CN113355707A - Electroplating additive containing copper salt and application and preparation method thereof - Google Patents
Electroplating additive containing copper salt and application and preparation method thereof Download PDFInfo
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- CN113355707A CN113355707A CN202110653238.4A CN202110653238A CN113355707A CN 113355707 A CN113355707 A CN 113355707A CN 202110653238 A CN202110653238 A CN 202110653238A CN 113355707 A CN113355707 A CN 113355707A
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- 238000009713 electroplating Methods 0.000 title claims abstract description 80
- 239000000654 additive Substances 0.000 title claims abstract description 63
- 230000000996 additive effect Effects 0.000 title claims abstract description 61
- 150000001879 copper Chemical class 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 83
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 72
- 238000007747 plating Methods 0.000 claims abstract description 52
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 35
- -1 copper salt compound Chemical class 0.000 claims abstract description 34
- 239000008139 complexing agent Substances 0.000 claims abstract description 30
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 27
- 238000002156 mixing Methods 0.000 claims abstract description 18
- 239000000203 mixture Substances 0.000 claims abstract description 16
- 239000000243 solution Substances 0.000 claims description 92
- 238000003756 stirring Methods 0.000 claims description 36
- 239000011259 mixed solution Substances 0.000 claims description 31
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 10
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- JFEVWPNAOCPRHQ-UHFFFAOYSA-N chembl1316021 Chemical compound OC1=CC=CC=C1N=NC1=CC=CC=C1O JFEVWPNAOCPRHQ-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- OARRHUQTFTUEOS-UHFFFAOYSA-N safranin Chemical compound [Cl-].C=12C=C(N)C(C)=CC2=NC2=CC(C)=C(N)C=C2[N+]=1C1=CC=CC=C1 OARRHUQTFTUEOS-UHFFFAOYSA-N 0.000 claims description 5
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229940116318 copper carbonate Drugs 0.000 claims description 4
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- 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 claims description 3
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 claims description 3
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- TWHFLJSUZZJTQY-UHFFFAOYSA-N prop-1-enylthiourea Chemical compound CC=CNC(N)=S TWHFLJSUZZJTQY-UHFFFAOYSA-N 0.000 claims description 2
- KCXFHTAICRTXLI-UHFFFAOYSA-N propane-1-sulfonic acid Chemical compound CCCS(O)(=O)=O KCXFHTAICRTXLI-UHFFFAOYSA-N 0.000 claims description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 abstract description 41
- 239000010949 copper Substances 0.000 abstract description 41
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 40
- 230000008569 process Effects 0.000 abstract description 17
- 239000010935 stainless steel Substances 0.000 abstract description 13
- 229910001220 stainless steel Inorganic materials 0.000 abstract description 13
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 abstract description 10
- 229910000831 Steel Inorganic materials 0.000 abstract description 9
- 239000010959 steel Substances 0.000 abstract description 9
- 239000000758 substrate Substances 0.000 abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 15
- 229910001431 copper ion Inorganic materials 0.000 description 15
- 239000000463 material Substances 0.000 description 15
- 230000000694 effects Effects 0.000 description 11
- 230000002378 acidificating effect Effects 0.000 description 6
- 229960001484 edetic acid Drugs 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- IYRDVAUFQZOLSB-UHFFFAOYSA-N copper iron Chemical compound [Fe].[Cu] IYRDVAUFQZOLSB-UHFFFAOYSA-N 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 230000004913 activation Effects 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 229920000056 polyoxyethylene ether Polymers 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 3
- 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 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 description 2
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 238000005580 one pot reaction Methods 0.000 description 2
- 238000002161 passivation Methods 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OCVLSHAVSIYKLI-UHFFFAOYSA-N 3h-1,3-thiazole-2-thione Chemical compound SC1=NC=CS1 OCVLSHAVSIYKLI-UHFFFAOYSA-N 0.000 description 1
- RGLYKWWBQGJZGM-ZCXUNETKSA-N 4-[(z)-4-(4-hydroxyphenyl)hex-3-en-3-yl]phenol Chemical compound C=1C=C(O)C=CC=1C(/CC)=C(/CC)C1=CC=C(O)C=C1 RGLYKWWBQGJZGM-ZCXUNETKSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910000975 Carbon steel Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- IPPKPBRKIKWIPN-UHFFFAOYSA-N acetic acid ethane-1,1-diamine Chemical compound CC(N)N.CC(O)=O.CC(O)=O.CC(O)=O.CC(O)=O IPPKPBRKIKWIPN-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000003113 dilution method Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- MBKDYNNUVRNNRF-UHFFFAOYSA-N medronic acid Chemical compound OP(O)(=O)CP(O)(O)=O MBKDYNNUVRNNRF-UHFFFAOYSA-N 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 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 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000546 pharmaceutical excipient Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000010129 solution processing Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000001360 synchronised effect Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 239000011135 tin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004804 winding 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Abstract
The invention provides a copper salt-containing electroplating additive and a using and preparing method thereof; the electroplating additive comprises a copper salt compound, a complexing agent and an auxiliary agent, and comprises the following components in parts by volume based on 100 parts: 10-70 parts by volume of copper salt compound, 10-80 parts by volume of complexing agent and 0.1-5 parts by volume of auxiliary agent; when in use, the electroplating additive is mixed with an acid solution, wherein the acid solution comprises sulfuric acid or a mixture of sulfuric acid and hydrochloric acid; the preparation method comprises the steps of dividing the acid solution into two parts, dissolving and mixing the copper salt compound and the auxiliary agent in one part, and dissolving and mixing the complexing agent in the other part, and then mixing. The electroplating additive does not contain cyanide, can meet the high-end process requirement of direct copper plating of steel substrates, particularly stainless steel, and has strong binding force of a copper plating layer.
Description
Technical Field
The invention relates to the field of consumable manufacturing of a copper plating process, in particular to a copper salt-containing electroplating additive and a using and preparing method thereof.
Background
Electroplating techniques are widely used, and are commonly used to plate copper or other metals on surfaces of steel and other substrates. Cyanide is a good additive of the traditional electroplating process, but has high toxicity, and the elimination of the cyanide is a great trend of the electroplating industry; the non-cyanide electro-coppering process is also seen in some alkaline electroplating materials, mainly zinc plating, and the copper plating products generally have the known defects of poor coating binding force and low industrial efficiency and are ineffective for removing the passive film of the stainless steel.
Some copper plating solutions in the market have good complexing ability on plain carbon steel and cast iron base materials, but have poor effect on stainless steel, and the technical reason is that a compact passive film with firm adhesive force exists on the surface of the stainless steel, and the passive film needs to be removed before copper plating, so that the industrial efficiency is low; the industry puts forward a plurality of valuable electroplating additive formulas and copper plating solutions while trying to eliminate cyanides, the main technical flow is alkaline solution, and the invention is put forward based on the electroplating market demand.
Disclosure of Invention
The technical purpose of the invention is to provide a cyanide-free additive containing copper salt aiming at the market demand of the electroplating industry, the cyanide-free additive containing copper salt can be conveniently mixed with acid solution to form acidic electroplating solution, the use is convenient, the complexing ability is strong, and the industrial technical problem of stainless steel caused by passive film can be solved.
In order to achieve the technical object, the invention provides a copper salt-containing electroplating additive, which comprises a copper salt compound, a complexing agent and an auxiliary agent, wherein the electroplating additive comprises the following components in parts by volume based on 100 parts by volume: 10-70 parts by volume of copper salt compound, 10-80 parts by volume of complexing agent and 0.1-5 parts by volume of auxiliary agent; the complexing agent comprises EDTA, sodium hexametaphosphate, formic acid, hydrofluoric acid, thiourea, perchloric acid, cucurbituril and the like: the copper salt compound comprises copper chloride, copper carbonate, copper sulfate and other copper salts; the auxiliary agent comprises sodium dodecyl sulfate, safranine azophenol, sodium polydithio-dipropyl sulfonate, polyethylene glycol, polyethyleneimine propane sulfonate, propenyl thiourea and the like.
One of the components of the additive is characterized by containing no cyanide, and the other is characterized by using a copper salt compound, and the skilled person knows that copper ions can generate precipitates in an alkaline solution, so the existing alkaline copper plating solution additive uses less copper salt compounds. The components comprise materials and volume parts; the technical meaning of the materials is one or more of the materials, and a plurality of the materials refer to the mixture of the materials of the same type; the listed materials, etc., are meant to be not limited to the list, for example, complexing agents also include ammonium bromide, methylene diphosphonic acid, ethylene diamine tetramethylene phosphoric acid, hydroxyethylidene diphosphonic acid, aminotrimethylene phosphoric acid, glycolic acid, stannous sulfate, etc., which are common in the industry, and adjuvants also include ethylene thiourea, basic sophorae yellow, diethyl safranine azodimethylphenol, thiazolidinethione, fatty amine polyoxyethylene ethers, thiourea, hydrolyzed protein, alkylphenol polyoxyethylene ethers, etc., which are common in the industry.
When in use, the electroplating additive is mixed with an acid solution, and the volume ratio of the electroplating additive in the mixed solution is not less than 2%. The volume ratio of the electroplating additive in the mixed liquid with the acid solution is not less than 2 percent, which means that the selectable range of the acid solution is wider, and the mixed amount of the acid solution can be selected according to the actual production requirement and the commodity circulation requirement.
In the mixed solution of the electroplating additive and the acid solution, the mass fraction of pure acid of the acid solution is not less than 1.5%; the pure acid comprises sulfuric acid or a mixture of sulfuric acid and hydrochloric acid. The market acid solution is measured by pure acid mass fraction, contains rated amount of industrial pure water, and the pure acid mass fraction is not less than 1.5% means that the relative density of the acid solution has a large selectable range, for example, electroplating industry users select low density matched with the process, and commodity circulation users can select relatively high density.
In the mixture of the sulfuric acid and the hydrochloric acid, the sulfuric acid accounts for 70-90 parts by volume, and the hydrochloric acid accounts for 10-30 parts by volume.
The invention also provides a using and preparing method of the electroplating additive, which comprises the following steps:
step 1) dividing an acid solution with a certain density into two parts by volume;
step 2) adding one volume part of the acid solution in the step 1) into a container, adding a copper salt compound, and stirring until the solution is mixed; then adding an auxiliary agent in a stirring state, and fully and uniformly stirring to obtain a first mixed solution;
step 3) adding another volume part of the acid solution obtained in the step 1) into another container, adding a complexing agent in a stirring state, and fully stirring uniformly to obtain a second mixed solution;
and 4) mixing the first mixed solution obtained in the step 2) and the second mixed solution obtained in the step 3), and uniformly stirring to obtain the acid electroplating solution.
The electroplating additive and the acid solution are mixed preferably, and are recommended to be used for copper plating in wide markets, the existing main copper plating process is alkaline solution, and acid solution or the electroplating additive containing copper salt is rare. The traditional additive for plating copper on the steel substrate usually contains highly toxic cyanide, the cyaniding process is still used as the mainstream internationally at present, and the cyanide has the careless consequence in the storage, transportation and production links; the electroplating industry in China is dedicated to eliminating cyanide in recent decades, and technical documents also describe some non-cyanide alkaline copper plating solutions, but the technical defects of small current density, low speed, heating of the plating solution, high energy consumption and the like exist in the copper plating process, the activation capability is insufficient, and the binding force of a copper plating layer is poor.
The invention has the advantages that the electroplating additive is free of cyanide, convenient to store and transport and convenient to use; the additive has good activation and complexing ability on steel base materials when mixed with acid solution, can inhibit copper-iron replacement reaction, solves the technical problem of directly plating copper on stainless steel, and has strong copper plating binding force and high industrial efficiency.
Detailed Description
The material components and the methods of preparation used in the present invention are further described in detail below.
As is well known to those skilled in the art, copper ions precipitate in alkaline solutions, so that the existing alkaline copper plating solutions use less copper salt compounds; the copper salt compound is a general term of all salts with cations as copper ions, is usually obtained by reacting copper hydroxide with corresponding acid industrially, and can also be replaced by salts formed by simple substance copper and metals with higher activity than copper; the material replaced by the salts is generally called main salt in the electroplating industry, chemical substances of copper salt are present on copper ions, the copper ions can generate copper through reduction reaction, the copper can generate copper ions through oxidation reaction, and the copper salt can also obtain the copper ions by dissolving in water or melting. In acidic process conditions, the copper ion of the copper salt compound plays an auxiliary role in rapidly forming a copper plating layer before the conventional copper-iron displacement reaction.
The complexing agent is also known as chelating agent, chelating dispersant, metal sealing agent, water softener, etc. in printing and dyeing industry, and is also known as complexing agent in electroplating industry. The complexing agent can form a compound of complex ions with metal ions, and the optional quantity is numerous, for example, EDTA is short for ethylenediaminetetraacetic acid (called diamino ethane tetraacetate) and is a representative substance of the complexing agent, and the compound has six coordination atoms and can form a stable water-soluble complex with alkali metals, rare earth elements, transition metals and the like; the complexing ability of the complexing agent varies greatly at different pH values, and the complexing agent can be hydrolyzed even reacted to lose the complexing ability if not selected properly, and various combinations are recommended.
The medical meaning of the auxiliary agent refers to an excipient and an additive used in the production of medicines and the preparation of a prescription, namely the materials except the main medicine components are collectively called; the industry generally refers to the addition of auxiliary chemicals to a manufacturing process to increase the quantity, yield, or to impart certain application characteristics to a product. The application range of the auxiliary agent is wide, and the selection of the auxiliary agent for metal surface treatment has common properties (such as appearance, smell, pollution, weather resistance, processing condition adaptability and the like) and special requirements of the industry, such as compatibility with polymers, miscibility, stability and electrical properties, particularly synergistic action or resistance action among the auxiliary agents. The relationship between the amount of the auxiliary agent and the selection of the components is extremely large, the improper selection can cause poor compounding effect, and if the selection is proper, various auxiliary agents can mutually enhance and reduce the amount of the auxiliary agent.
The electroplating additive is prepared by mixing a copper salt compound, a complexing agent and an auxiliary agent according to a certain component proportion, in the former method, copper ions can generate precipitates in an alkaline solution, so that the alkaline copper plating solution uses less copper salt compounds, and the electroplating additive containing copper salt is recommended to be mixed with an acid solution to prepare an acid electroplating solution.
The acid solution contains water, the mass fraction of pure acid on the market is measured by the convention of calibrating the corresponding relative density, the relative density is a value related to the ambient temperature, and the specific implementation should pay attention to the difference between the mass fraction of the pure acid and the relative density. The invention limits the technical purpose that the mass fraction of pure acid of the acid solution is not less than 1.5 percent, emphasizes that the acid solution needs to have certain acid-containing mass on one hand, and implies the recommendation of low acid density for safe operation of product production on the other hand. The quality grade of the acid solution can be industrial pure for common workpieces, and analytical pure is recommended for fine workpiece electroplating.
The acid solution comprises sulfuric acid or its mixture with hydrochloric acid, sulfuric acid (formula H)2 SO4) Is a chemical material well known to those skilled in the art, and is active binary inorganic strong acid, wherein the mass fraction of pure concentrated sulfuric acid is 98.3 percent relativelyDensity 1.84; hydrochloric acid is commonly known as hydrochloric acid, is an aqueous solution of hydrogen chloride (HCl) gas, is colorless and transparent monobasic strong acid, has the mass fraction of about 36-38 percent and the relative density of 1.20; the sulfuric acid and hydrochloric acid commonly used in the market are various aqueous solutions with different densities, can react with a plurality of metals, and can generate a large amount of heat when being mixed with water.
Industrial pure water in an acid solution is well known to those skilled in the art, and after common raw water is pretreated by filtration, an active carbon unit, a water softener unit and the like, fine treatment and post-treatment are continued according to process requirements, and the technical aim is to greatly reduce the content of impurities such as suspended matters, colloids, organic matters, hardness, microorganisms and the like in the water; the electroplating industry sets up the technical standard requirements of industrial pure water, and the electroplating industry can be applied as long as the industrial technical standard is met.
The electroplating additive and the acid solution are mixed to obtain an acid electroplating solution which is preferably used for copper plating in wide markets, but the application of the electroplating additive is not limited to copper plating, and for example, the electroplating additive can also be used for gold plating. For a long time, the direct copper plating of steel substrates under acidic conditions is generally considered to be infeasible by the same community; according to the activity sequence of metals K, Na, Ca, Mg, Al, Zn, Fe, Sn, Pb, (H), Cu, Hg, Ag, Pt and Au, the steel base material can generate replacement reaction in an acid solution, and a replacement copper layer with loose tissue and extremely poor binding force is generated.
The mechanism of the acid electroplating solution for realizing direct copper plating and inhibiting copper-iron replacement reaction on stainless steel can be understood as follows: the acid electroplating solution contains enough strong acid components, can quickly dissolve a compact passivation film layer on the surface of stainless steel, and activates the surface to expose a crystal structure, thereby providing more deposition points for copper ions; under the coexistence effect of complexing agents, copper ions can be quickly complexed by matching with an electroplating process, and the copper-iron displacement reaction is inhibited by reducing the potential of the copper ions, so that bivalent copper ions are quickly reduced to a copper coating on the surface of the stainless steel; in other words, in the acid electroplating solution, the steel substrate does not generate the conventional replacement reaction, and a copper plating layer with compact crystallization and super-strong binding force is quickly formed, so that the new copper plating layer is theoretically called, and the quick electrodeposition of copper ions on the new copper plating layer is realized.
The density of the acid solution for mixing the electroplating additive is selected based on the process requirements and different matrixes, for example, the density is selected by an industrial user according to the current density and the environmental temperature of the actual process matching requirements; the commodity circulation user can regard the electroplating additive as a packaged commodity, and downstream users can use the electroplating additive only by adding the acid solution meeting the density requirement, so that the storage and transportation cost is saved. Because the environments of the electroplating additives are different, the dispersion effect of the one-pot mixed acid solution of the electroplating additives is generally poor, the quality of the electroplating products is easy to be unstable, and the defective rate is high.
One use and preparation method of the provided electroplating additive comprises the following steps:
step 1) dividing an acid solution with a certain density into two parts by volume;
step 2) adding one volume part of the acid solution in the step 1) into a container, adding a copper salt compound, and stirring until the solution is mixed; then adding an auxiliary agent in a stirring state, and fully and uniformly stirring to obtain a first mixed solution;
step 3) adding another volume part of the acid solution obtained in the step 1) into another container, adding a complexing agent in a stirring state, and fully stirring uniformly to obtain a second mixed solution;
and 4) mixing the first mixed solution obtained in the step 2) and the second mixed solution obtained in the step 3), and uniformly stirring to obtain the acid electroplating solution.
When the preparation method is implemented, the acid solution with certain density in the step 1) can be transformed into pure water diluted by high-density acid solution processing industry and then divided into two parts by volume; for example, the copper salt compound, the auxiliary agent and the complexing agent are respectively diluted by an acid solution with the density higher than the optimal density of the process, and the pure water is further processed for dilution when the method is used, which also belongs to the technical implementation deformation of the preparation method; the acid solution has a certain density which is selected by people and is suitable for flexible application.
The present invention will be described in further detail with reference to examples, which are merely preferred.
Example 1
Preparing an electroplating additive of the invention, based on 100 parts by volume of the components, comprises:
copper salt compound: copper sulfate 33.5 parts by volume
Complexing agent: 20 parts by volume of sodium hexametaphosphate, 25 parts by volume of EDTA (ethylene diamine tetraacetic acid) and 20 parts by volume of hydrofluoric acid
Auxiliary agent: sodium dodecyl sulfate 1.4 parts by volume and safranine azophenol 0.1 part by volume
The components can be mixed in proportion to be used as an electroplating additive, and the electroplating additive is mixed with a rated amount of acid solution when in use.
Example 2
Another electroplating additive was prepared comprising, based on 100 parts by volume of the composition:
copper salt compound: copper sulfate 46 parts by volume
Complexing agent: 30 parts by volume of formic acid, 5 parts by volume of thiourea and 15 parts by volume of perchloric acid
Auxiliary agent: 3 parts by volume of polyethylene glycol and 1 part by volume of stannous sulfate
The components of this example were mixed in proportions to obtain another electroplating additive.
Example 3
Each of the components of the plating additive of example 1 was mixed stepwise with 1100 parts by volume of a sulfuric acid solution containing 80 parts by volume of sulfuric acid having a nominal density of 1.84 and the balance of industrial pure water; the preparation method comprises the following steps:
step 1) dividing 1100 parts by volume of sulfuric acid solution into 500 parts by volume and 600 parts by volume;
step 2) adding 500 volume parts of sulfuric acid solution obtained in the step 1) into one container, adding 33.5 volume parts of copper salt compound (copper sulfate), stirring and mixing, continuously adding 1.5 volume parts of auxiliary agent (1.4 volume parts of sodium dodecyl sulfate and 0.1 volume part of safranine azophenol) in a stirring state, wherein the adding sequence is not limited, and fully stirring to obtain the first mixed solution:
step 3) adding 600 parts by volume of the dilute sulfuric acid solution obtained in the step 1) into another container, adding 65 parts by volume of complexing agents (20 parts by volume of sodium hexametaphosphate, 25 parts by volume of EDTA and 20 parts by volume of hydrofluoric acid) in a stirring state, wherein the adding sequence is not limited, and fully stirring uniformly to obtain a second mixed solution:
and 4) mixing the first mixed solution obtained in the step 2) and the second mixed solution obtained in the step 3), and uniformly stirring to obtain the acid electroplating solution.
The acid electroplating solution of the embodiment can be used for copper plating of steel substrates, such as copper plating of stainless steel sheets, the stainless steel sheets are subjected to oil removal, acid cleaning and activation treatment according to conventional procedures and then placed in an electroplating bath, electroplating solution is placed in the electroplating bath, and the dilution and auxiliary materials are adjusted according to a matched electroplating process; the electroplating solution contains sulfuric acid, can quickly dissolve a compact passivation film layer on the surface of the stainless steel sheet, quickly activate the surface and expose a crystal structure, and provides more deposition points for copper ions; the electroplating process allows for relatively large current densities to be used.
Example 4
In example 3, 1100 parts by volume of the acid solution contained 80 parts by volume of sulfuric acid having a density of 1.84, and this example was replaced with a mixture of sulfuric acid and hydrochloric acid, wherein 50 parts by volume of sulfuric acid having a relative density of 1.84 and 30 parts by volume of hydrochloric acid having a relative density of 1.18; the composition of the plating additive is unchanged.
In this example, the use of the plating additive preparation step 1) was modified to dilute concentrated sulfuric acid and concentrated hydrochloric acid with 1020 parts by volume of industrial pure water: slowly adding 30 parts by volume of hydrochloric acid with the density of 1.18 into 1020 parts by volume of industrial pure water, stirring uniformly, continuously and slowly adding 50 parts by volume of sulfuric acid with the density of 1.80, and continuously stirring uniformly in the dilution process to obtain 1100 parts by volume of diluted mixed acid solution of the sulfuric acid and the hydrochloric acid; the mixed acid solution was divided into 500 parts by volume and 600 parts by volume, and the method for preparing the step 2), the step 3) and the step 4) was similar to that of example 3, and the industrial effect of the acid plating solution prepared was similar to that of example 3.
Example 5
Mixing each component of the electroplating additive of example 2 with 550 parts by volume of sulfuric acid solution in steps, wherein the sulfuric acid solution contains 50 parts by volume of pure sulfuric acid by mass fraction, and the preparation method comprises the following steps:
step 1) 550 parts by volume of sulfuric acid solution is firstly divided into two parts of 300 parts by volume and 250 parts by volume:
step 2) adding 300 parts by volume of dilute sulfuric acid solution into a container, adding 46 parts by volume of copper salt compound (copper sulfate), stirring and mixing, adding 4 parts by volume of auxiliary agent (3 parts by volume of polyethylene glycol and 1 part by volume of stannous sulfate) in a stirring state, wherein the adding sequence is not limited, and fully stirring uniformly to obtain the first mixed solution:
step 3) adding 250 parts by volume of sulfuric acid solution into another container, adding 50 parts by volume of complexing agent (30 parts by volume of formic acid, 5 parts by volume of thiourea and 15 parts by volume of perchloric acid) in a stirring state, wherein the adding sequence is not limited, and fully stirring uniformly to obtain a second mixed solution:
and 4) mixing the first mixed solution obtained in the step 2) and the second mixed solution obtained in the step 3), and uniformly stirring to obtain 650 parts by volume of another acid electroplating solution.
The acidic electroplating solution obtained in the embodiment is a concentrated solution, is beneficial to reducing storage and transportation cost of products, brings flexibility to end industrial users, and is diluted by pure water in the processing industry when in use. The effect of the plating solution for copper plating of stainless steel sheet was similar to that of example 3, for example, the current density was set to 1A/dm2The steel pipe with the diameter of 5mm is continuously plated with copper, the copper plating effect of the conventional process of rack plating for 5-10 minutes can be obtained within about 1 minute, and the copper plating layer is fine and bright and has good bonding force. The copper plating time is short, so that synchronous winding is realized, and the industrial efficiency is improved.
Example 6
Yet another electroplating additive was prepared comprising, based on 100 parts by volume of the composition:
copper salt compound: 45 parts by volume of copper chloride
Complexing agent: 14.8 parts by volume of perchloric acid and 40 parts by volume of hydroxy ethylidene diphosphonic acid
Auxiliary agent: 0.1 part by volume of ethylene thiourea and 0.1 part by volume of sodium polydithio-dipropanesulfonate
In the electroplating additive of this example, copper salt compound is copper chloride, and acid electroplating solution is prepared by mixing 100 parts by volume of electroplating additive component with 2500 parts by volume of sulfuric acid solution (containing 50 parts by volume of pure sulfuric acid) and mixing the components by one pot, and the preferable preparation process is similar to that of example 5: dividing 2500 parts by volume of sulfuric acid solution into 1250 parts by volume of two parts, wherein one part is mixed with a copper salt compound and an auxiliary agent, and fully stirring to obtain a first mixed solution; mixing the other part of sulfuric acid solution with a complexing agent, and fully stirring uniformly to obtain a second mixed solution; then, the first mixed solution and the second mixed solution were mixed and stirred uniformly to obtain 2600 parts by volume of another acidic plating solution.
Example 7
Based on the electroplating additive composition of example 6, copper chloride of the copper salt compound was replaced with copper carbonate, which was also 45 parts by volume, to obtain an analogous electroplating additive; the preparation process by mixing with the acid solution was the same as in example 6, and the industrial effect of the resulting acid plating solution was the same as in example 6.
Example 8
A further electroplating additive was prepared comprising, based on 100 parts by volume of the composition:
copper salt compound: copper carbonate 25 parts by volume
Complexing agent: 20 parts by volume of hydrofluoric acid, 20 parts by volume of formic acid, 1.4 parts by volume of cucurbituril and 8 parts by volume of ethylenediamine tetramethylenephosphoric acid
Auxiliary agent: 0.1 part by volume of safranine azophenol and 0.5 part by volume of sodium dodecyl sulfate
The components of the electroplating additive are mixed with 2000 parts by volume of acid solution (containing 15 parts by volume of pure hydrochloric acid and 20 parts by volume of pure sulfuric acid), and the preparation method comprises the following steps: dividing 2000 parts by volume of dilute acid solution into two equal parts, wherein one part is mixed with a copper salt compound and an auxiliary agent, and fully stirring to obtain a first mixed solution; mixing the other part of dilute acid solution with a complexing agent, and fully stirring uniformly to obtain a second mixed solution; the first mixed solution and the second mixed solution were mixed and stirred uniformly to obtain 2100 parts by volume of an acidic plating solution.
Example 9
In the composition of the plating additive of example 8, sodium lauryl sulfate as an auxiliary was replaced with an aliphatic amine polyoxyethylene ether, and the composition was also 0.5 parts by volume, to obtain another composition having another plating additive. The components of the plating additive were mixed with 2000 parts by volume of the acid solution described in example 8, and the same preparation method was used, and another acid plating solution having different components was obtained, and the industrial effect was similar to example 8.
Claims (5)
1. A copper salt-containing electroplating additive is characterized in that a copper salt compound comprises a complexing agent and an auxiliary agent, and the electroplating additive comprises the following components based on 100 parts by volume: 10-70 parts by volume of copper salt compound, 10-80 parts by volume of complexing agent and 0.1-5 parts by volume of auxiliary agent; the complexing agent comprises EDTA, sodium hexametaphosphate, formic acid, hydrofluoric acid, thiourea, perchloric acid, cucurbituril and the like: the copper salt compound comprises copper chloride, copper carbonate, copper sulfate and other copper salts; the auxiliary agent comprises sodium dodecyl sulfate, safranine azophenol, sodium polydithio-dipropyl sulfonate, polyethylene glycol, polyethyleneimine propane sulfonate, propenyl thiourea and the like.
2. The additive for plating according to claim 1, wherein the additive for plating is mixed with an acid solution at the time of use, and the volume ratio in the mixed solution is not less than 2%.
3. The plating additive of claim 2 wherein the acid solution has a pure acid mass fraction of no less than 1.5%; the pure acid comprises sulfuric acid or a mixture of sulfuric acid and hydrochloric acid.
4. The plating additive as recited in claim 3 wherein the mixture of sulfuric acid and hydrochloric acid comprises sulfuric acid in a ratio of 70 to 90 parts by volume and hydrochloric acid in a ratio of 10 to 30 parts by volume.
5. A method of using the electroplating additive of any of claims 1-4, comprising the steps of:
step 1) dividing an acid solution with a certain density into two parts by volume;
step 2) adding one volume part of the acid solution in the step 1) into a container, adding a copper salt compound, and stirring until the solution is mixed; then adding an auxiliary agent in a stirring state, and fully and uniformly stirring to obtain a first mixed solution;
step 3) adding another volume part of the acid solution obtained in the step 1) into another container, adding a complexing agent in a stirring state, and fully stirring uniformly to obtain a second mixed solution;
and 4) mixing the first mixed solution obtained in the step 2) and the second mixed solution obtained in the step 3), and uniformly stirring to obtain the acid electroplating solution.
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| CN112899738A (en) * | 2021-02-10 | 2021-06-04 | 张志梁 | Steel matrix direct cyanide-free copper plating electroplating solution under strong acid condition and preparation method thereof |
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| CN101665962A (en) * | 2009-09-04 | 2010-03-10 | 厦门大学 | Alkaline non-cyanide plating solution for copper-plating used on iron and steel base and preparation method thereof |
| CN104975311A (en) * | 2015-07-01 | 2015-10-14 | 张志梁 | Copper plating liquid and process for direct cyanide-free acid copper plating on steel substrate |
| CN111321436A (en) * | 2020-03-09 | 2020-06-23 | 张志梁 | Cyanide-free copper plating solution assistant and copper plating solution |
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Application publication date: 20210907 |