CN106498463A - A kind of new cyanideless electro-plating signal bronze technique - Google Patents
A kind of new cyanideless electro-plating signal bronze technique Download PDFInfo
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- CN106498463A CN106498463A CN201611212155.7A CN201611212155A CN106498463A CN 106498463 A CN106498463 A CN 106498463A CN 201611212155 A CN201611212155 A CN 201611212155A CN 106498463 A CN106498463 A CN 106498463A
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- Prior art keywords
- copper
- plating solution
- acid
- carboxyethyl
- carboxyethyl thiosuccinic
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- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 title claims abstract description 18
- 229910000906 Bronze Inorganic materials 0.000 title claims abstract description 14
- 239000010974 bronze Substances 0.000 title claims abstract description 14
- 238000009713 electroplating Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 6
- 238000007747 plating Methods 0.000 claims abstract description 27
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 21
- QLCAGXDTDCDEGN-UHFFFAOYSA-N 3-sulfanylcarbonylhexanedioic acid Chemical group OC(=O)CCC(C(O)=S)CC(O)=O QLCAGXDTDCDEGN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000010949 copper Substances 0.000 claims abstract description 19
- 229910052802 copper Inorganic materials 0.000 claims abstract description 19
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 16
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 claims abstract description 6
- 229910000375 tin(II) sulfate Inorganic materials 0.000 claims abstract description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- KCIDZIIHRGYJAE-YGFYJFDDSA-L dipotassium;[(2r,3r,4s,5r,6r)-3,4,5-trihydroxy-6-(hydroxymethyl)oxan-2-yl] phosphate Chemical compound [K+].[K+].OC[C@H]1O[C@H](OP([O-])([O-])=O)[C@H](O)[C@@H](O)[C@H]1O KCIDZIIHRGYJAE-YGFYJFDDSA-L 0.000 claims abstract description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims abstract description 3
- 239000002253 acid Substances 0.000 claims description 11
- 150000003839 salts Chemical class 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 235000011180 diphosphates Nutrition 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 229940079864 sodium stannate Drugs 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- -1 carboxyethyl Chemical group 0.000 claims description 4
- TVQLLNFANZSCGY-UHFFFAOYSA-N disodium;dioxido(oxo)tin Chemical compound [Na+].[Na+].[O-][Sn]([O-])=O TVQLLNFANZSCGY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 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
- 229940116318 copper carbonate Drugs 0.000 claims description 3
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical class [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 3
- 239000001177 diphosphate Substances 0.000 claims description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-J diphosphate(4-) Chemical compound [O-]P([O-])(=O)OP([O-])([O-])=O XPPKVPWEQAFLFU-UHFFFAOYSA-J 0.000 claims description 3
- 239000010439 graphite Substances 0.000 claims description 3
- 229910002804 graphite Inorganic materials 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- TXUICONDJPYNPY-UHFFFAOYSA-N (1,10,13-trimethyl-3-oxo-4,5,6,7,8,9,11,12,14,15,16,17-dodecahydrocyclopenta[a]phenanthren-17-yl) heptanoate Chemical compound C1CC2CC(=O)C=C(C)C2(C)C2C1C1CCC(OC(=O)CCCCCC)C1(C)CC2 TXUICONDJPYNPY-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 2
- 239000005751 Copper oxide Substances 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 2
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910000431 copper oxide Inorganic materials 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical class Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical class [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- GQDHEYWVLBJKBA-UHFFFAOYSA-H copper(ii) phosphate Chemical class [Cu+2].[Cu+2].[Cu+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GQDHEYWVLBJKBA-UHFFFAOYSA-H 0.000 claims description 2
- PTVDYARBVCBHSL-UHFFFAOYSA-N copper;hydrate Chemical compound O.[Cu] PTVDYARBVCBHSL-UHFFFAOYSA-N 0.000 claims description 2
- IOUCSUBTZWXKTA-UHFFFAOYSA-N dipotassium;dioxido(oxo)tin Chemical compound [K+].[K+].[O-][Sn]([O-])=O IOUCSUBTZWXKTA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011574 phosphorus Substances 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 239000001119 stannous chloride Substances 0.000 claims description 2
- 235000011150 stannous chloride Nutrition 0.000 claims description 2
- IUTCEZPPWBHGIX-UHFFFAOYSA-N tin(2+) Chemical compound [Sn+2] IUTCEZPPWBHGIX-UHFFFAOYSA-N 0.000 claims description 2
- 125000000446 sulfanediyl group Chemical group *S* 0.000 claims 2
- ILROLYQPRYHHFG-UHFFFAOYSA-N 1-$l^{1}-oxidanylprop-2-en-1-one Chemical group [O]C(=O)C=C ILROLYQPRYHHFG-UHFFFAOYSA-N 0.000 claims 1
- UGWKCNDTYUOTQZ-UHFFFAOYSA-N copper;sulfuric acid Chemical class [Cu].OS(O)(=O)=O UGWKCNDTYUOTQZ-UHFFFAOYSA-N 0.000 claims 1
- 238000002360 preparation method Methods 0.000 claims 1
- 238000000576 coating method Methods 0.000 abstract description 6
- 239000011248 coating agent Substances 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 229910052725 zinc Inorganic materials 0.000 abstract description 2
- 239000011701 zinc Substances 0.000 abstract description 2
- 239000008199 coating composition Substances 0.000 abstract 1
- 239000012535 impurity Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 229910001432 tin ion Inorganic materials 0.000 description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- PEVJCYPAFCUXEZ-UHFFFAOYSA-J dicopper;phosphonato phosphate Chemical compound [Cu+2].[Cu+2].[O-]P([O-])(=O)OP([O-])([O-])=O PEVJCYPAFCUXEZ-UHFFFAOYSA-J 0.000 description 3
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229940048084 pyrophosphate Drugs 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- GEZAUFNYMZVOFV-UHFFFAOYSA-J 2-[(2-oxo-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetan-2-yl)oxy]-1,3,2$l^{5},4$l^{2}-dioxaphosphastannetane 2-oxide Chemical compound [Sn+2].[Sn+2].[O-]P([O-])(=O)OP([O-])([O-])=O GEZAUFNYMZVOFV-UHFFFAOYSA-J 0.000 description 1
- QRNATDQRFAUDKF-UHFFFAOYSA-N 2-carbamothioylsulfanylethyl carbamodithioate Chemical compound NC(=S)SCCSC(N)=S QRNATDQRFAUDKF-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- VYYNTLYRXIRILN-UHFFFAOYSA-N OC(=O)CC[S] Chemical compound OC(=O)CC[S] VYYNTLYRXIRILN-UHFFFAOYSA-N 0.000 description 1
- ULUAUXLGCMPNKK-UHFFFAOYSA-N Sulfobutanedioic acid Chemical compound OC(=O)CC(C(O)=O)S(O)(=O)=O ULUAUXLGCMPNKK-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000012851 eutrophication Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229940005657 pyrophosphoric acid Drugs 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000003643 water by type 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
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
The invention discloses a kind of technique of the electroplating copper tin alloy without cyanogen, new part has been used, part is carboxyethyl thiosuccinic acid root, typical formula is：Copper sulfate 0.17mol/L, stannous sulfate 0.023mol/L, carboxyethyl thiosuccinic acid hydrogen dipotassium 1.2mol/L, plating solution composition is simple, and copper and tin shares same part, stable performance, in plating solution, each component concentration upper and lower 20% fluctuates on Coating composition almost without impact, it is easy to manage.Insensitive to usual impurities such as zinc, nickel, ferrum.Coating is stanniferous 10 15% signal bronze, and electric current density is wide in range.
Description
Technical field
The present invention relates to field of electroplating, especially cyanideless electro-plating field.
Background technology
Signal bronze is commonly called as bronze, is one of alloy layer for being most widely used, and the stanniferous amount of low tin bronze is 8-15%,
Corrosion resisting property is excellent, and outward appearance is commonly used for the decorative coatings such as imitative gold in golden yellow.
Signal bronze is mainly plated from Cupricin .-sodium stannate system at present and is taken, as cyanide is extremely toxic substance, not only
Pollution environment, and often production development security incident, find the focus that the electroplating technology of substitute is always studied in the industry.
Flavous copper and tin can also be plated out from the Copper pyrophosphate. with pyrophosphate as complexant-ditin diphosphate system
Alloy layer, but its opereating specification is quite narrow, the slight change of each component concentration in plating solution, and alloy compositions will occur huge
Big change.After plating solution long-time is placed, the bivalent cupric ion in plating solution can be reduced into monovalence copper or copper list by divalent tin ion
Matter, and make copper powder in plating solution, occur.Due to difficult management, it is rarely employed in actual production.And pyrophosphate contains phosphorus, sewage
Difficult treatment, enters.
One kind is found without cyanogen, stable, not phosphorous bronze (copper-tin alloy) electroplating technique is the urgent needss in market.
The present invention exactly such a technique.
Content of the invention
Bivalent cupric ion and divalent tin ion or tetravalence tin ion deposition potential difference larger, from free metal from
The signal bronze of required ratio cannot be effectively deposited in sub- mixed liquor, so must be added to part becomes complex,
Change deposition potential, allow both deposition potentials to be close to, and the selection of part is crucial, when a kind of part is unable to reach requirement
When, often multicomponent complex is formed using multiple ligands.Based on such as pyrophosphoric acid during part, in addition it is also necessary to add nitrilotriacetic acid just meeting electricity
Deposit alloy.And the present invention only can just be achieved the goal with a kind of part, bath composition is simpler, more easily manage.
Signal bronze electroplating technology of the present invention includes electroplate liquid, in electroplate liquid containing carboxyethyl thiosuccinic acid root,
Copper and tin element.
Part used in the present invention is carboxyethyl thiosuccinic acid root, and its molecular structural formula is as shown in the figure.Carboxyethyl sulfur
Stable complex can be formed with copper ion and divalent tin ion for succinic under the conditions of multiple pH, make both precipitations
Current potential is close to and causes electro-deposition to go out signal bronze and be possibly realized.The carboxyethyl thiosuccinic acid root includes dissociating carboxylic
The series compound of ethylenebis dithiocarbamate succinic, when preparing plating solution the raw material that uses be carboxyethyl thiosuccinic acid and its copper,
One or more in stannum, potassium, sodium, lithium, rubidium, caesium, calcium, magnesium, the salt of ammonium or acid salt, preferably carboxyethyl thiosuccinic acid hydrogen
Di-potassium.In plating solution, the content of carboxyethyl thiosuccinic acid root is 0.1-2mol/L.
In electroplate liquid, the content of copper is 0.01-1mol/L, using the raw material containing copper for following when preparing plating solution
One or more in material：Copper simple substance, copper oxide, Copper hydrate, basic copper carbonate, copper sulfate, copper nitrate, copper chloride,
Copper pyrophosphate., Copper pyrophosphate. potassium, cupric phosphate and its acid salt, carboxyethyl thiosuccinic acid mantoquita and its acid salt, carboxyethyl sulfur
For succinic and the complex compound of copper, preferably copper sulfate.
In electroplate liquid, the content of tin element is 0.005-0.8mol/L, prepares the raw material containing tin element used during plating solution and is
One or more in following material：Stannum simple substance, stannous sulfate, stannous chloride, ditin diphosphate, stannous pyrophosphate potassium, carboxyethyl
The complex compound of sulfosuccinate stannous and its acid salt, carboxyethyl thiosuccinic acid and stannous ion, potassium stannate, stannic acid
Sodium, preferably stannous sulfate or sodium stannate.
The anode of electroplating copper tin alloy technique of the present invention is copper, signal bronze, stannum or graphite, and negative electrode is plating piece,
The cathode-current density for using is 0.01-2 amperes/square decimeter, in this current density range, high/low currents density region coating
Solid colour.
The present invention can obtain following gain effect：The plating solution place through long-time after still clear stable, occur without copper powder,
When in plating solution, the concentration of each component upper and lower 20% changes, the composition of coating and outward appearance are not changed substantially, and nickel, zinc, ferrum etc. are common
A small amount of addition of foreign metal ion will not also cause the significantly change of plating solution performance.
Carboxyethyl thiosuccinic acid root toxicity is very low, and raw material is easy to get, not phosphorous in molecule, nitrogen, will not cause water body
Eutrophication and pollute environment, in sewage disposal commonly use decomposing bacteria nonhazardouss effect, it is easy to degrade.
Description of the drawings
Chemical structural formulas of the Fig. 1 for carboxyethyl thiosuccinic acid root.
Specific embodiment
Embodiment 1：
Plating solution mixed dissolution according to the following formulation：
Carboxyethyl thiosuccinic acid hydrogen dipotassium 1.2mol/L
Copper sulfate 0.17mol/L
Stannous sulfate 0.023mol/L
Water surplus
A copper sheet is taken, acetone soak oil removing is used, then with dilute hydrochloric acid immersion activation, is cleaned and be followed by the negative pole of DC source,
Signal bronze plate with Theil indices 12% is connected on the positive pole of DC source as anode, and positive pole is collectively disposed at negative pole
In the plating solution that face is prepared, cathode-current density is controlled in 0.3A/dm2, plating was taken out after 10 minutes, clean, dried up.
Coating even compact light, color are golden yellow.
Embodiment 2：
500ml deionized waters are put in container with a scale, add carboxyethyl thiosuccinic acid 100g, then slow under agitation
7.5 grams of addition basic copper carbonate, after being completely dissolved again under agitation slowly add sodium hydroxide, determine pH be equal to 10 when,
Stopping adding, adding 40 grams of sodium stannate, deionized water is added after stirring and dissolving to 1000ml scales.Bath temperature is controlled for 50
℃.
A copper sheet is taken, alcohol-pickled oil removing is used, then with dilute sulfuric acid immersion activation, is cleaned the negative pole being followed by DC source
On, with a graphite cake as anode, it is connected on the positive pole of DC source, positive pole is collectively disposed at the plating solution for preparing above with negative pole
In, cathode-current density is controlled in 0.2A/dm2, plating was taken out after 10 minutes, clean, dried up.
Coating even compact light, color are golden yellow.
Claims (5)
1. a kind of cyanide-free copper-tin alloy electroplating bath, is characterized in that in plating solution containing carboxyethyl thiosuccinic acid root, copper, stannum unit
Element.
2. according to claim 1 carboxyethyl thiosuccinic acid root include dissociating carboxyethyl thiosuccinic acid root be
Row compound, when preparing plating solution the raw material that uses be carboxyethyl thiosuccinic acid and its copper, stannum, potassium, sodium, lithium, rubidium, caesium, calcium,
One or more in magnesium, the salt of ammonium or acid salt, preferably carboxyethyl thiosuccinic acid hydrogen dipotassium, in plating solution, carboxyethyl is thio
The content of succinic is 0.1-2mol/L.
3. copper content in the plating solution is 0.01-1mol/L according to claim 1, prepares the cupric used during plating solution
The raw material of element is one or more in following material：Copper simple substance, copper oxide, Copper hydrate, basic copper carbonate, sulphuric acid
Copper, copper nitrate, copper chloride, cupric phosphate and its acid salt, carboxyethyl thiosuccinic acid mantoquita and its thio fourth of acid salt, carboxyethyl
Two acid groups and the complex compound of copper, preferably copper sulfate.
4. tin element content in the plating solution is 0.005-0.8mol/L according to claim 1, uses during preparation plating solution
Raw material containing tin element is one or more of following material：Stannum simple substance, stannous sulfate, stannous chloride, ditin diphosphate, burnt phosphorus
Sour stannum potassium, the complex compound of carboxyethyl thiosuccinic acid stannous and its acid salt, carboxyethyl thiosuccinic acid and stannous ion,
Potassium stannate, sodium stannate, preferably stannous sulfate or sodium stannate.
5. the electroplating technology of electroplate liquid according to claim 1, anode is copper, signal bronze, stannum or graphite, and negative electrode is
Plating piece, the cathode-current density for using are 0.01-2 amperes/square decimeter.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611212155.7A CN106498463A (en) | 2016-12-25 | 2016-12-25 | A kind of new cyanideless electro-plating signal bronze technique |
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| CN1302921A (en) * | 1999-12-22 | 2001-07-11 | 日本麦克德米德株式会社 | Bright tin-copper alloy electroplating liquid and its preparation method |
| JP2010059508A (en) * | 2008-09-04 | 2010-03-18 | Bridgestone Corp | Copper-zinc alloy electroplating bath |
| CN103789803A (en) * | 2014-01-13 | 2014-05-14 | 孙松华 | Cyanide-free copper-tin alloy electroplate liquid and preparation method thereof |
| CN105596614A (en) * | 2016-01-22 | 2016-05-25 | 李先强 | Traditional Chinese medicine composition for treating adenoviral pneumonia |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1302921A (en) * | 1999-12-22 | 2001-07-11 | 日本麦克德米德株式会社 | Bright tin-copper alloy electroplating liquid and its preparation method |
| JP2010059508A (en) * | 2008-09-04 | 2010-03-18 | Bridgestone Corp | Copper-zinc alloy electroplating bath |
| CN103789803A (en) * | 2014-01-13 | 2014-05-14 | 孙松华 | Cyanide-free copper-tin alloy electroplate liquid and preparation method thereof |
| CN105596614A (en) * | 2016-01-22 | 2016-05-25 | 李先强 | Traditional Chinese medicine composition for treating adenoviral pneumonia |
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