CN114108040A - Cyanide-free gold plating solution and gold electroforming part manufactured by cyanide-free electroplating process - Google Patents
Cyanide-free gold plating solution and gold electroforming part manufactured by cyanide-free electroplating process Download PDFInfo
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- CN114108040A CN114108040A CN202010861882.6A CN202010861882A CN114108040A CN 114108040 A CN114108040 A CN 114108040A CN 202010861882 A CN202010861882 A CN 202010861882A CN 114108040 A CN114108040 A CN 114108040A
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- Prior art keywords
- gold
- cyanide
- gold plating
- plating solution
- free
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- 239000010931 gold Substances 0.000 title claims abstract description 128
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 126
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 238000007747 plating Methods 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims description 31
- 238000009713 electroplating Methods 0.000 title abstract description 21
- 238000005323 electroforming Methods 0.000 title description 18
- 239000008139 complexing agent Substances 0.000 claims abstract description 16
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 5
- 150000007519 polyprotic acids Polymers 0.000 claims abstract description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 39
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 36
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 27
- 229910052816 inorganic phosphate Inorganic materials 0.000 claims description 23
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 22
- 229940081974 saccharin Drugs 0.000 claims description 22
- 235000019204 saccharin Nutrition 0.000 claims description 22
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 22
- QVYARBLCAHCSFJ-UHFFFAOYSA-N butane-1,1-diamine Chemical compound CCCC(N)N QVYARBLCAHCSFJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000008363 phosphate buffer Substances 0.000 claims description 20
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 claims description 18
- 239000004471 Glycine Substances 0.000 claims description 18
- 235000010265 sodium sulphite Nutrition 0.000 claims description 18
- 229960001124 trientine Drugs 0.000 claims description 18
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 13
- XTOQOJJNGPEPMM-UHFFFAOYSA-N o-(2-oxo-1,3,2$l^{5}-dioxaphosphinan-2-yl)hydroxylamine Chemical compound NOP1(=O)OCCCO1 XTOQOJJNGPEPMM-UHFFFAOYSA-N 0.000 claims description 13
- 229940026189 antimony potassium tartrate Drugs 0.000 claims description 12
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 claims description 12
- 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 description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000000654 additive Substances 0.000 claims description 4
- 230000000996 additive effect Effects 0.000 claims description 4
- 239000000872 buffer Substances 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 230000000536 complexating effect Effects 0.000 claims 1
- 239000000463 material Substances 0.000 claims 1
- 238000002360 preparation method Methods 0.000 abstract description 4
- 239000002360 explosive Substances 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 49
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 48
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 27
- 239000000203 mixture Substances 0.000 description 17
- 229940001482 sodium sulfite Drugs 0.000 description 17
- -1 hydrogen ions Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- FDGBQHCDMSYZRC-UHFFFAOYSA-N 2-hydroxy-2-oxo-1,3,2$l^{5}-dioxaphosphinan-4-amine Chemical compound NC1CCOP(O)(=O)O1 FDGBQHCDMSYZRC-UHFFFAOYSA-N 0.000 description 9
- 238000004616 Pyrometry Methods 0.000 description 8
- DDAQLPYLBPPPRV-UHFFFAOYSA-N [4-(hydroxymethyl)-2-oxo-1,3,2lambda5-dioxaphosphetan-2-yl] dihydrogen phosphate Chemical compound OCC1OP(=O)(OP(O)(O)=O)O1 DDAQLPYLBPPPRV-UHFFFAOYSA-N 0.000 description 8
- 238000009472 formulation Methods 0.000 description 8
- 239000001993 wax Substances 0.000 description 8
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 6
- 229910001152 Bi alloy Inorganic materials 0.000 description 5
- 239000002585 base Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000011265 semifinished product Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 229960002449 glycine Drugs 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 229940101006 anhydrous sodium sulfite Drugs 0.000 description 3
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 3
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 description 3
- WDZVNNYQBQRJRX-UHFFFAOYSA-K gold(iii) hydroxide Chemical compound O[Au](O)O WDZVNNYQBQRJRX-UHFFFAOYSA-K 0.000 description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 description 3
- 235000019799 monosodium phosphate Nutrition 0.000 description 3
- 229940093932 potassium hydroxide Drugs 0.000 description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- DMOXNIKYXJYCFQ-UHFFFAOYSA-N (2-hydroxy-1-phosphonooxyethyl) dihydrogen phosphate Chemical compound OP(=O)(O)OC(CO)OP(O)(O)=O DMOXNIKYXJYCFQ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 229940012017 ethylenediamine Drugs 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 239000006174 pH buffer Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229940083608 sodium hydroxide Drugs 0.000 description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PTLXXCCTGURQMN-UHFFFAOYSA-N CC1OP(O)(=O)OP(=O)(OO)O1 Chemical compound CC1OP(O)(=O)OP(=O)(OO)O1 PTLXXCCTGURQMN-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical class OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000006179 pH buffering agent Substances 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004018 waxing Methods 0.000 description 1
- 238000005303 weighing 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
- 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
- C25D1/00—Electroforming
Landscapes
- 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
A cyanide-free gold plating solution comprises a gold salt, a complexing agent and a plurality of hydroxyl organic polybasic acids. The components of the cyanide-free gold plating solution have synergistic effect, and are superior to the existing cyanide-free gold plating solution. The working temperature range of the cyanide-free gold plating solution is between 30 and 70 ℃, the pH value is between 7.2 and 8.7, and the current density range is between 0.05 and 0.55 ASD. The electroplating solution does not produce explosive bronsted in the preparation process, and is environment-friendly and safe.
Description
Technical Field
The invention relates to a cyanide-free gold plating solution, a cyanide-free gold plating process and a gold electroformed product manufactured by the cyanide-free electroplating process.
Background
Gold is metal with high value retention and high ornamental value. Gold articles, particularly football articles such as ornaments and other articles are popular with the general public . For the person skilled in the art who is familiar with the production of gold objects, the term gold means that the gold content is equal to or higher than 99.5 parts per hundred. Consumers also occasionally refer to the term "pure" as the term "pure". However, the conventional metal has a lower hardness and strength (greater hardness of about , 20-40Hv), and is easily deformed. This physical property limits to some extent the shape, substantial shape, plasticity, and volume of a platinum article, particularly a hollow platinum article.
The cyanide-free plating process allows the preparation of high-hardness gold without using a cyanide-containing gold plating solution.
Summary of The Invention
The invention provides a cyanide-free gold plating solution which comprises organic polyacid with a plurality of hydroxyl groups.
The organic polybasic acid, especially the organic polybasic acid containing a plurality of hydroxyl groups, can ionize a plurality of hydrogen ions in water, form a plurality of coordinated oxygen atoms after ionization, and form coordinate bonds with gold ions with empty orbitals to form a stable space geometry structure, so as to generate a gold ion chelate. The chelate has good chemical stability, is not easy to hydrolyze, can resist higher temperature, and can optimize the electroplating temperature range. Both hydroxyethylidene diphosphoric acid (HEDP) and aminotrimethylene phosphoric Acid (ATMP) belong to the class of organic polyacids with multiple hydroxyl groups. Chelating agents, also known as complexing agents, are compounds that provide molecules, atoms, or ions that coordinate lone electron pairs.
The organic polyacid may be an organic phosphoric acid.
The organic polyacid may include aminotrimethylene phosphate and/or hydroxyethylidene diphosphate.
The organic phosphoric acid may include 15 to 80g/L aminotrimethylene phosphoric acid and/or 10 to 80g/L hydroxyethylidene diphosphonic acid.
The cyanide-free gold plating solution also comprises a gold salt and a complexing agent when in electroplating.
The gold salt provides a source of gold ions in the electroplating bath and may be a gold sulfite salt.
The complexing agent may comprise a first complexing agent and/or a second complexing agent, the primary function of which is to complex gold ions.
The first complexing agent may include a sulfite salt, including a sodium, potassium and/or ammonium salt, as the primary complexing agent.
The complexing agent may comprise sodium sulfite, for example 30 to 160g/L sodium sulfite.
The second complexing agent may comprise an organic amine or amine salt. Organic amines such as: the ethylene diamine, the butanediamine and the propane diamine are easy to dissolve in water and have small toxicity, and have the main effects of chelating gold ions in the plating solution, namely stably fixing free gold ions in the plating solution, and the molecular chains of the ethylene diamine, the butanediamine and the propane diamine are easily decomposed into short-chain organic matters after being small in failure, have small influence on the specific gravity of the plating solution, and are beneficial to operations such as crystallization and impurity removal in the later period. One or two of ethylenediamine, propylenediamine and butylenediamine can improve the property of the plating layer, increase the luster and prevent the formation of pinholes. The complexing agent can comprise 1-15g/L of ethylenediamine, butanediamine and/or organic amine substances of propanediamine such as ethylenediamine, propanediamine, butanediamine and the like which are easy to volatilize.
Glycerol may be added to the plating bath to control the effects of volatile components in the bath. The glycine can act synergistically with the volatile organic amines in the plating solution to play a role in brightening and homogenizing. At the same time, it can also buffer the pH of the plating solution, as with inorganic phosphate, and control it within a predetermined range.
The cyanide-free gold plating solution can comprise a hardening agent to prepare high-hardness pure gold.
The hardening agent may include a combination of saccharin, antimony potassium tartrate, triethylene tetramine, and/or butynediol. Triethylene tetramine and butynediol contain unsaturated carbon bonds and can be hardened.
The combination of hardening agents may be: saccharin + triethylenetetramine + potassium antimony tartrate, saccharin + butynediol + potassium antimony tartrate, saccharin + triethylenetetramine, and butynediol + potassium antimony tartrate.
The cyanide-free gold plating solution can comprise 4g/L butynediol.
The cyanide-free gold plating solution can comprise 2g/L of saccharin.
The cyanide-free gold plating solution can comprise 5-40g/L of inorganic phosphate buffer. The inorganic phosphate buffer may include sodium dihydrogen phosphate and disodium hydrogen phosphate in a mass ratio of 0.5 to 5.
The cyanide-free gold plating solution may comprise sodium hydroxide, potassium hydroxide and/or sulfuric acid for adjusting pH, such as 200-250g/L sodium hydroxide, potassium hydroxide and/or 1-5% sulfuric acid. The cyanide-free gold plating solution can comprise an additive for preparing a plating mirror. The additive for making the coated mirror can include an organophosphonic acid as a primary mirror additive.
The cyanide-free gold plating solution may include a pH buffer to buffer pH fluctuations caused by the gold being electrolyzed. The pH buffering agent of the cyanide-free gold plating solution can comprise inorganic phosphate. The pH buffer can be set to a buffer range of pH 5.5-8.5. Inorganic phosphate buffers may include sodium dihydrogen phosphate and disodium hydrogen phosphate. The mass ratio of sodium dihydrogen phosphate to disodium hydrogen phosphate may be 0.5-5.
The cyanide-free gold plating solution may include bath intermediates to control and stabilize the pH of the bath within a predetermined range. The bath intermediate may include one or more of sodium hydroxide, potassium hydroxide, sulfuric acid, and may be used to adjust the pH of the gold plating bath to 7.2-8.7, including 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, or any pH range selected from any of the foregoing values. When the electroplating is carried out within the pH range, each component is stable, so that the electroplating effect of hardening and smooth and bright surface can be exerted. Meanwhile, the frequency of correcting the pH meter can be reduced, and the requirement on the precision of the pH meter is low; the cost and the actual operation difficulty are reduced to a certain degree.
The concentration of sulfuric acid for adjusting the pH value of the gold plating solution can be between 1% and 5%.
The components of the cyanide-free gold plating solution have synergistic effect, and are superior to the existing cyanide-free gold plating solution.
The working temperature range of the cyanide-free gold plating solution is between 30 and 70 ℃ (including 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, or any temperature range formed by selecting any value), the pH value is between 7.2 and 8.7, and the current density range is between 0.05 and 0.55 ASD.
The electroplating solution does not produce explosive bronsted in the preparation process, and is environment-friendly and safe.
The content ranges of the plating bath components may be: 7-18g/L gold, 30-160g/L sodium sulfite, 0-2g/L saccharin, 0-4g/L butynediol, 1-15g/L butanediamine, 1-15g/L ethylenediamine, 1-15g/L glycine, 15-80g/L hydroxyethylidene diphosphonic acid, 10-80g/L aminotrimethylene phosphoric acid, 0-2g/L triethylene tetramine, 25-40 g/L inorganic phosphate, 0-2g/L antimony potassium tartrate and 0-20g/L glycerol.
Description of the invention
Base liquid
The gold plating solution for making electroformed gold contains gold (Au) ions. The gold plating solution may be made of a base solution containing gold (Au) ions. The plating solution may be prepared on the basis of sodium gold sulfite. The basic liquid can be prepared by adding high-purity gold fragments into aqua regia.
For example, 99.99% gold fragments weighing 60g and analytically pure aqua regia (a mixture of nitric acid and hydrochloric acid) are added to a reaction kettle for reaction. After the gold and the aqua regia completely react, a small amount of hydrochloric acid is dripped until no colored gas escapes from the reaction kettle, and the solution (a) is obtained. After the solution (a) was left to cool to room temperature (e.g., 25 ℃), pure water was added and stirred uniformly, and a sodium hydroxide solution (e.g., 100 g/L) was added until complete reaction to obtain a solution (a 1). The solution (a 1) was allowed to stand and cooled to room temperature to obtain gold hydroxide emulsion (b). Standing the emulsion (b), and demixing the precipitate to obtain a gold hydroxide precipitate (c). Adding pure water (300 mL) in a sufficient amount to wash the solid precipitate (c), adding analytically pure anhydrous sodium sulfite powder (150 g) after washing, stirring at constant temperature (1 hour, for example), adding dilute sulfuric acid (2% dilute sulfuric acid, for example), adjusting the pH to 8.5-9.5, continuing the constant temperature reaction (6 hours of constant temperature reaction, for example), clarifying the solid suspension, and obtaining clear and transparent gold sodium sulfite base solution (d) containing gold ions.
200-250g/L sodium hydroxide or potassium hydroxide can be used in the preparation process of the gold sodium sulfite basic solution (d) to generate gold hydroxide solid by controlling the reaction speed and the reaction temperature.
Gold plating solution
Adding the prepared medicament into the gold sodium sulfite base solution to form a gold plating solution.
Electroplating process
The module was placed in an electroforming tank filled with a gold plating solution, and a current density value, an electroplating temperature, an electroplating time, and a pH value (basic acid value) were set to perform electroplating. After the power is turned on, the module which is immersed in the gold plating solution and connected with the cathode of the electroforming bath is electrified, electroplating is carried out on the module, and gold ions complexed in the electroplating solution are slowly precipitated on the module to form a gold plating layer with a certain thickness. The anode of the electroforming cell may be a titanium mesh. The mold is typically a wax mold or a tin-bismuth alloy mold.
When the wax mould is used as an electroforming mould, the wax mould is placed in an electroforming tank filled with gold plating solution, the wax mould is coated with conductive oil, and the wax mould coated with the conductive oil is placed on a hanging rod of the electroforming tank and is connected with the cathode of the electroforming tank. After the power supply is turned on for electroplating, the gold ions complexed in the electroplating solution slowly precipitate on the wax mould to form a gold-plated layer with a certain thickness, the gold semi-finished product after electroplating is put into paraffin removal water, after the wax in the plating layer is removed, the gold semi-finished product is put into a de-waxing solution to remove the conducting layer, and after the gold semi-finished product is cleaned by clear water, the electroformed gold piece with the cyanide-free hard gold plating layer is obtained.
When the tin-bismuth alloy module is used as an electroforming module, the module is placed in an electroforming tank filled with gold plating solution, and the tin-bismuth alloy module is arranged on a hanging rod and connected with the cathode of the electroforming tank. After the power supply is turned on, gold ions complexed in the electroplating solution slowly precipitate on the module to form a gold-plated layer with a certain thickness, the electroplated gold semi-finished product is placed in an oven to be heated, the tin-bismuth alloy in the plating layer is removed, then the gold semi-finished product is placed in nitric acid and sulfuric acid to remove the residual conductive layer, and the cyanide-free hard gold plating layer is obtained after being cleaned by clear water. Before plating the tin-bismuth mould with gold, a layer of protective copper may be electroplated, and if necessary, a layer of nickel may be electroplated.
The capacity of the gold plating solution in the electroforming bath used in the examples was 5L (liters). Electroforming is carried out in an electroforming tank by using the gold plating solution. Dilute sulfuric acid was used to adjust the pH to the slight basic value when the electroplating of the examples was performed.
Example 1
The following formulation agent components of example 1 were added to the base solution to constitute a gold plating solution: anhydrous sodium sulfite, aminotrimethylene phosphate, hydroxyl ethylidene diphosphate, inorganic phosphate buffer, butanediamine, sodium hydroxide, antimony potassium tartrate, triethylene tetramine and saccharin.
One specific example of the composition of example 1 is: 90g of anhydrous sodium sulfite, 100g of aminotrimethylene phosphoric acid, 60g of hydroxyethylidene diphosphonic acid, 104g of inorganic phosphate buffer, 30g of butanediamine, 45g of sodium hydroxide, 0.015g of potassium antimony tartrate, 1g of triethylene tetramine and 0.5g of saccharin.
The process conditions for this example 1 were set as: the plating temperature was 25 ℃, the plating current value was 0.2ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 7.2.
The electroformed gold product produced by the process of example 1 had a thickness of 230 μm, a vickers hardness of 160HV, a gold purity of 99.70% as determined by pyrometry, a smooth surface, a brightness level B, and a mirror effect.
Example 2
The formulation of example 2 includes sodium sulfite, aminotrimethylene phosphate, hydroxyethylidene diphosphate, inorganic phosphate buffers, ethylenediamine, glycine, triethylenetetramine, potassium hydroxide, saccharin.
An example of a specific composition of example 2 is: 140g of sodium sulfite, 180g of aminotrimethylene phosphoric acid, 100g of hydroxyethylidene diphosphonic acid, 104g of an inorganic phosphate buffer, 27g of ethylenediamine, 27g of glycine, 0.5g of triethylenetetramine, 125g of potassium hydroxide and 0.3g of saccharin.
The process conditions for this example 2 were set as: the plating temperature was 25 ℃, the plating current value was 0.25ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 8.2.
The electroformed gold product produced by the process of this example 2 had a thickness of 220 μm, a vickers hardness of 110HV, a gold purity of 99.50% as determined by pyrometry, a smooth surface, a bright grade a, and a mirror effect.
Example 3
The formulation of example 3 included sodium sulfite, aminotrimethylene phosphate, hydroxyethylidene diphosphate, inorganic phosphate buffers, ethylenediamine, glycine, triethylenetetramine, sodium hydroxide, saccharin, and antimony potassium tartrate.
An example of a specific composition of example 3 is: 140g of sodium sulfite, 90g of aminotrimethylene phosphoric acid, 150g of hydroxyethylidene diphosphonic acid, 104g of inorganic phosphate buffer, 35g of ethylenediamine, 50g of glycine, 0.5g of triethylene tetramine, 200g of sodium hydroxide, 0.3g of saccharin, 0.025g of antimony potassium tartrate.
The process conditions for this example 3 were set as: the plating temperature was 45 ℃, the plating current value was 0.3ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 7.5.
The electroformed gold product produced by the process of this example 3 has a thickness of 240 μm, a vickers hardness of 170HV, a gold purity of 99.70% as determined by a pyrometry, a smooth surface, a bright grade a, and a specular effect.
Example 4
The formulation of example 4 included sodium sulfite, aminotrimethylene phosphate, hydroxyethylidene diphosphate, inorganic phosphate buffers, butanediamine, glycine, potassium hydroxide, saccharin, antimony potassium tartrate, butynediol.
An example of a specific composition of example 4 is: 140g of sodium sulfite, 120g of aminotrimethylene phosphoric acid, 150g of hydroxyethylidene diphosphonic acid, 200g of inorganic phosphate buffer, 35g of butanediamine, 50g of glycine, 150g of potassium hydroxide, 0.3g of saccharin, 0.025g of potassium antimony tartrate and 1.2g of butynediol.
The process conditions for example 4 were set as: the plating temperature was 55 ℃, the plating current value was 0.3ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 8.2.
The thickness of the electroformed gold product produced by the process of example 4 is 240 μm, its vickers hardness is 170HV, the gold purity as determined by pyrometry is 99.93%, the surface is smooth, the brightness level is a, and it has a mirror effect.
Example 5
The formulation of example 5 included sodium sulfite, aminotrimethylene phosphate, hydroxyethylidene diphosphate, inorganic phosphate buffers, butanediamine, glycine, potassium hydroxide, antimony potassium tartrate, glycerol.
An example of a specific composition of example 5 is: 100g of sodium sulfite, 200g of aminotrimethylene phosphoric acid, 150g of hydroxyethylidene diphosphonic acid, 100g of inorganic phosphate buffer, 40g of butanediamine, 40g of glycine, 150g of potassium hydroxide, 0.04g of antimony potassium tartrate and 10g of glycerol.
The process conditions for this example 5 were set as: the plating temperature was 70 ℃, the plating current value was 0.3ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 8.7.
The electroformed gold product produced by the process of this example 5 has a thickness of 240 μm, a vickers hardness of 130HV, a gold purity of 99.94% as determined by pyrometry, a smooth surface, a brightness level B, and a specular effect.
Example 6
The formulation of example 6 includes sodium sulfite, aminotrimethylene phosphate, hydroxyethylidene diphosphate, inorganic phosphate buffers, butanediamine, glycine, potassium hydroxide, saccharin, antimony potassium tartrate, glycerol, butynediol.
An example of a specific composition of example 6 is: 100g of sodium sulfite, 200g of aminotrimethylene phosphoric acid, 180g of hydroxyethylidene diphosphonic acid, 120g of an inorganic phosphate buffer, 40g of butanediamine, 40g of glycine, 150g of potassium hydroxide, 0.3g of saccharin, 0.06g of antimony potassium tartrate, 10g of glycerol, 1.2g of butynediol.
The process conditions for this example 6 were set as: the plating temperature was 70 ℃, the plating current value was 0.3ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 8.2.
The electroformed gold product produced by the process of this example 6 has a thickness of 240 μm, a vickers hardness of 125HV, a gold purity of 99.92% as determined by pyrometry, a smooth surface, a bright grade a, and a specular effect.
Example 7
The formulation of example 7 includes sodium sulfite, aminotrimethylene phosphate, hydroxyethylidene diphosphate, inorganic phosphate buffers, butanediamine, ethylenediamine, glycine, potassium hydroxide, saccharin, triethylene tetramine, glycerol.
An example of a specific composition of example 7 is: 115g of sodium sulfite, 100g of aminotrimethylene phosphoric acid, 120g of hydroxyethylidene diphosphonic acid, 120g of inorganic phosphate buffer, 30g of butanediamine, 40g of ethylenediamine, 60g of glycine, 120g of potassium hydroxide, 0.3g of saccharin, 0.5g of triethylene tetramine, 10g of glycerol.
The process conditions for this example 7 were set as: the plating temperature was 35 ℃, the plating current value was 0.3ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 8.0.
The electroformed gold product produced by the process of this example 7 had a thickness of 240 μm, a vickers hardness of 125HV, a gold purity of 99.96% as determined by pyrometry, a smooth surface, a bright grade a, and a mirror effect.
Example 8
The formulation of example 8 includes sodium sulfite, aminotrimethylene phosphate, hydroxyethylidene diphosphate, inorganic phosphate buffers, butanediamine, glycine, potassium hydroxide, antimony potassium tartrate, butynediol.
An example of a specific composition of example 8 is: 110g of sodium sulfite, 180g of aminotrimethylene phosphoric acid, 150g of hydroxyethylidene diphosphonic acid, 120g of inorganic phosphate buffer, 40g of butanediamine, 50g of glycine, 120g of potassium hydroxide, 0.03g of potassium antimony tartrate and 0.8g of butynediol.
The process conditions for this example 8 were set as: the plating temperature was 40 ℃, the plating current value was 0.3ASD (amperes per square decimeter), the plating time was 18 hours (hours), and the plating was carried out while adjusting the pH value using 3% dilute sulfuric acid to maintain a level of 7.6.
The electroformed gold product produced by the process of this example 8 had a thickness of 240 μm, a vickers hardness of 125HV, a gold purity of 99.90% as determined by pyrometry, a smooth surface, a bright grade a, and a mirror effect.
Table 1 below shows the characteristics of the electroformed gold articles of the various embodiments. Among them, examples 1 to 3 used a wax mold as an electroforming mold, and examples 4 to 8 used a tin-bismuth alloy as an electroforming mold.
TABLE 1
The gold electroforming part formed by the process of the embodiment has a gold plating layer with the thickness of 10-300 mu m.
The hardness of the gold-plating layer is in the range of 110HV or more, 120HV or more, 130HV or more, 140HV or more, 150HV or more, 160HV or more, 170HV or more, 180HV or more, 190HV or any value selected from the foregoing.
The gold electroformed product produced by the process and the module according to the embodiment is hollow.
The description of the invention uses examples for illustration. These are merely illustrative and should not be construed as limiting the scope of the disclosure.
Claims (20)
1. A cyanide-free gold plating solution comprises an organic polyacid containing a plurality of hydroxyl groups.
2. The cyanide-free gold plating solution according to claim 1, wherein the organic polybasic acid is an organic polybasic phosphoric acid comprising aminotrimethylene phosphoric acid and/or hydroxyethylidene diphosphonic acid as an additive for a plated mirror surface.
3. The cyanide-free gold plating solution according to claim 1 or 2, further comprising a complexing agent for complexing the alloy ions, the complexing agent comprising sodium sulfite.
4. The cyanide-free gold plating solution according to claim 3, the complexing agent further comprising an organic amine dissolved in water as a second complexing agent.
5. The cyanide-free gold plating solution according to claim 3, the complexing agent comprising ethylenediamine, butanediamine, and/or propanediamine.
6. The cyanide-free gold plating solution according to any one of the preceding claims, further comprising potassium antimony tartrate as a hardening agent for adjusting the vickers hardness of the gold article.
7. The cyanide-free gold plating solution according to claim 6 wherein the hardening agent further comprises triethylene tetramine and/or butynediol.
8. The cyanide-free gold plating solution according to claim 1, further comprising a hardening agent comprising saccharin and triethylene tetramine, and/or saccharin and butynediol.
9. The cyanide-free gold plating solution according to claim 1, further comprising a hardening agent comprising antimony potassium tartrate, saccharin and triethylene tetramine, saccharin and butynediol either one out of three or two out of three.
10. The cyanide-free gold plating solution according to claim 1, further comprising butanediamine and glycine or triethylene tetramine, wherein the mass ratio of butanediamine to glycine or triethylene tetramine is 0.1-2.
11. The cyanide-free gold plating solution according to any one of the preceding claims, further comprising an inorganic phosphate buffer to buffer the influence of the electro-generated pH fluctuation on gold.
12. The cyanide-free gold plating solution according to any one of the preceding claims, further comprising 0-20g/L of glycerol.
13. A cyanide-free gold plating method comprising plating gold with the cyanide-free gold plating solution of any one of the preceding claims.
14. The gold plating method according to claim 13, comprising gold plating with 7-18g/L pure gold material.
15. A gold plating method according to claim 13 or 14, comprising plating gold at a ph between 7.2 and 8.7.
16. The gold plating method according to any one of claims 13 to 15, comprising plating gold at between 30-70 ℃.
17. A gold electroform produced by the gold plating method according to any one of claims 13 to 16, which includes a gold plating layer in an amount of 99.5% or more and a hardness of 110HV or more.
18. A gold electroform made by the gold plating method according to any one of claims 13 to 17 having a gold plating layer hardness in the range of 110HV or more, 120HV or more, 130HV or more, 140HV or more, 150HV or more, 160HV or more, 170HV or more, 180HV or more, 190HV or more, or the foregoing values.
19. A gold electroform produced by the gold plating method according to any one of claims 13 to 18, having a gold plating layer thickness of 10 μm to 300 μm.
20. The gold electroform of claim 19 having a surface that is a hard mirror surface.
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