CN111893528A - Bright platinizing solution for electroplating on base metal - Google Patents
Bright platinizing solution for electroplating on base metal Download PDFInfo
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- CN111893528A CN111893528A CN202010655870.8A CN202010655870A CN111893528A CN 111893528 A CN111893528 A CN 111893528A CN 202010655870 A CN202010655870 A CN 202010655870A CN 111893528 A CN111893528 A CN 111893528A
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- electroplating
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- solution
- metal
- platinizing
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- 238000009713 electroplating Methods 0.000 title claims abstract description 41
- 239000010953 base metal Substances 0.000 title claims abstract description 18
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical class [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 150000003839 salts Chemical class 0.000 claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 19
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 15
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 12
- 239000000654 additive Substances 0.000 claims abstract description 11
- 230000000996 additive effect Effects 0.000 claims abstract description 11
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 238000007747 plating Methods 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 31
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 26
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 22
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 239000000758 substrate Substances 0.000 claims description 14
- 239000010936 titanium Substances 0.000 claims description 13
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 12
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 12
- 229910052719 titanium Inorganic materials 0.000 claims description 12
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 235000010288 sodium nitrite Nutrition 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- 235000015165 citric acid Nutrition 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 8
- 239000004471 Glycine Substances 0.000 claims description 7
- 229910052708 sodium Inorganic materials 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 4
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 229910019029 PtCl4 Inorganic materials 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 239000000956 alloy Substances 0.000 claims description 4
- 229910045601 alloy Inorganic materials 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 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
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 3
- -1 compound rare earth Chemical class 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical class [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 claims description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 claims description 2
- 239000000174 gluconic acid Substances 0.000 claims description 2
- 235000012208 gluconic acid Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims description 2
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical class [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical class [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium 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
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical class [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052703 rhodium Inorganic materials 0.000 claims description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 239000011975 tartaric acid Substances 0.000 claims description 2
- 235000002906 tartaric acid Nutrition 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical class [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000003002 pH adjusting agent Substances 0.000 claims 1
- 239000011248 coating agent Substances 0.000 abstract description 8
- 238000000576 coating method Methods 0.000 abstract description 8
- 229910000510 noble metal Inorganic materials 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 14
- 229910052697 platinum Inorganic materials 0.000 description 10
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 239000003788 bath preparation Substances 0.000 description 5
- 230000003750 conditioning effect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 3
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 238000009835 boiling Methods 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000005488 sandblasting Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 229910002621 H2PtCl6 Inorganic materials 0.000 description 1
- 229910020437 K2PtCl6 Inorganic materials 0.000 description 1
- 244000137852 Petrea volubilis Species 0.000 description 1
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- UMWYYMCOBYVEPY-UHFFFAOYSA-N azanide;platinum(2+) Chemical compound [NH2-].[NH2-].[Pt+2] UMWYYMCOBYVEPY-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000010612 desalination reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 229910000397 disodium phosphate Inorganic materials 0.000 description 1
- 235000019800 disodium phosphate Nutrition 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000004544 sputter deposition Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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 bright platinizing solution for electroplating on base metal comprises the following components in percentage by mass: platinum metal salts, calculated as platinum metal: 0.1-1%, composite rare earth additive: 0.001% -0.01%; conductive salt: 0.1-0.6 g%; pH value regulator: 0.1% -7.8%; deionized water: the balance; the method has the advantages of improving the integral uniformity of the coating, improving the quality of the coating, reducing the consumption of noble metal and reducing the cost.
Description
Technical Field
The invention belongs to the technical field of platinized anode products, and particularly relates to a bright platinizing solution for electroplating on base metal, which is used for high-end electroplating, electrolysis, metallurgy, seawater desalination, battery and wastewater treatment.
Background
Platinum is a versatile precious metal and has very wide application in both industrial and non-industrial fields. Platinum is known to have high gloss, rust and oxidation resistance, and is popular with the people in the jewelry field; it is more widely and irreplaceable in the industrial field. However, since platinum is very expensive, platinum is often plated on base metal substrates in order to reduce cost and waste. The plating method comprises various modes such as sintering, vacuum plating, ion sputtering, electroplating, chemical plating and the like, wherein the electroplating method is most widely applied due to convenient operation, low early investment and mature process.
However, because of the inherent characteristics of electroplating and different appearances of workpieces, the current is unevenly distributed on the base metal, the uniformity of the plating layer is poor, the plating layer is thicker at places with high current density and multiple active points, and sometimes scorching, peeling and the like occur, and at places with low current density, the plating layer is thinner, has poor coverage, even leaks the base material, and particularly shows outstanding performance when the plating layer is thinner.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a bright platinizing solution for electroplating on base metal, which improves the defects in the electroplating process, adds a small amount of composite rare earth active elements on the basis of the traditional platinizing system, improves the integral uniformity of a plating layer, improves the quality of the plating layer, reduces the consumption of noble metals and reduces the cost.
In order to achieve the purpose, the invention adopts the technical scheme that:
a bright platinizing solution for electroplating on base metal comprises the following components in percentage by weight:
0.1 to 1 percent of platinum metal salt (calculated by platinum metal);
compound rare earth additive: 0.001% -0.01%;
conductive salt: 0.1 to 0.6 percent;
pH value regulator: 0.1% -7.8%;
deionized water: the balance;
the composite rare earth additive comprises one or more high-valence water-soluble salts of lanthanum, cerium, praseodymium, neodymium and yttrium.
The composite rare earth additive adopts Ce3+、La3+One or two of sulfate or chlorate of (A) and an organic complex compound.
The conductive salt comprises: one of ammonium nitrate, sodium nitrite, potassium phosphate, potassium hydrogen phosphate, sodium carbonate, sodium phosphate, hydrochloric acid and sodium bicarbonate.
Said platinum metal salts comprise, depending on their oxidation state: pt (II) metal salt or Pt (IV) gold platinum metal salt. Platinum metal salts are more common.
Examples of pt (ii) platinum metal salts include, but are not limited to, the following: sodium tetrachloroplatinate Na2PtCl4(ii) a And diammonium tetrachloroplatinate (NH)4)2[PtCl4](ii) a Potassium tetrachloroplatinate K2Pt4Cl4(ii) a Ammonium tetrachloroplatinate (NH)4)2PtCl4(ii) a And diamido-platinum (NH)3)2(NO2)2。
Examples of pt (iv) platinum metal salts include, but are not limited to, the following: hexachloroplatinic acid H2PtCl6Sodium hexachloroplatinate Na2PtCl6Potassium hexachloroplatinate K2PtCl6Or ammonium hexachloroplatinate (NH)4)2PtCl6One kind of (1).
The organic complex comprises one or more carboxylic acid groups.
The organic complex also contains one or more amine or amine oxide groups. Preferably: two or more of citric acid, oxalic acid, tartaric acid, gluconic acid, thiourea, EDTA, glycine, urea and other organic matters.
The metal substrate is made of metal or alloy; the metals include: copper Cu, tin Sn, nickel Ni, ruthenium Ru, titanium Ti, aluminum Al, tantalum Ta, palladium Pd, rhodium Rh, iridium Ir, silver Ag, gold Au, cobalt Co or an alloy consisting of any two of the above.
The platinum metal salt is preferably P salt (diamino-platinum (NH))3)2(NO2)2。)
The pH regulator is ammonia water.
The invention has the beneficial effects that:
compared with the prior art, the invention adds a small amount of composite rare earth active elements on the basis of the traditional platinizing system, so the surface brightness can reach the mirror surface brightness, the cathode current efficiency can be improved by more than 2 percent, the coverage rate of an electroplating matrix is improved by 30 to 35 percent in 5min, the uniformity of a plating layer is improved by more than 10 percent, and the bonding force of the plating layer is equivalent to that of the traditional electroplating solution.
According to the invention, a small amount of composite rare earth active elements are added on the basis of the traditional platinizing system, so that the defects of poor coating uniformity and poor covering capability of the traditional platinizing process are overcome, the integral uniformity of the coating is improved, the coating quality is improved, the consumption of precious metals is reduced, and the cost is reduced.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1:
p salt: 0.1% (calculated by platinum metal)
Ammonium nitrate: 0.06 percent;
sodium nitrite: 0.5 percent;
cerium sulfate: 0.003% by weight of Ce3+Counting;
citric acid: 0.008 percent;
pH value regulator: adjusting ammonia water to 2.8%;
deionized water: the balance;
pH value: 11-12 (Ammonia adjustment)
The electroplating method of the embodiment comprises the following steps:
step 1, placing Ta1 industrial pure titanium into 1% dilute hydrochloric acid solution for later use after pretreatment steps of sand blasting, degreasing, acid washing, activation and the like
Step 2, sequentially adding the calculated amount of ammonium nitrate, sodium nitrite and P salt into deionized water with the calculated amount of two-thirds volume, boiling for 30min, adding the rest deionized water after all the salts are dissolved to be transparent solution, and adding rare earth metal complex (Ce)3+Calculated) 0.003%.
And 3, standing and aging the electroplating solution for 24 hours, and filtering for later use.
Step 4, heating the plating solution to more than 60 ℃, taking platinum as an anode, taking the titanium material treated by the step 1 as a cathode, and carrying out cathode current density: 2A/dm2Electroplating for 90 min.
Example 2:
p salt: 0.5% (in terms of platinum metal);
ammonium nitrate: 0.1 percent;
sodium nitrite: 0.5 percent;
cerium sulfate: 0.005% as Ce3 +;
citric acid: 0.005 percent;
pH value regulator: adjusting ammonia water to 3.5%;
deionized water: the balance;
pH value: 11-12 (ammonia conditioning);
the titanium substrate treatment, bath preparation and electroplating process were the same as in "example 1".
Example 3:
p salt: 1% (in terms of platinum metal);
ammonium nitrate: 0.05 percent;
sodium nitrite: 0.5 percent;
cerium sulfate: 0.01% by Ce3 +;
citric acid: 0.008 percent;
deionized water: the balance;
pH value regulator: adjusting ammonia water to 3.6%;
pH value: 11-12 (Ammonia adjustment)
The titanium substrate treatment, bath preparation and electroplating process were the same as in "example 1".
Example 4:
the plating solution comprises the following components:
p salt: 0.5% (in terms of platinum metal);
ammonium nitrate: 0.04 percent;
sodium nitrite: 0.4 percent;
deionized water: the balance;
pH value regulator: adjusting ammonia water to 5%;
pH regulators: 11-12 (ammonia conditioning).
The implementation steps are as follows:
the titanium substrate treatment, plating solution configuration and electroplating process parameters were the same as in "example 1", except that the rare earth complex additive was not added.
And (3) evaluating the performance of the plating layer:
as can be seen from the data in the table, rare earth Se is added3+After the additive of the citric acid compound, the surface brightness can reach mirror surface brightness, the cathode current efficiency can be improved by more than 2 percent, the coverage rate of an electroplating matrix is improved by 30 to 35 percent in 5min, the uniformity of a plating layer is improved by more than 10 percent, and the bonding force of the plating layer and the adhesion force of the plating layer are improved by more than 10 percentThe electroplating solution without the rare earth element additive is equivalent.
Description of evaluation index:
and (3) appearance detection: the plating was visually observed outdoors in bright places.
Current efficiency: the ratio of the weight difference of the plated part before and after electroplating to the theoretically calculated weight gain.
First 5min coverage: electroplating the plated part in the plating solution for 5min, and sintering in a box-type resistance furnace at 450 ℃ for 10min in an atmospheric environment. Ratio of white portion (with platinum) area to cathode area
Coating uniformity: and (4) taking 9 points on the plated piece after electroplating according to the following graph, and respectively testing the absolute value of the thickness of the plating layer, [ the maximum thickness or the minimum thickness ] -the average thickness of the plating layer of the plated piece ]/the average thickness of the plating layer of the plated piece.
Coating binding force: and (3) heating the electroplated part in a box type resistance furnace at 450 ℃ for 15min, quickly taking out, immersing into tap water at room temperature, and repeatedly repeating for three times until no plating layer falls off, thus obtaining the qualified product.
Example 5:
p salt: 0.1% (in terms of platinum metal);
ammonium nitrate: 0.06 percent;
sodium nitrite: 0.5 percent;
lanthanum chloride: 0.003% by weight of La3+Counting;
glycine: 0.1 percent;
deionized water: balance of
pH value regulator: adjusting ammonia water to 2%;
pH value: 11-12 (Ammonia adjustment)
The titanium substrate treatment, bath preparation and electroplating process were the same as in "example 1".
Example 6:
p salt: 0.5% (in terms of platinum metal);
ammonium nitrate: 0.06 percent;
sodium nitrite: 0.5 percent;
lanthanum chloride: 0.003% by weight of La3+Counting;
glycine: 0.5 percent;
deionized water: the balance;
pH value regulator: 4.2% of ammonia water;
pH value: 11-12 (ammonia conditioning);
the titanium substrate treatment, the plating solution preparation and the electroplating process are the same.
Example 7:
p salt: 0.1% (in terms of platinum metal);
ammonium nitrate: 0.05 percent;
sodium nitrite: 0.4 percent;
lanthanum chloride: 0.003%, calculated as La3 +;
glycine: 0.01 percent;
deionized water: the balance;
pH value regulator: 5.1 percent;
pH value: 11-12 (ammonia conditioning);
the titanium substrate treatment, bath preparation and electroplating process were the same as in example 1.
Example 8
P salt: 0.1% (in terms of platinum metal);
ammonium nitrate: 0.05 percent;
sodium nitrite: 0.1 percent;
glycine: 0.01 percent;
pH value regulator: adjusting ammonia water to 2%;
deionized water: the balance;
pH value: 11-12;
the titanium substrate treatment, bath preparation and electroplating process were the same as in example 1.
And (3) evaluating the performance of the plating layer:
as can be seen from the data in the table, rare earth La is added3+Post-electroplating effect of-glycine compound additive and Se3+The citric acid system is similar.
Example 9
A bright platinizing solution for plating on base metal is used in platinizing process of common metal and valve type metal substrate, and is characterized by comprising the following components by mass percent:
chloroplatinic acid: 0.1 percent; (in terms of platinum metal);
cerium chloride: 0.001 percent; (with Ce)3+A meter);
citric acid: 0.003%;
hydrochloric acid (37%): 0.1 percent;
pH value regulator: the pH was adjusted with 0.1% aqueous sodium hydroxide to: 2.5;
deionized water: and (4) the balance.
The electroplating method of the embodiment comprises the following steps:
step 1, polishing burrs and surfaces of a red copper plate by 600-mesh and 1200-mesh sand paper, then pickling in 10% aqueous solution of sodium nitrate, repeatedly washing with distilled water, and airing for later use.
And 2, sequentially adding the calculated amount of chloroplatinic acid and citric acid into the calculated amount of deionized water with two-thirds volume of the calculated amount, boiling for 30min, adding the rest deionized water after all salts are dissolved to be transparent solution, and adding 0.003% of cerium chloride (calculated as Ce3 +).
And 3, adjusting the pH value to 2.5 by using a 1% sodium hydroxide aqueous solution, standing and aging the electroplating solution for 24 hours, and filtering for later use.
Step 4, heating the plating solution to above 60 ℃, taking platinum as an anode, taking the titanium material treated by the step 1 as a cathode, and carrying out cathode current density: electroplating for 70min at 2A/dm 2.
Example 10
Sodium hexachloroplatinate (Na)2PtCl6): 0.15 percent; (in terms of platinum metal);
cerium chloride: 0.003%; (in Ce3 +);
sodium phosphate: 0.3 percent;
sodium hydrogen phosphate: 0.35 percent;
pH value regulator: 3.6 percent of sodium hydroxide aqueous solution;
PH：10.8；
deionized water: and (4) the balance.
Plating solution preparation and plating method reference example 9
Example 11
Sodium chloroplatinate (Na2 PtCl 4): 0.2% (in Pt);
lanthanum sulfate: 0.002%;
sodium carbonate: 0.6 percent;
EDTA-2Na：0.008％；
oxalic acid: 0.001 percent;
pH value regulator: adjusting with 5% ammonia water;
PH：10-11.3；
deionized water: the balance;
preparing a plating solution: dissolving the calculated amount of sodium tetrachloroplatinate and oxalic acid in two thirds of deionized water, heating to 80 ℃, stirring and preserving heat for 30 min; after the solid is completely dissolved, adding the calculated amount of EDTA-2Na and lanthanum sulfate, continuously stirring and keeping the temperature for 20 min. And finally, adding the calculated amount of sodium carbonate, and stirring to dissolve. Standing, cooling to room temperature, adjusting pH to 10-11.3 with 20% ammonia water, standing for 12 hr, aging, and filtering to remove insoluble substances to obtain the electroplating solution.
The substrate is made of pure nickel plate, and after sand blasting and degreasing treatment, the substrate is soaked in 0.5% dilute hydrochloric acid solution for 2 hours to remove a surface oxide layer.
The treated nickel plate is used as a cathode, platinum is used as an anode, and the current density of the cathode is 15A/dm2And electrifying and electroplating for 90min to obtain a bright platinum coating.
Claims (10)
1. A bright platinizing solution for plating on base metal is used in platinizing process of common metal and valve type metal substrate, and is characterized by comprising the following components by mass percent:
platinum metal salts, calculated as platinum metal: 0.1 to 1 percent;
compound rare earth additive: 0.001% -0.01%;
conductive salt: 0.1 to 0.6 percent;
pH value regulator: 0.1% -7.8%;
deionized water: and (4) the balance.
2. The bright platinizing solution for electroplating on a base metal as claimed in claim 1, wherein the composite rare earth additive comprises one or two high valence water soluble salts of lanthanum, cerium, praseodymium, neodymium, yttrium.
3. The method of claim 1, wherein the composite rare earth additive is Ce3+、La3+One or two of sulfate or chlorate of (A) and an organic complex compound.
4. A bright platinizing solution for electroplating on a base metal according to claim 1 wherein said conductive salt comprises: one of ammonium nitrate, sodium nitrite, potassium phosphate, potassium hydrogen phosphate, sodium carbonate, sodium phosphate, hydrochloric acid and sodium bicarbonate.
5. A bright platinizing solution for electroplating on a base metal according to claim 1 wherein said platinum metal salt comprises, depending on its oxidation state: pt (II) metal salt or Pt (IV) gold platinum metal salt.
6. The bright platinizing solution for electroplating on a base metal as claimed in claim 1, wherein said Pt (II) metal salt is sodium tetrachloroplatinate Na2PtCl4One of diammonium tetrachloroplatinate, potassium tetrachloroplatinate, ammonium tetrachloroplatinate or diamido platinate.
7. The bright platinizing solution for electroplating on a base metal according to claim 1, wherein the Pt (IV) metal salt is one of hexachloroplatinic acid, sodium hexachloroplatinate, potassium hexachloroplatinate or ammonium hexachloroplatinate.
8. The bright platinizing solution for electroplating on a base metal according to claim 1, wherein said metal substrate is a metal or an alloy; the metals include: copper, tin, nickel, ruthenium, titanium, aluminum, tantalum, palladium, rhodium, iridium, silver, gold, cobalt or an alloy of any two of the above.
9. A bright platting solution for electroplating on a base metal according to claim 3 wherein said organic complex comprises at least one carboxylic acid group; the organic complex further comprising at least one amine or amine oxide group; the organic complex comprises two or more of citric acid, oxalic acid, tartaric acid, gluconic acid, thiourea, EDTA-2Na, urea and glycine organic matters.
10. A bright platinizing solution for plating on a base metal according to claim 1, wherein said PH adjusting agent is 25% ammonia water, 1% sodium hydroxide aqueous solution.
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| CN114016097A (en) * | 2021-11-26 | 2022-02-08 | 湖南兴弘新材料科技有限公司 | Platinum plating solution and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0243393A (en) * | 1988-08-01 | 1990-02-13 | Electroplating Eng Of Japan Co | Palladium plating solution |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0243393A (en) * | 1988-08-01 | 1990-02-13 | Electroplating Eng Of Japan Co | Palladium plating solution |
Non-Patent Citations (1)
| Title |
|---|
| 张业明等: "钛板电沉积铂工艺的研究", 《材料保护》 * |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114016097A (en) * | 2021-11-26 | 2022-02-08 | 湖南兴弘新材料科技有限公司 | Platinum plating solution and preparation method and application thereof |
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