid, 0.3g/L of hydrochloric acid, 0.2g/L of polyethylene glycol, 0.4g/L of sodium silicate, 0.6g/L of sodium gluconate, 0.06g/L of mercaptoethane sulfonate, 0.04g/L of dithio-p-phthalic acid piperidine salt and 0.2g/L of 1-ethyl-1H-imidazole-2-thiol.
In the step (5), the solution components of the nickel plating solution are as follows: 200g/L of nickel chloride, 40g/L of potassium sodium tartrate, 1g/L of diphenylsulfonimide, 0.3g/L of beta-naphthalenesulfonic acid and 100mL/L of hydrochloric acid.
In the step (6), the gold plating solution comprises the following components: 10g/L of gold sodium sulfite, 30g/L of potassium citrate, 40g/L of potassium thiosulfate, 10g/L of citric acid, 3g/L of sodium ethylene diamine tetracetate, 4mg/L of sodium propynyl sulfonate, 1g/L of mercaptopropane sulfonic acid and 0.2g/L of N-nitrosophenylhydroxylamine.
In the step (7), the rhodium ruthenium plating solution comprises the following components: 3g/L of rhodium sulfate, 40mL/L of sulfuric acid, 1g/L of ruthenium trichloride and 60g/L of sulfamic acid.
In the step (8), the hole sealing is carried out by adopting a water-based hole sealing agent polyvidone.
Example 3
This embodiment is different from embodiment 1 described above in that:
in the step (1), the ultrasonic degreasing uses an alkaline solution, and the components are as follows: 6% of fatty acid methyl ester ethoxylate sulfonate, 25% of sodium hydroxide and the balance of water.
In the step (2) and the step (4), a sulfuric acid solution with the mass fraction of 20% is adopted for acid washing activation.
In the step (3), the solution components of the copper plating solution are as follows: 120g/L of copper sulfate, 180g/L of sulfuric acid, 0.5g/L of hydrochloric acid, 0.3g/L of polyethylene glycol, 0.6g/L of sodium silicate, 0.8g/L of sodium gluconate, 0.08g/L of mercaptoethane sulfonate, 0.06g/L of dithio-terephthalic acid piperidine salt and 0.3g/L of 1-ethyl-1H-imidazole-2-thiol.
In the step (5), the solution components of the nickel plating solution are as follows: 250g/L of nickel chloride, 60g/L of potassium sodium tartrate, 1.5g/L of diphenylsulfonimide, 0.5g/L of beta-naphthalenesulfonic acid and 120mL/L of hydrochloric acid.
In the step (6), the gold plating solution comprises the following components: 15g/L of gold sodium sulfite, 40g/L of potassium citrate, 50g/L of potassium thiosulfate, 15g/L of citric acid, 5g/L of sodium ethylene diamine tetracetate, 6mg/L of sodium propynyl sulfonate, 1.5g/L of mercaptopropane sulfonic acid and 0.3g/L of N-nitrosophenylhydroxylamine.
In the step (7), the rhodium ruthenium plating solution comprises the following components: 5g/L of rhodium sulfate, 60mL/L of sulfuric acid, 1.5g/L of ruthenium trichloride and 80g/L of sulfamic acid.
In the step (8), the hole sealing is performed by adopting an oily hole sealing agent of triethanolamine oleate soap.
The results of testing the plated metal articles produced in examples 1-3 of the present invention are shown in the following table:
as can be seen from the above, the electroplated metal product of the invention has smooth appearance without scratches, excellent adherence and solderability, and can pass a high temperature test and a salt spray test for 48 hours.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (8)
1. A rhodium ruthenium alloy electroplating process is characterized in that: the method comprises the following steps:
(1) ultrasonic degreasing: carrying out ultrasonic thermal degreasing treatment on the metal product, and then washing and drying the metal product;
(2) primary activation: carrying out acid washing and activation on the metal product subjected to ultrasonic oil removal, and then washing and drying;
(3) copper plating: carrying out copper plating treatment on the metal product subjected to primary activation, and then washing and drying;
(4) and (3) secondary activation: carrying out acid washing and activation on the metal product after copper plating, and then washing and drying;
(5) nickel plating: carrying out nickel plating treatment on the metal product subjected to secondary activation, and then washing and drying;
(6) gold plating: carrying out gold plating treatment on the nickel-plated metal product, and then washing and drying;
(7) rhodium-ruthenium plating: carrying out rhodium-ruthenium plating treatment on the metal product after gold plating, and then washing and drying;
(8) protection: and (4) sealing holes of the electroplated metal product, and then washing and drying.
2. The plating process of the rhodium-ruthenium alloy according to claim 1, wherein: in the step (1), the ultrasonic degreasing uses an alkaline solution, and the components are as follows: 2-6% of fatty acid methyl ester ethoxylate sulfonate, 15-25% of sodium hydroxide and the balance of water.
3. The plating process of the rhodium-ruthenium alloy according to claim 1, wherein: in the step (2) and the step (4), sulfuric acid solution with the mass fraction of 10% -20% is adopted for acid washing activation.
4. The plating process of the rhodium-ruthenium alloy according to claim 1, wherein: in the step (3), the solution components of the copper plating solution are as follows: 80-120g/L of copper sulfate, 180g/L of sulfuric acid 140-.
5. The plating process of the rhodium-ruthenium alloy according to claim 1, wherein: in the step (5), the solution components of the nickel plating solution are as follows: 250g/L of nickel chloride 150-.
6. The plating process of the rhodium-ruthenium alloy according to claim 1, wherein: in the step (6), the gold plating solution comprises the following components: 5-15g/L of gold sodium sulfite, 20-40g/L of potassium citrate, 30-50g/L of potassium thiosulfate, 5-15g/L of citric acid, 1-5g/L of sodium ethylene diamine tetracetate, 2-6mg/L of sodium propynyl sulfonate, 0.5-1.5g/L of mercaptopropane sulfonic acid and 0.1-0.3g/L of N-nitrosophenylhydroxylamine.
7. The plating process of the rhodium-ruthenium alloy according to claim 1, wherein: in the step (7), the rhodium ruthenium plating solution comprises the following components: 1-5g/L rhodium sulfate, 20-60mL/L sulfuric acid, 0.5-1.5g/L ruthenium trichloride and 40-80g/L sulfamic acid.
8. The plating process of the rhodium-ruthenium alloy according to claim 1, wherein: in the step (8), the hole sealing is carried out by adopting a water-based hole sealing agent of hydroxypropyl cellulose or polyvidone; or, an oily hole sealing agent of triethanolamine oleate soap is used for hole sealing.
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