CN117071010A - Electroforming additive for gold-copper-indium ternary alloy and preparation method thereof - Google Patents
Electroforming additive for gold-copper-indium ternary alloy and preparation method thereof Download PDFInfo
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- CN117071010A CN117071010A CN202311032948.0A CN202311032948A CN117071010A CN 117071010 A CN117071010 A CN 117071010A CN 202311032948 A CN202311032948 A CN 202311032948A CN 117071010 A CN117071010 A CN 117071010A
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- 238000005323 electroforming Methods 0.000 title claims abstract description 55
- 239000000654 additive Substances 0.000 title claims abstract description 33
- DIVOJCSOJHXUMT-UHFFFAOYSA-N [Au].[Cu].[In] Chemical compound [Au].[Cu].[In] DIVOJCSOJHXUMT-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 230000000996 additive effect Effects 0.000 title claims abstract description 31
- 229910002058 ternary alloy Inorganic materials 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000007822 coupling agent Substances 0.000 claims abstract description 50
- BYMUNNMMXKDFEZ-UHFFFAOYSA-K trifluorolanthanum Chemical class F[La](F)F BYMUNNMMXKDFEZ-UHFFFAOYSA-K 0.000 claims abstract description 35
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000005282 brightening Methods 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 239000000080 wetting agent Substances 0.000 claims abstract description 8
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims abstract description 7
- 229930006000 Sucrose Natural products 0.000 claims abstract description 7
- 239000005720 sucrose Substances 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 5
- NLKNQRATVPKPDG-UHFFFAOYSA-M potassium iodide Chemical compound [K+].[I-] NLKNQRATVPKPDG-UHFFFAOYSA-M 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- YTQVHRVITVLIRD-UHFFFAOYSA-L thallium sulfate Chemical compound [Tl+].[Tl+].[O-]S([O-])(=O)=O YTQVHRVITVLIRD-UHFFFAOYSA-L 0.000 claims description 6
- 229940119523 thallium sulfate Drugs 0.000 claims description 6
- 229910000374 thallium(I) sulfate Inorganic materials 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- KNCYXPMJDCCGSJ-UHFFFAOYSA-N piperidine-2,6-dione Chemical compound O=C1CCCC(=O)N1 KNCYXPMJDCCGSJ-UHFFFAOYSA-N 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 238000000967 suction filtration Methods 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- FTLYMKDSHNWQKD-UHFFFAOYSA-N (2,4,5-trichlorophenyl)boronic acid Chemical compound OB(O)C1=CC(Cl)=C(Cl)C=C1Cl FTLYMKDSHNWQKD-UHFFFAOYSA-N 0.000 claims description 2
- XXSPGBOGLXKMDU-UHFFFAOYSA-N 2-bromo-2-methylpropanoic acid Chemical compound CC(C)(Br)C(O)=O XXSPGBOGLXKMDU-UHFFFAOYSA-N 0.000 claims description 2
- QOSMNYMQXIVWKY-UHFFFAOYSA-N Propyl levulinate Chemical compound CCCOC(=O)CCC(C)=O QOSMNYMQXIVWKY-UHFFFAOYSA-N 0.000 claims description 2
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical compound OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 claims description 2
- 230000001681 protective effect Effects 0.000 claims description 2
- 229940085605 saccharin sodium Drugs 0.000 claims description 2
- DGSDBJMBHCQYGN-UHFFFAOYSA-M sodium;2-ethylhexyl sulfate Chemical compound [Na+].CCCCC(CC)COS([O-])(=O)=O DGSDBJMBHCQYGN-UHFFFAOYSA-M 0.000 claims description 2
- GOLORTLGFDVFDW-UHFFFAOYSA-N 3-(1h-benzimidazol-2-yl)-7-(diethylamino)chromen-2-one Chemical compound C1=CC=C2NC(C3=CC4=CC=C(C=C4OC3=O)N(CC)CC)=NC2=C1 GOLORTLGFDVFDW-UHFFFAOYSA-N 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 abstract description 20
- 239000000956 alloy Substances 0.000 abstract description 20
- 230000007797 corrosion Effects 0.000 abstract description 12
- 238000005260 corrosion Methods 0.000 abstract description 12
- 230000008021 deposition Effects 0.000 abstract description 8
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052716 thallium Inorganic materials 0.000 abstract 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 abstract 1
- 229910052738 indium Inorganic materials 0.000 description 11
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- 150000002603 lanthanum Chemical class 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 238000007747 plating Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000013078 crystal Substances 0.000 description 4
- 229910021645 metal ion Inorganic materials 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- QRJOYPHTNNOAOJ-UHFFFAOYSA-N copper gold Chemical compound [Cu].[Au] QRJOYPHTNNOAOJ-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- ZYGHJZDHTFUPRJ-UHFFFAOYSA-N coumarin Chemical compound C1=CC=C2OC(=O)C=CC2=C1 ZYGHJZDHTFUPRJ-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 150000003949 imides Chemical group 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 description 1
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 description 1
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000005642 Oleic acid Substances 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 206010049155 Visual brightness Diseases 0.000 description 1
- 229910001361 White metal Inorganic materials 0.000 description 1
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229960000956 coumarin Drugs 0.000 description 1
- 235000001671 coumarin Nutrition 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- -1 modified lanthanum-1, 4-butynediol Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229910000679 solder Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009469 supplementation Effects 0.000 description 1
- 239000010969 white metal Substances 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
- C25D1/00—Electroforming
-
- 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
Abstract
The invention discloses an electroforming additive for a gold-copper-indium ternary alloy and a preparation method thereof, wherein the electroforming additive for the gold-copper-indium ternary alloy comprises thallium sulfite, sucrose, citric acid, coupling agent modified lanthanum fluoride, a brightening agent, a buffering agent, a wetting agent and deionized water; the coupling agent modified lanthanum fluoride is prepared by modifying the surface of nano lanthanum fluoride by a modified coupling agent; the modified coupling agent has a structure shown in the following formula A. The electroforming additive for the gold-copper-indium ternary alloy can improve the surface quality of a deposition layer and enhance the corrosion resistance of the alloy.
Description
Technical Field
The invention relates to the technical field of electroforming processes, in particular to an electroforming additive for a gold-copper-indium ternary alloy and a preparation method thereof.
Background
Electroforming is the process of depositing a metal, alloy or composite material on a conductive master using the metal ion cathodic electrodeposition principle and separating it from the master to produce an article. The basic principle is the same as that of electroplating, but the electroplating needs to obtain a metal coating firmly combined with the matrix to achieve the purposes of protection, decoration and the like, and the electroformed layer is separated from the mandrel, and the thickness of the electroformed layer is far greater than that of the electroplated layer.
Typically, the conductive master is used as the cathode and the metal to be electroformed is used as the anode. The electroforming solution is a solution containing anode metal ions, and under the action of a power supply, the metal ions in the electroforming solution are reduced to metal on a cathode conductive master die and deposited on the surface of the conductive master die. Meanwhile, the anode metal is continuously changed into ions to be dissolved into the electroforming solution for supplementation, so that the concentration of metal ions in the electroforming solution is kept unchanged. When the electroforming layer on the cathode conductive master mould is gradually increased to reach the required thickness, stopping electroforming, and separating the electroforming part from the master mould to obtain the electroforming part opposite to the master mould surface.
Indium is a soft and glossy silvery white metal, and has strong plasticity, good ductility and good corrosion resistance. The melting point of indium is 156.6 ℃ lower than that of other metals, the boiling point is high, and the melting point is 2080 ℃. It has very low hardness, is softer than lead, and can be scratched by nails. Indium is about 4/5 less conductive than copper and has a coefficient of thermal expansion almost exceeding one time that of copper. Indium has unique and excellent physical and chemical properties, indium-containing products are supplied to markets in the forms of Indium Tin Oxide (ITO), pure indium ingots, semiconductor compounds, solders, alloys and the like, are widely used in the high-tech fields of solar cells, electronic computers, high-temperature superconductivity, photoelectricity, aerospace, modern information industry and the like, play an increasingly important role in economic development,
indium can be electrodeposited on lead, silver-lead, gold-copper or copper-lead plating layers, and is thermally diffused to form a solid solution alloy with the bottom plating layer, so that the wear resistance and dry lubricity of the solid solution alloy are utilized to improve the service life of the bearing and the piston ring. The indium coating has good corrosion resistance, and the bearing coated with the lead coating is prevented from being corroded strongly by oleic acid and combustion products of an engine.
The indium plating solution has three types of cyanide type, sulfate type and fluoroborate type. Although the sulfate type electroforming solution can electroform gold-copper alloy to form gold-copper-indium ternary alloy, the deposited layer on the surface of the alloy has coarse grains and nonuniform shape, the surface quality of the deposited layer is affected, and the corrosion resistance of the prepared alloy still needs to be further improved.
Therefore, there is a need for electroforming additives for gold-copper-indium ternary alloys that can improve the surface quality of the deposited layer and enhance the corrosion resistance of the alloy.
Disclosure of Invention
The invention aims to: aiming at the defects of the prior art, the invention aims to provide an electroforming additive for gold-copper-indium ternary alloy and a preparation method thereof, wherein the electroforming additive can improve the surface quality of a deposition layer and enhance the corrosion resistance of the alloy.
The technical scheme is as follows:
an electroforming additive for gold-copper-indium ternary alloy comprises thallium sulfate, sucrose, citric acid, coupling agent modified lanthanum fluoride, brightening agent, buffering agent, wetting agent and deionized water;
the coupling agent modified lanthanum fluoride is prepared by modifying the surface of nano lanthanum fluoride by a modified coupling agent;
the modified coupling agent has a structure shown in the following formula A:
according to the invention, by adding the modified coupling agent surface modified nano lanthanum fluoride, the uniformity of the growth of crystal grains on the surface of the deposition layer in the electroforming process can be improved, the crystal grains of the deposition layer are refined, and the electroforming effect is improved, so that the alloy has more excellent surface quality of the deposition layer.
Further, the brightening agent is at least one selected from 1, 4-butynediol, coumarin or saccharin sodium.
Further, the wetting agent is at least one selected from sodium dodecyl sulfate and sodium 2-ethylhexyl sulfate.
Further, the buffer is selected from at least one of acetic acid or boric acid.
Further, the modified coupling agent is prepared by the steps of: adding 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon-based) propyl ester, glutarimide, potassium carbonate, potassium iodide and an organic solvent into a reactor, heating to 70-85 ℃ in a protective gas environment, carrying out suction filtration after reacting for 16-18 hours, removing the organic solvent, washing and drying to obtain the modified coupling agent.
The modified coupling agent is used in the invention, has a long-chain structure, can enhance the self-dispersing capability and stability, and can form a protective coating on the alloy surface after electroforming based on the imide structure in the structure, so that oxygen and water in air are prevented from directly contacting the alloy surface, oxidation-reduction reaction is prevented, and the corrosion resistance of the alloy can be further improved.
Further, the mass ratio of the 2-bromo-2-methylpropanoic acid (3-trimethoxysilyl) propyl ester to the glutarimide is 3:1.1-1.3.
Further, the coupling agent modified lanthanum fluoride is prepared by the following steps: in a reactor, dissolving nano lanthanum fluoride in deionized water, heating to 40-60 ℃, stirring and dissolving, adding a modified coupling agent, heating to 70-80 ℃, stirring and reacting for 3-4 hours, filtering, washing and drying to obtain the coupling agent modified lanthanum fluoride.
According to the invention, the surface of the nano lanthanum fluoride is modified by the modified coupling agent, so that the dispersibility of the nano lanthanum fluoride can be improved, the aggregation phenomenon of nano particles is reduced, and the surface-modified nano lanthanum fluoride has excellent stability and is suitable for an electroforming environment.
Further, the mass ratio of the nano lanthanum fluoride to the modified coupling agent is 1:0.3-0.5.
Further, the mass percent of each component is as follows, calculated as 100% of the total mass percent:
the balance of deionized water.
The preparation method of the electroforming additive for the gold-copper-indium ternary alloy comprises the following steps: weighing thallium sulfate, sucrose, citric acid, coupling agent modified lanthanum fluoride, brightening agent, buffering agent and wetting agent according to a certain proportion, adding into deionized water, stirring and dissolving to obtain the electroforming additive for gold-copper-indium ternary alloy.
The beneficial effects are that:
(1) According to the electroforming additive for the gold-copper-indium ternary alloy, provided by the invention, the nano lanthanum fluoride modified on the surface of the modified coupling agent is added, so that the uniformity of the growth of crystal grains on the surface of a deposition layer in the electroforming process can be improved, the crystal grains of the deposition layer are thinned, the electroforming effect is further improved, and the alloy has more excellent surface quality of the deposition layer.
(2) According to the electroforming additive for the gold-copper-indium ternary alloy, the modified coupling agent is used for carrying out surface modification on the nano lanthanum fluoride, so that the dispersibility of the nano lanthanum fluoride can be improved, the aggregation phenomenon of nano particles is reduced, and the surface-modified nano lanthanum fluoride has excellent stability and is suitable for electroforming environments.
(3) The modified coupling agent is used in the electroforming additive for the gold-copper-indium ternary alloy, has a long-chain structure, can enhance the self dispersion capacity and stability, can form a protective coating on the surface of the alloy after electroforming based on the imide structure in the structure, prevents oxygen and water in air from directly contacting the surface of the alloy, prevents oxidation-reduction reaction, and further can improve the corrosion resistance of the alloy.
Detailed Description
The invention will be described below in connection with specific embodiments. The following examples are illustrative of the present invention and are not intended to limit the present invention. Other combinations and various modifications within the spirit of the invention may be made without departing from the spirit or scope of the invention.
The commercial additive is 1N Jin Tieyin acid regulating salt purchased from Shenzhen Jikang technology Co., ltd; nanometer lanthanum fluoride is purchased from Xuan Chengjing Rui New Material Co., ltd; the rest reagents and equipment are conventional reagents and equipment in the technical field.
Preparation of modified coupling agent
The modified coupling agent is prepared by the following steps:
in a round bottom flask, 30g of 2-bromo-2-methylpropanoic acid (3-trimethoxysilyl) propyl ester, 12g of glutarimide, 60g of potassium carbonate, 3g of potassium iodide and 300mL of anhydrous toluene are added, the mixture is heated to 80 ℃ under the protection of nitrogen, and after 16 hours of reaction, the anhydrous toluene is removed by suction filtration, washed and dried, and the modified coupling agent is prepared.
Mass spectrum data of the product: the product was analyzed by LC-MS and m/z was 361.16 (100.0%), 362.22 (23.4%), 363.17 (6.1%).
Preparation of coupling agent modified lanthanum fluoride-1
The coupling agent modified lanthanum fluoride-1 is prepared by the following steps:
dissolving 1g of nano lanthanum fluoride in 30mL of deionized water, heating to 60 ℃, stirring and dissolving, adding 0.5g of modified coupling agent, heating to 80 ℃, stirring and reacting for 3 hours, filtering, washing and drying to obtain the coupling agent modified lanthanum fluoride.
Preparation of coupling agent modified lanthanum fluoride-2
Basically, the modified lanthanum fluoride-1 is prepared by the same coupling agent, except that the modified coupling agent is changed into gamma-aminopropyl triethoxysilane with the same amount.
Example 1
The electroforming additive for the gold-copper-indium ternary alloy is prepared by the following steps:
weighing thallium sulfate, sucrose, citric acid, coupling agent modified lanthanum-1, 4-butynediol, boric acid and sodium dodecyl sulfate according to a proportion, adding into deionized water, stirring and dissolving to obtain the electroforming additive for the gold-copper-indium ternary alloy;
the total mass fraction is 100%, and the mass percentage of each component is as follows:
the balance of deionized water.
Example 2
Substantially as in example 1, except that the total mass fraction was 100%, the components and the mass percentages thereof were as follows:
the balance of deionized water.
Example 3
Substantially as in example 1, except that the total mass fraction was 100%, the components and the mass percentages thereof were as follows:
the balance of deionized water.
Comparative example 1
Commercial additives.
Comparative example 2
Substantially the same as in example 1, except that the coupling agent modified lanthanum fluoride-1 was changed to an equivalent amount of deionized water.
Comparative example 3
Substantially as in example 1, except that the coupling agent modified lanthanum fluoride-1 was changed to an equivalent amount of nano lanthanum fluoride.
Comparative example 4
Substantially as in example 1, except that the coupling agent modified lanthanum fluoride-1 was changed to an equivalent amount of the coupling agent modified lanthanum fluoride-2.
Performance testing
An aqueous solution of 15g/L of metallic indium and 10g/L of sodium sulfate was prepared as an electroforming solution, and the products of examples 1 to 3 and comparative examples 1 to 4, each having a mass fraction of 5%, were added.
At pH 2.2-2.6, cathode current density 1-2A/dm 2 And (3) electroforming the gold-copper alloy with the same specification under the process condition that the temperature is 18-25 ℃ and the anode is indium, and detecting a sample.
And (3) binding force detection: according to the thermal shock test, the test specimens were placed in an oven at 200-300℃for about 30 minutes, taken out, immersed in water at 25℃and quenched, and the plating was examined for signs of blistering or detachment under an illumination observation system at 8-fold or 4-fold magnification.
And (3) corrosion resistance detection: 250mL of concentrated nitric acid was added to the IOL dryer, the vessel was capped, the sample was placed and capped again after 30 minutes for 60 minutes, after testing, the sample was removed and placed in an oven at 125+ -3deg.C for 30 minutes, and the sample surface was inspected under a 10-fold magnifier.
Appearance of the plating layer: judging the brightness of the plating layer according to the grading reference standard of the visual brightness experience assessment method, and carrying out first-level: the surface of the layer is bright like a mirror, and the second level is that: the surface of the plating layer is bright, and the steps are as follows: the surface of the coating has slight brightness, four grades: the coating is substantially matt.
According to comparison of the detection results of examples 1-3 and comparative example 1, the electroforming additive for the gold-copper-indium ternary alloy provided by the invention can obviously improve the electroforming surface quality and enhance the corrosion resistance of the alloy.
According to comparison of the detection results of examples 1-3 and comparative example 2, the electroforming additive for gold-copper-indium ternary alloy provided by the invention can be added with the coupling agent modified lanthanum fluoride to improve the electroforming surface quality and enhance the corrosion resistance of the alloy.
According to comparison of the detection results of examples 1-3 and comparative examples 3 and 4, the surface modification of the nano lanthanum fluoride by the modified coupling agent in the electroforming additive for gold-copper-indium ternary alloy provided by the invention can improve the dispersibility of the lanthanum fluoride, enhance the electroforming effect, and improve the corrosion resistance of the alloy.
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and to implement it, but not limit the scope of the present invention, and all equivalent changes or modifications made according to the spirit of the present invention should be included in the scope of the present invention.
Claims (10)
1. An electroforming additive for gold-copper-indium ternary alloy is characterized by comprising thallium sulfate, sucrose, citric acid, coupling agent modified lanthanum fluoride, brightening agent, buffering agent, wetting agent and deionized water;
the coupling agent modified lanthanum fluoride is prepared by modifying the surface of nano lanthanum fluoride by a modified coupling agent;
the modified coupling agent has a structure shown in the following formula A:
。
2. the electroforming additive for a gold-copper-indium ternary alloy according to claim 1, wherein the brightening agent is selected from at least one of 1, 4-butynediol, coumarin, or saccharin sodium.
3. The electroforming additive for a gold-copper-indium ternary alloy according to claim 1, wherein the wetting agent is selected from at least one of sodium dodecyl sulfate or sodium 2-ethylhexyl sulfate.
4. The electroforming additive for a gold-copper-indium ternary alloy according to claim 1, wherein the buffer is selected from at least one of acetic acid or boric acid.
5. The electroforming additive for a gold-copper-indium ternary alloy according to claim 1, wherein the modified coupling agent is prepared by: adding 2-bromo-2-methylpropanoic acid (3-trimethoxy silicon-based) propyl ester, glutarimide, potassium carbonate, potassium iodide and an organic solvent into a reactor, heating to 70-85 ℃ in a protective gas environment, carrying out suction filtration after reacting for 16-18 hours, removing the organic solvent, washing and drying to obtain the modified coupling agent.
6. The electroforming additive for a gold-copper-indium ternary alloy according to claim 5, wherein the mass ratio of 2-bromo-2-methylpropanoic acid (3-trimethoxysilyl) propyl ester to glutarimide is 3:1.1-1.3.
7. The electroforming additive for a gold-copper-indium ternary alloy according to claim 1, wherein the coupling agent modified lanthanum fluoride is prepared by: in a reactor, dissolving nano lanthanum fluoride in deionized water, heating to 40-60 ℃, stirring and dissolving, adding a modified coupling agent, heating to 70-80 ℃, stirring and reacting for 3-4 hours, filtering, washing and drying to obtain the coupling agent modified lanthanum fluoride.
8. The electroforming additive for a gold-copper-indium ternary alloy according to claim 7, wherein the mass ratio of the nano lanthanum fluoride to the modified coupling agent is 1:0.3-0.5.
9. The electroforming additive for a gold-copper-indium ternary alloy according to claim 1, wherein the mass percentage of each component is as follows, based on 100% of the total mass fraction:
thallium sulfate 3-5%
Sucrose 1-2%
Citric acid 2-3%
3-5% of coupling agent modified lanthanum fluoride
1-2% of brightening agent
Buffer 5-8%
Wetting agent 1-3%
The balance of deionized water.
10. The method for preparing the electroforming additive for the gold-copper-indium ternary alloy according to any one of claims 1 to 9, characterized by comprising the following steps: weighing thallium sulfate, sucrose, citric acid, coupling agent modified lanthanum fluoride, brightening agent, buffering agent and wetting agent according to a certain proportion, adding into deionized water, stirring and dissolving to obtain the electroforming additive for gold-copper-indium ternary alloy.
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