CN117512716B - Preparation of green sustainable cyanide-free gold plating solution and electroplating method thereof - Google Patents
Preparation of green sustainable cyanide-free gold plating solution and electroplating method thereof Download PDFInfo
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- CN117512716B CN117512716B CN202410012631.9A CN202410012631A CN117512716B CN 117512716 B CN117512716 B CN 117512716B CN 202410012631 A CN202410012631 A CN 202410012631A CN 117512716 B CN117512716 B CN 117512716B
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- 239000010931 gold Substances 0.000 title claims abstract description 123
- 238000007747 plating Methods 0.000 title claims abstract description 114
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 112
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 107
- 238000009713 electroplating Methods 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 39
- BAERPNBPLZWCES-UHFFFAOYSA-N (2-hydroxy-1-phosphonoethyl)phosphonic acid Chemical compound OCC(P(O)(O)=O)P(O)(O)=O BAERPNBPLZWCES-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 7
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 75
- 229910052802 copper Inorganic materials 0.000 claims description 75
- 239000010949 copper Substances 0.000 claims description 75
- 239000003921 oil Substances 0.000 claims description 34
- 238000004140 cleaning Methods 0.000 claims description 29
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 29
- 239000012498 ultrapure water Substances 0.000 claims description 29
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 28
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000012535 impurity Substances 0.000 claims description 6
- 238000005498 polishing Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 208000032544 Cicatrix Diseases 0.000 claims description 5
- 244000137852 Petrea volubilis Species 0.000 claims description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- 239000003518 caustics Substances 0.000 claims description 5
- 231100001010 corrosive Toxicity 0.000 claims description 5
- 238000005554 pickling Methods 0.000 claims description 5
- 231100000241 scar Toxicity 0.000 claims description 5
- 230000037387 scars Effects 0.000 claims description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 5
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 5
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 4
- 238000005238 degreasing Methods 0.000 claims description 3
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000005282 brightening Methods 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 2
- 235000011009 potassium phosphates Nutrition 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000000080 wetting agent Substances 0.000 claims description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims 1
- 239000004327 boric acid Substances 0.000 claims 1
- 239000007788 liquid Substances 0.000 claims 1
- 239000008139 complexing agent Substances 0.000 abstract description 17
- 230000008569 process Effects 0.000 abstract description 7
- 150000003839 salts Chemical class 0.000 abstract description 7
- 239000000654 additive Substances 0.000 abstract description 6
- 239000012752 auxiliary agent Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 3
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 238000012360 testing method Methods 0.000 description 12
- 230000000694 effects Effects 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 gold ion Chemical class 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- MXZVHYUSLJAVOE-UHFFFAOYSA-N gold(3+);tricyanide Chemical compound [Au+3].N#[C-].N#[C-].N#[C-] MXZVHYUSLJAVOE-UHFFFAOYSA-N 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000000861 blow drying Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000970 chrono-amperometry Methods 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 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
- 230000002688 persistence Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 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 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229940006280 thiosulfate ion Drugs 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 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
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
- C25D3/14—Electroplating: Baths therefor from solutions of nickel or cobalt from baths containing acetylenic or heterocyclic compounds
- C25D3/18—Heterocyclic compounds
-
- 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
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention belongs to the technical field of gold plating, and discloses a preparation method and an electroplating method of green sustainable cyanide-free gold plating solution, wherein the green sustainable cyanide-free gold plating solution uses 2-4 g/L HAu (GSH) 2 As main salt, GSH of 30-32 g/L is used as main complexing agent, hydroxyethylidene diphosphonic acid of 10-12 g/L is used as auxiliary complexing agent, distilled water is used as solvent, potassium hydroxide of 20 g/L is used as auxiliary agent to adjust the pH value of the gold plating solution to 8.5-9.5, and no additive is used. The invention develops a novel cyanide-free gold plating process which takes the glossiness and thickness of a gold plating layer into consideration through optimizing an electroplating route and process parameters on the basis of the developed green sustainable cyanide-free gold plating solution, and the obtained gold plating layer has bright appearance, fine crystallization and good conductivity.
Description
Technical Field
The invention belongs to the technical field of gold plating, and particularly relates to a preparation method and an electroplating method of green sustainable cyanide-free gold plating solution.
Background
The gold plating layer has excellent electrical conductivity, thermal conductivity, ductility and corrosion resistance, and is widely applied to the fields of electronic industry, aerospace, finishing processing and the like. At present, cyanide-containing technology is basically still adopted for gold plating, and although cyanide gold plating has the advantages of strong impurity resistance, stable gold plating solution, excellent plating compactness and the like, cyanide has extremely toxicity, so that the cyanide not only seriously threatens the health of production operators, but also seriously pollutes the environment, and meanwhile, the cyanide has a plurality of hidden dangers in links of transportation, storage and the like. In order to realize environmental protection and green sustainable development of electroplating industry, the development of cyanide-free gold plating technology to replace the existing cyanide gold plating technology has great social value and economic benefit.
Sulfite ion (SO) 3 2- ) And thiosulfate ion (S) 2 O 3 2- ) As a complexing agent for a monovalent gold ion, au (SO) can be formed by complexing with the monovalent gold ion 3 ) 2 3- And Au (S) 2 O 3 ) 2 3- Ions, their corresponding stability constants (K f ) The values are respectively 10 10 And 10 26 . However, since the gold ion undergoes disproportionation and SO under weaker coordination 3 2- 、S 2 O 3 2- Ion decomposition to make main salt of sodium gold sulfite and SO 3 2- 、S 2 O 3 2- The complexing agent for the ions is not sufficiently stable. The cyanide-free gold plating technology has a certain limit in large-scale popularization and application because of more or less defects in the stability of gold plating solution or the quality of gold plating.
Disclosure of Invention
Aiming at the situation, the invention provides a preparation method of green sustainable cyanide-free gold plating solution and an electroplating method thereof, and HAu (GSH) 2 The cyanide-free gold plating solution with good persistence and dispersion is developed by taking GSH as a main complexing agent, taking hydroxyethylidene diphosphonic acid as an auxiliary complexing agent, taking distilled water as a solvent and taking potassium hydroxide as an auxiliary agent to adjust the pH value of the gold plating solution to 9.0-10.0, and no additive. The invention develops a novel cyanide-free gold plating process which takes the glossiness and thickness of a gold plating layer into consideration through optimizing an electroplating route and process parameters on the basis of the developed green sustainable cyanide-free gold plating solution.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows: the invention provides a green sustainable cyanide-free gold plating solution, which comprises the following components in mass concentration: HAu (GSH) 2 2-4 g/L, GSH 30-32 g/L, hydroxyethylidene diphosphonic acid 10-12 g/L, potassium hydroxide 20 g/L, distilled water as solvent, pH 9.0-10.0, HAu (GSH) 2 The preparation method specifically comprises the following steps:
i, ready to configure HAu (GSH) 2 The required reagents: chloroauric acid solution 3 g/L, sodium thiosulfate solution 10 g/L, GSH 30-32 g/L, potassium hydroxide 20 g/L, dilute sulfuric acid with mass fraction of 5%;
II, dissolving chloroauric acid in sodium thiosulfate in S 2 O 3 2- Ions and Au 3+ Mixing the ions in a molar ratio of 5:2, and uniformly stirring to obtain a solution 1;
III, mixing GSH and solution 1 prepared in step II with GSH and Au 3+ Mixing the ions in a molar ratio of 3:1, and uniformly stirring to obtain a solution 2;
IV, mixing potassium hydroxide with the solution 2 prepared in the step III until the pH value is adjusted to 8.0-9.0, and uniformly stirring to obtain a solution 3;
v, mixing 5% of dilute sulfuric acid with the solution 3 prepared in the step IV until the pH value is regulated to 3.5, and obtaining HAu (GSH) after centrifugation, filtration and washing after uniform stirring 2 。
Preferably, the electroplating method of the green sustainable cyanide-free gold plating solution specifically comprises the following steps:
s1, selecting a red copper sheet as a base material, mechanically polishing the surface of the red copper sheet by using 1200-mesh silicon carbide sand paper, and cleaning the red copper sheet by using ultrapure water after burrs, weld scars, corrosives and impurities are removed;
s2, putting the red copper sheet treated in the step S1 into an oil removal solution, heating the red copper sheet to chemically remove oil, and then cleaning the red copper sheet with ultrapure water;
s3, placing the red copper sheet treated in the step S2 into an oil removal solution, heating the red copper sheet to carry out electrolytic oil removal, and then cleaning the red copper sheet with ultrapure water;
s4, placing the red copper sheet treated in the step S3 into dilute sulfuric acid with the mass fraction of 5% for pickling for 1 min until the red copper sheet becomes bright, and then cleaning with ultrapure water;
s5, putting the red copper sheet treated in the step S4 into electroplating solution, taking the red copper sheet as a cathode, taking a sulfur-containing nickel sheet as an anode, carrying out nickel preplating, and then sequentially carrying out ultrapure water cleaning, dilute sulfuric acid activation with the mass fraction of 5% and ultrapure water cleaning;
s6, placing the red copper sheet treated in the step S5 into a Hall groove, wherein 250 ml cyanide-free gold plating solution is contained in the Hall groove, and the red copper sheet is used as a cathode, so that insoluble Ti-IrO is formed 2 The anode was subjected to electro-gold plating, then washed with distilled water and dried with hot air.
Preferably, in step S2 and step S3, the degreasing solution comprises the following components in mass concentration: 30/g/L potassium carbonate, 65/g/L potassium phosphate, 20/g/L potassium hydroxide and 5/mg/L cetyltrimethylammonium bromide as surfactant.
Preferably, in step S2 and step S3, the heating temperature is 60-65℃and the degreasing time is 16-18 min.
Preferably, in step S5, the mass concentration of the plating solution components is: 100-200 g/L nickel sulfate, 20-32 g/L nickel chloride and boric acid15-22 g/L, 2-3-mg/L brightening agent 2-mercaptobenzothiazole and 1-2 mg/L wetting agent ISS, wherein the pH value of the electroplating solution is 3.5-3.7.
Preferably, in step S5, the plating solution is at a temperature of 57-60deg.C for a plating time of 10-12 min and a current density of 3-5A/dm 2 。
Preferably, in step S6, the cyanide-free gold plating solution is at a temperature of 40-50deg.C, the electroplating time is 10-12 min, and the current density is 0.6-1.0A/dm 2 。
The beneficial effects obtained by the invention are as follows: the invention adopts a novel method by adding GSH to Au (S 2 O 3 ) 2 3- Ligand exchange reaction occurs in the ion solution and is carried out with Au + GSH with ion having high coordination degree is prepared by substituting Au (S 2 O 3 ) 2 3- S in ion 2 O 3 2- Ions further form main salt HAu (GSH) required by the cyanide-free gold plating solution of the invention 2 。
The gold plating solution of the present invention uses HAu (GSH) 2 Is mainly salt and GSH is mainly complexing agent, SO that SO in the gold plating process of sulfite and thiosulfate in the market is completely eradicated 3 2- And S is 2 O 3 2- Ions and Au + The defects of poor continuous performance caused by disproportionation reaction due to insufficient ion coordination degree are overcome, no precipitate is precipitated after the gold plating solution is stood for 6 months, and the gold plating solution has the characteristics of safety, no toxicity, simple preparation, strong sustainability and the like.
The gold plating solution provided by the invention uses the hydroxy ethylidene diphosphonic acid as an auxiliary coordination agent to interact with the main coordination agent GSH, the formed stable complex can further improve the conductivity of the gold plating solution, and the addition of the hydroxy ethylidene diphosphonic acid can effectively improve the glossiness of a gold plating layer.
The gold plating solution of the invention has no addition of any additive and Au + The ionic solubility is low, the manufacturing cost is lower than that of the conventional gold plating solution in the market, but the covering capacity of the gold plating solution can reach 100%, the dispersing capacity can reach 70%, and the manufacturing cost is low but the performance is high.
The green sustainable cyanide-free gold plating solution is based on the invention, the electroplating route and the technological parameters are optimized through a Hall groove experiment, the novel cyanide-free gold plating process is developed, the glossiness and the thickness of the gold plating layer are considered, and the obtained gold plating layer has bright appearance, fine crystallization and good conductivity.
Drawings
FIG. 1 shows a gold plating layer obtained by a right angle cathode method according to example 2 of the present invention;
FIG. 2 is a comparison of CV curves of the gold plating solution of example 2 of the present invention for different times;
FIG. 3 shows the thickness of the centers of the points of the gold plating layer according to example 2 of the present invention;
FIG. 4 is a schematic view showing the appearance of a gold plating layer for Hall groove test in examples 1-3 of the present invention;
FIG. 5 is a graph showing the effect of the auxiliary complexing agent hydroxyethylidene diphosphonic acid of examples 1-3 of the present invention on the appearance of a gold plating layer;
FIG. 6 is a graph showing the effect of the values of examples 1-3 pH of the present invention on the appearance of a gold plating layer;
FIG. 7 shows the effect of temperature on the appearance of gold plating in examples 1-3 of the present invention.
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention.
Detailed Description
The following description of the embodiments of the present invention will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all embodiments of the invention; all other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art. In addition, any methods and materials similar or equivalent to those described herein can be used in the present invention. The preferred methods and materials described herein are illustrative only and should not be construed as limiting the scope of the present application.
The experimental methods in the following examples are all conventional methods unless otherwise specified; the test materials used in the examples described below, unless otherwise specified, were purchased from commercial sources.
Example 1: the green sustainable cyanide-free gold plating solution comprises the following components in percentage by mass: main salt HAu (GSH) 2 2 g/L, main complexing agent GSH 30 g/L, auxiliary complexing agent hydroxyethylidene diphosphonic acid 10 g/L, distilled water as solvent, and 20 g/L potassium hydroxide as auxiliary agent to adjust the pH value of the gold plating solution to 9.0, without adding additives.
The green sustainable cyanide-free gold plating solution electroplating method specifically comprises the following steps:
s1, selecting a red copper sheet as a base material, mechanically polishing the surface of the red copper sheet by using 1200-mesh silicon carbide sand paper, and cleaning the red copper sheet by using ultrapure water after burrs, weld scars, corrosives and impurities are removed;
s2, putting the red copper sheet treated in the step S1 into an oil removing solution, heating the red copper sheet to chemically remove oil, wherein the temperature of the oil removing solution is 60 ℃, the oil removing time is 16 min, and then cleaning the red copper sheet with ultrapure water;
s3, placing the red copper sheet treated in the step S2 into an oil removing solution, heating the oil removing solution to carry out electrolytic oil removal, wherein the temperature of the oil removing solution is 60 ℃, the oil removing time is 16 min, and then cleaning the red copper sheet with ultrapure water;
s4, placing the red copper sheet treated in the step S3 into dilute sulfuric acid with the mass fraction of 5% for pickling for 1 min until the red copper sheet becomes bright, and then cleaning with ultrapure water;
s5, placing the red copper sheet processed in the step S4 into electricityIn the plating solution, copper sheet is used as cathode, sulfur-containing nickel plate is used as anode to carry out nickel preplating, the temperature of the plating solution is 57 ℃, the electroplating time is 10 min, and the current density is 3A/dm 2 Then sequentially carrying out ultrapure water cleaning, dilute sulfuric acid activation with the mass fraction of 5% and ultrapure water cleaning;
s6, placing the red copper sheet treated in the step S5 into a Hall groove, wherein 250 ml cyanide-free gold plating solution is contained in the Hall groove, and the red copper sheet is used as a cathode, so that insoluble Ti-IrO is formed 2 Electroplating the anode with cyanide-free gold plating solution at 40deg.C for 10 min at current density of 0.6A/dm 2 Then washing with distilled water and drying with hot air.
Example 2: the green sustainable cyanide-free gold plating solution comprises the following components in percentage by mass: main salt HAu (GSH) 2 3 g/L, main complexing agent GSH 31 g/L, auxiliary complexing agent hydroxyethylidene diphosphonic acid 11 g/L, distilled water as solvent, and 20 g/L potassium hydroxide as auxiliary agent to adjust the pH value of the gold plating solution to 9.5, without adding additives.
The green sustainable cyanide-free gold plating solution electroplating method specifically comprises the following steps:
s1, selecting a red copper sheet as a base material, mechanically polishing the surface of the red copper sheet by using 1200-mesh silicon carbide sand paper, and cleaning the red copper sheet by using ultrapure water after burrs, weld scars, corrosives and impurities are removed;
s2, putting the red copper sheet treated in the step S1 into an oil removing solution, heating the red copper sheet to chemically remove oil, wherein the temperature of the oil removing solution is 63 ℃, the oil removing time is 17 min, and then cleaning the red copper sheet with ultrapure water;
s3, placing the red copper sheet treated in the step S2 into an oil removing solution, heating the copper sheet to carry out electrolytic oil removal, wherein the temperature of the oil removing solution is 63 ℃, the oil removing time is 17 min, and then cleaning the copper sheet with ultrapure water;
s4, placing the red copper sheet treated in the step S3 into dilute sulfuric acid with the mass fraction of 5% for pickling for 1 min until the red copper sheet becomes bright, and then cleaning with ultrapure water;
s5, placing the red copper sheet treated in the step S4 into an electroplating solution, and pre-plating nickel by taking the red copper sheet as a cathode and a sulfur-containing nickel plate as an anode, wherein the temperature of the electroplating solution is 58The electroplating time is 11 min, and the current density is 4A/dm 2 Then sequentially carrying out ultrapure water cleaning, dilute sulfuric acid activation with the mass fraction of 5% and ultrapure water cleaning;
s6, placing the red copper sheet treated in the step S5 into a Hall groove, wherein 250 ml cyanide-free gold plating solution is contained in the Hall groove, and the red copper sheet is used as a cathode, so that insoluble Ti-IrO is formed 2 Electroplating the anode with cyanide-free gold plating solution at 45deg.C for 11 min at current density of 0.8. 0.8A/dm 2 Then washing with distilled water and drying with hot air.
Example 3: the green sustainable cyanide-free gold plating solution comprises the following components in percentage by mass: main salt HAu (GSH) 2 4. 4 g/L, main complexing agent GSH 32 g/L, auxiliary complexing agent hydroxyethylidene diphosphonic acid 12 g/L, distilled water as solvent, and 20. 20 g/L potassium hydroxide as auxiliary agent to adjust the pH value of the gold plating solution to 10.0, without adding additives.
The green sustainable cyanide-free gold plating solution electroplating method specifically comprises the following steps:
s1, selecting a red copper sheet as a base material, mechanically polishing the surface of the red copper sheet by using 1200-mesh silicon carbide sand paper, and cleaning the red copper sheet by using ultrapure water after burrs, weld scars, corrosives and impurities are removed;
s2, putting the red copper sheet treated in the step S1 into an oil removing solution, heating the red copper sheet to chemically remove oil, wherein the temperature of the oil removing solution is 65 ℃, the oil removing time is 18 min, and then cleaning the red copper sheet with ultrapure water;
s3, placing the red copper sheet treated in the step S2 into an oil removing solution, heating the copper sheet to carry out electrolytic oil removal, wherein the temperature of the oil removing solution is 65 ℃, the oil removing time is 18 min, and then cleaning the copper sheet with ultrapure water;
s4, placing the red copper sheet treated in the step S3 into dilute sulfuric acid with the mass fraction of 5% for pickling for 1 min until the red copper sheet becomes bright, and then cleaning with ultrapure water;
s5, placing the red copper sheet treated in the step S4 into an electroplating solution, taking the red copper sheet as a cathode and a sulfur-containing nickel plate as an anode for nickel preplating, wherein the temperature of the electroplating solution is 60 ℃, the electroplating time is 12 min, and the current density is 5A/dm 2 Then sequentially passing through ultrapure waterWashing, namely activating dilute sulfuric acid with the mass fraction of 5% and cleaning with ultrapure water;
s6, placing the red copper sheet treated in the step S5 into a Hall groove, wherein 250 ml cyanide-free gold plating solution is contained in the Hall groove, and the red copper sheet is used as a cathode, so that insoluble Ti-IrO is formed 2 Electroplating the anode with cyanide-free gold plating solution at 50deg.C for 12 min at current density of 1.0. 1.0A/dm 2 Then washing with distilled water and drying with hot air.
Experimental example
1. In the embodiment 1-3 of the invention, CV test is carried out on the green sustainable cyanide-free gold plating solution before and after the placement, and the stability of the green sustainable cyanide-free gold plating solution is analyzed. Electrochemical testing during the experiment mainly included Cyclic Voltammogram (CV), linear Sweep Voltammogram (LSV) and Chronoamperometry (CA). The electrochemical test uses a three-electrode electrolytic cell made of glass, and the test instrument is a CHI750d electrochemical workstation. In the test process, a reference electrode and an auxiliary electrode respectively adopt a platinum wire (phi=0.38 mm) and a platinum sheet (1 cm ×1 cm), wherein the working electrode comprises a glassy carbon electrode (GCE, phi=3 mm), a rotary disk glassy carbon electrode (GC-RDE, phi=5 mm), a gold electrode (Au, phi=3 mm) and a platinum electrode (Pt, phi=3 mm), and the test temperature is 328K. The scanning speed of the linear sweep voltammogram is 1 mV s -1 The scanning speed of the cyclic voltammogram is 10 mV s -1 . In the course of the experiment, alpha-Al having a particle diameter of 0.5 μm was used before and after each experiment 2 O 3 Treating working electrode with polishing powder, sequentially washing with ethanol and distilled water, and using N 2 And (5) blow-drying.
2. In the embodiment 1-3, the dispersion capacity of the gold plating solution is measured by adopting a right-angle cathode method, and in the experiment, the red copper sheet after nickel preplating is bent into a right angle along the center line, and immersed into the square groove gold plating solution for electroplating. After electroplating, the cathode plate is unfolded, and the ratio of the coated area to the total area of the cathode is the dispersion capacity.
Analysis of results
FIG. 1 shows a gold plating layer obtained by the right angle cathode method according to example 2 of the present invention, it can be observed that the current density is0.8 A/dm 2 After the electroplating time is 11 min, the result shows that all areas of the cathode are covered by the gold plating layer, which indicates that the covering capacity of the gold plating solution reaches 100 percent.
FIG. 2 shows the CV curves of the gold plating solution of the embodiment 2 of the invention after being placed for different time periods, the CV curves are not obviously changed compared with the freshly prepared gold plating solution after being placed for 6 months, and the positions of the oxidation peak and the reduction peak are hardly moved, thus indicating that the stability of the gold plating solution is better.
FIG. 3 shows the thickness of the centers of the gold plating layers in example 2 of the present invention, and it can be observed that the thicknesses of the centers of the No. 1-8 gold plating layers of the Hall groove test piece are in the range of 0.23-0.58 and cm, and the dispersion capacity of the gold plating solution is 70%, which indicates that the dispersion capacity of the gold plating solution is good.
FIG. 5 is a graph showing the effect of the auxiliary complexing agent of hydroxyethylidene diphosphonic acid on the appearance of a gold coating according to the embodiment 1-3 of the present invention, and according to the schematic view of the appearance of the gold coating in the Hall cell experiment of FIG. 4, the fogging and reddening of the gold coating of the Hall cell test piece without the auxiliary complexing agent of hydroxyethylidene diphosphonic acid can be observed, and when the concentration of the added auxiliary complexing agent of hydroxyethylidene diphosphonic acid is in the range of 10 g/L-12 g/L, the gold coating of the Hall cell test piece is bright in the range of 2.5-10 cm, and the excellent bright effect of the gold coating is shown.
FIG. 6 is a graph showing the effect of the values of examples 1-3 and pH on the appearance of the gold plating layer, wherein the effect of the values of the gold plating layer on the appearance of the gold plating layer is observed to be almost full-scale red and hazy when the pH value of the gold plating solution is 7.0, and the appearance of the lower part 3-cm of the gold plating layer of the Hall cell test piece is bright when the pH value of the gold plating solution is 9.0-10.0, and the pH value of the gold plating solution is 9.0-10.0.
FIG. 7 is a graph showing the effect of the temperature of examples 1-3 on the appearance of the gold plating layer, wherein the effect of the temperature on the appearance of the gold plating layer is extremely insensitive to the effect of the temperature according to the schematic view of the appearance of the gold plating layer in the Hall cell experiment of FIG. 4, and the Hall cell test piece with consistent appearance and quality of the gold plating layer can be obtained when the temperature of the gold plating solution is 40-50 ℃.
Although embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made therein without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
The invention and its embodiments have been described above with no limitation, and the invention is illustrated in the figures of the accompanying drawings as one of its embodiments, without limitation in practice. In summary, those skilled in the art, having benefit of this disclosure, will appreciate that the invention can be practiced without the specific details disclosed herein.
Claims (7)
1. A green sustainable cyanide-free gold plating solution is characterized in that: comprises the following components in percentage by mass: HAu (GSH) 2 2-4 g/L, GSH 30-32 g/L, hydroxyethylidene diphosphonic acid 10-12 g/L, potassium hydroxide 20 g/L, distilled water as solvent, pH 9.0-10.0, HAu (GSH) 2 The preparation method specifically comprises the following steps:
i, ready to configure HAu (GSH) 2 The required reagents: chloroauric acid solution 3 g/L, sodium thiosulfate solution 10 g/L, GSH 30-32 g/L, potassium hydroxide 20 g/L, dilute sulfuric acid with mass fraction of 5%;
II, dissolving chloroauric acid in sodium thiosulfate in S 2 O 3 2- Ions and Au 3+ Mixing the ions in a molar ratio of 5:2, and uniformly stirring to obtain a solution 1;
III, mixing GSH and solution 1 prepared in step II with GSH and Au 3+ Mixing the ions in a molar ratio of 3:1, and uniformly stirring to obtain a solution 2;
IV, mixing potassium hydroxide with the solution 2 prepared in the step III until the pH value is adjusted to 8.0-9.0, and uniformly stirring to obtain a solution 3;
v, mixing 5% of dilute sulfuric acid with the solution 3 prepared in the step IV until the pH value is regulated to 3.5, and obtaining HAu (GSH) after centrifugation, filtration and washing after uniform stirring 2 。
2. A method for electroplating a green and sustainable cyanide-free gold plating bath according to claim 1, comprising the steps of:
s1, selecting a red copper sheet as a base material, mechanically polishing the surface of the red copper sheet by using 1200-mesh silicon carbide sand paper, and cleaning the red copper sheet by using ultrapure water after burrs, weld scars, corrosives and impurities are removed;
s2, putting the red copper sheet treated in the step S1 into an oil removal solution, heating the red copper sheet to chemically remove oil, and then cleaning the red copper sheet with ultrapure water;
s3, placing the red copper sheet treated in the step S2 into an oil removal solution, heating the red copper sheet to carry out electrolytic oil removal, and then cleaning the red copper sheet with ultrapure water;
s4, placing the red copper sheet treated in the step S3 into dilute sulfuric acid with the mass fraction of 5% for pickling for 1 min until the red copper sheet becomes bright, and then cleaning with ultrapure water;
s5, putting the red copper sheet treated in the step S4 into electroplating solution, taking the red copper sheet as a cathode, taking a sulfur-containing nickel sheet as an anode, carrying out nickel preplating, and then sequentially carrying out ultrapure water cleaning, dilute sulfuric acid activation with the mass fraction of 5% and ultrapure water cleaning;
s6, placing the red copper sheet treated in the step S5 into a Hall groove, wherein 250 ml cyanide-free gold plating solution is contained in the Hall groove, and the red copper sheet is used as a cathode, so that insoluble Ti-IrO is formed 2 The anode was subjected to electro-gold plating, then washed with distilled water and dried with hot air.
3. The electroplating method of the green sustainable cyanide-free gold plating bath according to claim 2, which is characterized in that: in the step S2 and the step S3, the oil removing solution comprises the following components in mass concentration: 30/g/L potassium carbonate, 65/g/L potassium phosphate, 20/g/L potassium hydroxide and 5/mg/L cetyltrimethylammonium bromide as surfactant.
4. A method for electroplating a green sustainable cyanide-free gold plating bath according to claim 3, wherein: in the step S2 and the step S3, the heating temperature is 60-65 ℃ and the degreasing time is 16-18 min.
5. The electroplating method of the green sustainable cyanide-free gold plating bath according to claim 4, which is characterized in that: in step S5, the mass concentration of the plating liquid components is: 100-200 g/L of nickel sulfate, 20-32 g/L of nickel chloride, 15-22 g/L of boric acid, 2-3 mg/L of brightening agent 2-mercaptobenzothiazole and 1-2 mg/L of wetting agent ISS, wherein the pH value of the electroplating solution is 3.5-3.7.
6. The electroplating method of the green sustainable cyanide-free gold plating bath according to claim 5, which is characterized in that: in step S5, the temperature of the electroplating solution is 57-60 ℃, the electroplating time is 10-12 min, and the current density is 3-5A/dm 2 。
7. The electroplating method of the green sustainable cyanide-free gold plating bath according to claim 6, which is characterized in that: in step S6, the cyanide-free gold plating solution has a temperature of 40-50deg.C, a plating time of 10-12 min, and a current density of 0.6-1.0A/dm 2 。
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