CN116988110A - Cyanide-free electroplating solution for preparing imitated shallow gold zipper, electroplating method and composite coating thereof - Google Patents
Cyanide-free electroplating solution for preparing imitated shallow gold zipper, electroplating method and composite coating thereof Download PDFInfo
- Publication number
- CN116988110A CN116988110A CN202310997574.XA CN202310997574A CN116988110A CN 116988110 A CN116988110 A CN 116988110A CN 202310997574 A CN202310997574 A CN 202310997574A CN 116988110 A CN116988110 A CN 116988110A
- Authority
- CN
- China
- Prior art keywords
- concentration
- plating
- copper
- electroplating
- cyanide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000009713 electroplating Methods 0.000 title claims abstract description 89
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 54
- 239000010931 gold Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 26
- 239000002131 composite material Substances 0.000 title claims abstract description 16
- 238000000576 coating method Methods 0.000 title description 16
- 239000011248 coating agent Substances 0.000 title description 15
- 238000007747 plating Methods 0.000 claims abstract description 144
- 238000005282 brightening Methods 0.000 claims abstract description 38
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 34
- 239000008139 complexing agent Substances 0.000 claims abstract description 32
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical class [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 150000003839 salts Chemical class 0.000 claims abstract description 27
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims abstract description 18
- 230000008569 process Effects 0.000 claims abstract description 14
- 229910021626 Tin(II) chloride Inorganic materials 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 9
- CARFETJZUQORNQ-UHFFFAOYSA-N 1h-pyrrole-2-thiol Chemical compound SC1=CC=CN1 CARFETJZUQORNQ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000010949 copper Substances 0.000 claims description 59
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 58
- 229910052802 copper Inorganic materials 0.000 claims description 55
- 229910052718 tin Inorganic materials 0.000 claims description 18
- 239000002253 acid Substances 0.000 claims description 17
- 229940120146 EDTMP Drugs 0.000 claims description 14
- NFDRPXJGHKJRLJ-UHFFFAOYSA-N edtmp Chemical compound OP(O)(=O)CN(CP(O)(O)=O)CCN(CP(O)(O)=O)CP(O)(O)=O NFDRPXJGHKJRLJ-UHFFFAOYSA-N 0.000 claims description 14
- WWNNZCOKKKDOPX-UHFFFAOYSA-N trigonelline Natural products C[N+]1=CC=CC(C([O-])=O)=C1 WWNNZCOKKKDOPX-UHFFFAOYSA-N 0.000 claims description 13
- MGFYIUFZLHCRTH-UHFFFAOYSA-N nitrilotriacetic acid Chemical compound OC(=O)CN(CC(O)=O)CC(O)=O MGFYIUFZLHCRTH-UHFFFAOYSA-N 0.000 claims description 11
- -1 polyethylene Polymers 0.000 claims description 11
- 125000003006 2-dimethylaminoethyl group Chemical group [H]C([H])([H])N(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 9
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 8
- 229960002635 potassium citrate Drugs 0.000 claims description 7
- 239000001508 potassium citrate Substances 0.000 claims description 7
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical group [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 7
- 235000011082 potassium citrates Nutrition 0.000 claims description 7
- 235000010290 biphenyl Nutrition 0.000 claims description 6
- 239000004305 biphenyl Substances 0.000 claims description 6
- 125000006267 biphenyl group Chemical group 0.000 claims description 6
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- GWZMWHWAWHPNHN-UHFFFAOYSA-N 2-hydroxypropyl prop-2-enoate Chemical compound CC(O)COC(=O)C=C GWZMWHWAWHPNHN-UHFFFAOYSA-N 0.000 claims description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- DBAMUTGXJAWDEA-UHFFFAOYSA-N Butynol Chemical group CCC#CO DBAMUTGXJAWDEA-UHFFFAOYSA-N 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920000768 polyamine Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 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
- 239000000758 substrate Substances 0.000 claims description 2
- FEJQDYXPAQVBCA-UHFFFAOYSA-J tetrasodium;ethane-1,2-diamine;tetraacetate Chemical compound [Na+].[Na+].[Na+].[Na+].CC([O-])=O.CC([O-])=O.CC([O-])=O.CC([O-])=O.NCCN FEJQDYXPAQVBCA-UHFFFAOYSA-J 0.000 claims description 2
- 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 1
- 239000003513 alkali Substances 0.000 claims 1
- 229910052751 metal Inorganic materials 0.000 abstract description 11
- 239000002184 metal Substances 0.000 abstract description 11
- 238000013461 design Methods 0.000 abstract description 7
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 abstract description 7
- 238000007772 electroless plating Methods 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 abstract 1
- 229910001431 copper ion Inorganic materials 0.000 abstract 1
- 229910001432 tin ion Inorganic materials 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 28
- 238000003756 stirring Methods 0.000 description 28
- 238000012360 testing method Methods 0.000 description 19
- 230000001276 controlling effect Effects 0.000 description 17
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 15
- RCIVOBGSMSSVTR-UHFFFAOYSA-L stannous sulfate Chemical compound [SnH2+2].[O-]S([O-])(=O)=O RCIVOBGSMSSVTR-UHFFFAOYSA-L 0.000 description 11
- 229910000375 tin(II) sulfate Inorganic materials 0.000 description 11
- 239000000047 product Substances 0.000 description 10
- 238000001556 precipitation Methods 0.000 description 9
- 239000002994 raw material Substances 0.000 description 8
- 229910001297 Zn alloy Inorganic materials 0.000 description 7
- 230000003213 activating effect Effects 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 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 7
- 238000005868 electrolysis reaction Methods 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- HXYVTAGFYLMHSO-UHFFFAOYSA-N palmitoyl ethanolamide Chemical compound CCCCCCCCCCCCCCCC(=O)NCCO HXYVTAGFYLMHSO-UHFFFAOYSA-N 0.000 description 7
- 230000037452 priming Effects 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000007921 spray Substances 0.000 description 6
- 238000011179 visual inspection Methods 0.000 description 6
- 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 5
- 238000004140 cleaning Methods 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000012544 monitoring process Methods 0.000 description 5
- IGRGEBBXERSCPC-UHFFFAOYSA-M sodium;3-(4-hydroxybut-2-ynoxy)propane-1-sulfonate Chemical compound [Na+].OCC#CCOCCCS([O-])(=O)=O IGRGEBBXERSCPC-UHFFFAOYSA-M 0.000 description 5
- 238000005299 abrasion Methods 0.000 description 4
- 230000032683 aging Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 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 3
- 230000000536 complexating effect Effects 0.000 description 3
- 230000001105 regulatory effect Effects 0.000 description 3
- 239000003086 colorant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000004900 laundering Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 208000014451 palmoplantar keratoderma and congenital alopecia 2 Diseases 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 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 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 101000774651 Naja atra Zinc metalloproteinase-disintegrin-like kaouthiagin-like Proteins 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229940116318 copper carbonate Drugs 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 150000002344 gold compounds Chemical class 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000012764 semi-quantitative analysis Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000001119 stannous chloride Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses an electroless plating solution for preparing a shallow gold-imitated slide fastener, an electroplating method and a composite plating layer thereof, wherein the electroless plating solution only takes copper salt and tin salt as main salts, the concentration of copper ions is 0.15-0.3mol/L, and the concentration of tin ions is 0.04-0.1mol/L; potassium pyrophosphate is used as a main complexing agent, and the concentration is 250-350g/L; the electroplating solution does not contain gold salt with higher price, and is prepared by specially configuring copper salt and tin salt, simultaneously assisting with a plurality of specific complexing agents, and combining with a brightening agent, namely mercaptoazole organic matters, so that crystal nuclei formed in the electroplating process of the cyanide-free electroplating solution are densely distributed, and further a bright and flat imitation light gold plating layer or light gold and texture similar to K gold are formed on a zipper metal part, so that the product design with the requirements of the light gold metal part is met, and meanwhile, the electroplating cost is lower, the market competitiveness is higher.
Description
Technical Field
The invention belongs to the technical field of electroplating, and particularly relates to cyanide-free electroplating solution for preparing a shallow-gold-imitated zipper, an electroplating method thereof and a composite coating.
Background
The zipper is a connecting element which is widely used and can be freely controlled to open and close, in practical application, in order to match with the overall design of products (such as clothes, bags and the like), the zipper which is one of the product elements also needs to be matched with the product design and concepts to customize special colors and textures, so that the zipper can meet more product design requirements, and in the field, metal parts of the zipper are generally colored and/or certain textures (such as matte, high reflection and the like) are realized by adopting methods such as electroplating, electroless plating, anodic oxidation and the like.
Gold gives people noble and gorgeous aesthetic feeling, is a common color in product design, and is generally designed in the field to electroplate the surface of the metal part of the zipper by using electroplating solution with gold salt so as to present gold with high texture.
The patent document with the application number of CN202310049479.7 discloses a plating solution of cyanide-free electroplated gold and a method for electroplating gold by adopting the plating solution of cyanide-free electroplated gold: the cyanide-free gold plating solution consists of 25g/L of gold salt, 150g/L of conductive salt, 50g/L of acid-base modifier, 20ppm of auxiliary agent, 10ppm of brightening agent and ultrapure water, and simultaneously, the Ni barrier layer is deposited on the surface of the brass foil substrate before electroplating, so that the gold plating layer has good durability and integrity.
As another patent document with application number CN202310016989.4, an environment-friendly cyanide-free electroplating solution and an electroplating process thereof are disclosed, and the formula comprises the following components in mass concentration: 3-10g/L of gold salt, 30-60mg/L of composite brightening agent, 2-6g/L of complexing agent, 0.3-0.9g/L of composite crystal nucleus refiner, 30-60mg/L of accelerator, 25-75mg/L of composite leveling agent, 35-70mg/L of dispersing agent, 30-60mg/L of stabilizer and 15-60mg/L of surfactant.
However, gold salt is a relatively expensive raw material, if the technology is adopted to plate gold on the zipper, the production cost is too high, and the selling of the zipper is not facilitated, so that the invention aims to form a high-quality imitated shallow gold plating layer on the surface of a metal part of the zipper under the condition that no gold salt is adopted by designing an electroplating solution system and a preparation process, so that the design of products with shallow gold requirements is met, and meanwhile, the electroplating cost is lower, and the invention has market competitiveness.
Disclosure of Invention
Aiming at the problems in the related art, the invention provides cyanide-free electroplating solution for preparing a shallow-gold-imitated zipper, an electroplating method and a composite coating thereof, so as to overcome the technical problems in the prior art.
The technical scheme of the invention is realized as follows:
an electroless plating solution for preparing a shallow gold-imitated slide fastener, which uses copper salt and tin salt as main salts only, comprises:
copper salt of 0.15-0.3mol/L in terms of copper content and tin salt of 0.04-0.1mol/L in terms of tin content;
potassium pyrophosphate is used as a main complexing agent, and the concentration is 250-350g/L;
the auxiliary complexing agents are first auxiliary complexing agents, second auxiliary complexing agents and third auxiliary complexing agents, wherein the first auxiliary complexing agents are citrate, the second auxiliary complexing agents are nitrilotriacetic acid, and the third auxiliary complexing agents are one of Ethylenediamine (EDA), ethylenediamine tetraacetic acid (EDTA), ethylenediamine tetraacetic acid disodium salt (EDTA-2 Na), ethylenediamine tetraacetic acid tetrasodium salt (EDTA-4 Na) and ethylenediamine tetramethylene phosphonic acid (EDTMPA);
at least one brightening agent is set as a first brightening agent, and the first brightening agent is a mercaptoazole organic matter.
Firstly, compared with the prior art, the electroplating solution does not contain gold salt with higher price, and is prepared specifically by only carrying out specific configuration on copper salt and tin salt, and simultaneously, a plurality of specific complexing agents are combined, and then, the brightening agent, namely mercapto-azole organic matters, are combined to ensure that crystal nuclei formed in the electroplating process of the cyanide-free electroplating solution are densely distributed, so that a bright and flat imitation light gold plating layer or a light gold and texture similar to K gold is formed on a zipper metal part, thereby meeting the product design with the requirements of the light gold metal part, and simultaneously, the electroplating cost is lower, the cyanide-free electroplating solution has the advantages of simple composition, strong uniform plating capability and covering capability and high stability.
And secondly, the invention is non-cyanide electroplating solution, does not contain highly toxic cyanide, and is environment-friendly.
Finally, the copper element content and the tin element content of the invention are selected specifically, if the copper element content and the tin element content are lower than the limit range of the invention, the plating layer is red, or the plating is leaked in a low area, and the plating layer is matt; if the temperature is higher than the limit range of the invention, the plating layer is silvery white, or the plating solution becomes muddy, or the plating layer is fragile and easy to burst, and the light gold of the target imitation K gold and the excellent plating performance cannot be obtained; on the other hand, the main complexing agent potassium pyrophosphate has stronger complexing effect on copper and tin, and the color of the plating layer is not easy to control, so that the invention can obtain the imitation light gold plating layer with excellent performance by designing a plurality of specific auxiliary complexing agents to stabilize a system and controlling the precipitation speed of copper and tin, and the metal texture of the imitation K gold can not be obtained without adopting the specific complex compound and the brightening agent.
Further, the copper salt is one or more of copper pyrophosphate, basic copper carbonate, copper sulfate and copper chloride.
Further, the tin salt is one or more of stannous pyrophosphate, stannous sulfate and stannous chloride.
Preferably, the plating layer also comprises a second brightening agent and a third brightening agent, wherein the second brightening agent is butynol ether propane sulfonate (HBOPS-Na), the CAS number is 90268-78-3, the concentration is 15-25ppm, and the plating layer can be smoother and the brightness of a low area can be increased; the third brightening agent is one or more than two polyethylene polyamines.
More preferably, the third brightening agent is a combination of diethylenetriamine and tetraethylenepentamine, the concentration of the diethylenetriamine is 0.01-0.03ml/L, the high-area brightness can be effectively improved, and the concentration of the tetraethylenepentamine is 0.03-0.05ml/L, the low-area brightness can be effectively improved.
The brightening agent has excellent combination effect, and can form adsorption on the electrode-plating solution interface to raise the overpotential and raise the performance of the plating layer.
Preferably, the second brightening agent and the third brightening agent have another technical scheme, the second brightening agent is diethyl propioamine and diphenyl sulphonimide adduct with the concentration of 50-80ppm, and the diethyl propioamine and diphenyl sulphonimide adduct is PEA diethyl propioamine and diphenyl sulphonimide adduct produced by Shanghai Shanxin chemical technology Co. The PEA and the mercaptoazole organic compound are cooperatively matched, so that the ductility of the coating can be effectively improved, and the coating is smoother and brighter.
The third brightening agent is modified methyl trigonelline with the concentration of 5-20ppm, and the modified methyl trigonelline adopts HOP-A modified methyl trigonelline produced by Shanghai Shanxin chemical technology Co., ltd.
From the above, it is known that the above-mentioned mercaptoazole organic compound and PEA are used as two brightening agents with synergistic effect to actually realize the optimal K-like gold gloss of the present invention, but the inventor finds that the combination effect is superior but can cause the internal stress of the plating layer to increase, and further the brittle fracture problem of the plating layer is easy to occur, in order to solve the problem, the cyanide-free electroplating solution of the present invention further comprises modified methyl trigonelline with concentration of 5-20ppm, which cooperates with PEA and mercaptoazole organic compound to make the plating layer crystallization fine and corrosion resistant, and can maximally reduce, even eliminate the brittle problem of the plating layer.
Preferably, the mercapto-azole organic matter is 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole, the CAS number is 61607-68-9, the concentration is 0.05-0.1g/L, the mercapto-azole organic matter can disperse and leave positions, the low area of the coating is uniform and bright, and the mercapto-azole organic matter and the brightening agent can be combined and cooperated with the brightening agent of the invention to obtain the best gloss and high-quality imitation light gold coating.
Preferably, the citrate is potassium citrate or ammonium citrate, the concentration is 10-50g/L, the thickness of the coating can be uniform, and the pH value of the system can be stabilized;
the concentration of the nitrilotriacetic acid is 5-10g/L;
the third auxiliary complexing agent is ethylenediamine tetramethylene phosphonic acid, and the concentration is 2-5g/L. Compared with other third auxiliary complexing agents, the ethylenediamine tetramethylene phosphonic acid (EDTMPA) has stronger complexing ability on copper, and can effectively control the precipitation speed of copper.
An electroplating method for preparing a shallow gold-imitated slide fastener adopts the cyanide-free electroplating solution to carry out electroplating, the pH is controlled to be 8.5-9.5, and the electroplating temperature is 25-45 ℃.
The electroplating solution system designed based on the invention further needs to control electroplating parameters, and when the pH is lower than the limit range of the invention, the complexing ability is insufficient, and the coating is reddish and rough; if the ratio is higher than the limit range of the present invention, the plating solution tends to become turbid, and precipitation occurs. If the temperature is lower than the limit range of the invention, plating is slow, the plating layer has different colors, and the low area shows red color; if it is higher than the limit of the present invention, the whole plating layer becomes red.
Preferably, when electroplating is carried out by barrel plating, the main salt is copper salt with copper content of 0.15-0.25mol/L and tin salt with tin content of 0.04-0.08mol/L, pH is controlled at 8.8-9.3, and current density is set at 0.2-1.5A/dm 2 The rotating speed is 6-10r/min, and the barrel plating time is 5-60min;
or, when plating is carried out by adopting the hanging plating process, the main salt is copper salt with the copper content of 0.2-0.3mol/L and tin salt with the tin content of 0.05-0.1mol/L, the pH is controlled to 8.8-9.3, and the current density is set to 0.1-2A/dm 2 The duration of the plating is 5-30min.
Based on the electroplating solution system designed by the invention, different electroplating processes are needed for setting electroplating parameters. If the current density is lower than the limit range of the invention, the plating layer reddening or the plating leakage in the low area; if the current density is higher than the limit of the present invention, the plating layer is white and is liable to crack. If the electroplating time is too long, the plating layer is too thick and is easy to burst; if the electroplating time is too short, the plating layer is thinner, the corrosion resistance is slightly poor, and the salt spray test is failed.
Because the concentration of the main salt of barrel plating is lower than that of rack plating, the current density range is required to be controlled to be smaller than that of rack plating.
A kind of imitative shallow gold compound plating, is the base copper plating layer, acid copper plating layer and imitative shallow gold plating layer that is the foundation bed to be electroplated outwards sequentially, imitative shallow gold plating layer is electroplated by above-mentioned non-cyanide plating solution and is formed.
Specifically, the imitation shallow gold plating layer comprises the following components in percentage by weight:
Cu 83-87wt％
Sn 10-14wt％
C 2-4wt％。
based on the electroplating solution system, the imitation shallow gold plating layer only contains three elements of copper, tin and carbon, but forms specific color and texture similar to K gold, has uniform color and luster, good brightness, fine and smooth crystallization, compact structure, firm combination with a metal matrix, high surface flatness and no peeling, falling or stripping phenomena.
Drawings
FIG. 1 is one of the electron microscope scans of the slider sample of example 2;
FIG. 2 is a spectrum of the square micro-region of FIG. 1;
FIG. 3 is a second electron microscope scan of the sample slider of example 2;
FIG. 4 is a graph of the square micro-region of FIG. 3;
FIG. 5 is a schematic diagram of the structure of the imitation shallow gold composite plating layer of the invention;
FIG. 6 is a metallographic section (200 times magnification) of example 2;
FIG. 7 is a metallographic section (200 times magnification) of example 4;
FIG. 8 is a sample view of a slider of example 2;
FIG. 9 is a sample view of the slider of comparative example 1;
fig. 10 is a drawing of a sample slider of comparative example 2.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is apparent that the described embodiments are only some of the embodiments of the present invention. All other embodiments obtained without inventive effort based on the embodiments of the present invention fall within the scope of the present invention.
Example 1
(1) Removing oil and activating the zipper head (zinc alloy zipper head blank) to be electroplated, preplating alkaline copper for priming, and then plating acid copper for increasing brightness.
(2) Preparation of cyanide-free electroplating solution
The cyanide-free electroplating solution comprises the following raw materials:
configuration operation:
A. weighing and pouring metered potassium pyrophosphate into a plating bath according to the concentration of a cylinder and the size of the bath volume, adding water to 1/2 of the bath volume, and fully stirring until the potassium pyrophosphate is completely dissolved for standby;
B. and additionally preparing an auxiliary complexing agent: dissolving the measured potassium citrate, nitrilotriacetic acid, EDTMPA and KOH with water with the volume of 1/4 of the tank volume, adjusting the PH to about 9 by KOH, slowly pouring into the electrolytic tank in the step A, and uniformly stirring;
C. slowly pouring the measured copper sulfate pentahydrate into an electrolytic tank, and stirring until the copper sulfate pentahydrate is completely dissolved;
D. slowly adding a small amount of the measured stannous sulfate into the electrolytic bath for many times, stirring while adding, and finally, using water to fix the volume to a target volume, and adjusting the PH to 9;
E. the metered amount of 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole was dissolved in water and then added to an electrolyzer for low density current electrolysis to remove impurities.
The prepared cyanide-free plating solution was allowed to stand for 24 hours, 48 hours, and 96 hours, and the presence or absence of precipitation was observed by visual inspection.
(3) The zipper puller has smaller volume and needs batch electroplating, so the embodiment adopts a barrel plating process
Step (2) is carried out on the step (II) by using the cyanide-free electroplating solution after standing for 96 hours1) Barrel plating is carried out on the pretreated zipper heads, the pH is controlled to be 8.5-9.5, the concentration of the pentahydrate copper sulfate is controlled to be 0.15-0.25mol/L based on the copper content, the concentration of the stannous sulfate is controlled to be 0.04-0.08mol/L based on the tin content, the pH and the main salt concentration which dynamically change are monitored in real time, if the pH and the main salt concentration are out of a limiting range, the electroplating temperature is adjusted in time to be 35 ℃, and the cathode current density is set to be 0.9A/dm 2 The anode is electrolytic copper, the rotating speed is 8r/min, and the barrel plating time is 15min.
(4) And cleaning the barrel-plated zipper head, and drying.
The surface of the electroplated zipper puller in the embodiment is covered with an imitation shallow gold composite plating layer, and referring to fig. 5, a bottoming alkaline copper plating layer 3, a brightening acid copper plating layer 2 and an imitation shallow gold plating layer 1 are sequentially arranged from the surface of the zipper puller 4 outwards.
Example 2
(1) Removing oil and activating the zipper head (zinc alloy zipper head blank) to be electroplated, preplating alkaline copper for priming, and then plating acid copper for increasing brightness.
(2) Preparation of cyanide-free electroplating solution
The cyanide-free electroplating solution comprises the following raw materials:
configuration operation:
A. weighing and pouring metered potassium pyrophosphate into a plating bath according to the concentration of a cylinder and the size of the bath volume, adding water to 1/2 of the bath volume, and fully stirring until the potassium pyrophosphate is completely dissolved for standby;
B. and additionally preparing an auxiliary complexing agent: dissolving the measured potassium citrate, nitrilotriacetic acid, EDTMPA and KOH with water with the volume of 1/4 of the tank volume, adjusting the PH to about 9 by KOH, slowly pouring into the electrolytic tank in the step A, and uniformly stirring;
C. slowly pouring the measured copper sulfate pentahydrate into an electrolytic tank, and stirring until the copper sulfate pentahydrate is completely dissolved;
D. slowly adding a small amount of the measured stannous sulfate into the electrolytic bath for many times, stirring while adding, and finally, using water to fix the volume to a target volume, and adjusting the PH to 9;
E. the metered 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole, HBOPS-Na, diethylenetriamine and tetraethylenepentamine are respectively dissolved in water and respectively added into an electrolytic tank, and low-density current is used for electrolysis to remove impurities.
The prepared cyanide-free plating solution was allowed to stand for 24 hours, 48 hours, and 96 hours, and the presence or absence of precipitation was observed by visual inspection.
(3) The zipper puller has smaller volume and needs batch electroplating, so the embodiment adopts a barrel plating process
Barrel plating the zipper head pretreated in the step (1) by using the cyanide-free electroplating solution which is subjected to standing for 96 hours in the step (2), controlling the pH value to be 8.5-9.5, controlling the concentration of copper sulfate pentahydrate to be 0.15-0.25mol/L based on the copper content, controlling the concentration of stannous sulfate to be 0.04-0.08mol/L based on the tin content, monitoring the dynamically-changed pH value and main salt concentration in real time, and adjusting the electroplating temperature to be 30 ℃ and setting the cathode current density to be 0.5A/dm in time if the pH value and the main salt concentration are out of a limited range 2 The anode is electrolytic copper, the rotating speed is 6r/min, and the barrel plating time is 10min.
(4) And cleaning the barrel-plated zipper head, and drying.
The surface of the electroplated zipper puller in the embodiment is covered with an imitation shallow gold composite plating layer, and referring to fig. 5, a bottoming alkaline copper plating layer 3, a brightening acid copper plating layer 2 and an imitation shallow gold plating layer 1 are sequentially arranged from the surface of the zipper puller 4 outwards.
Example 3
(1) Removing oil and activating the zipper head (zinc alloy zipper head blank) to be electroplated, preplating alkaline copper for priming, and then plating acid copper for increasing brightness.
(2) Preparation of cyanide-free electroplating solution
The cyanide-free electroplating solution comprises the following raw materials:
configuration operation:
A. weighing and pouring metered potassium pyrophosphate into a plating bath according to the concentration of a cylinder and the size of the bath volume, adding water to 1/2 of the bath volume, and fully stirring until the potassium pyrophosphate is completely dissolved for standby;
B. and additionally preparing an auxiliary complexing agent: dissolving the measured potassium citrate, nitrilotriacetic acid, EDTMPA and KOH with water with the volume of 1/4 of the tank volume, adjusting the PH to about 9 by KOH, slowly pouring into the electrolytic tank in the step A, and uniformly stirring;
C. slowly pouring the measured copper sulfate pentahydrate into an electrolytic tank, and stirring until the copper sulfate pentahydrate is completely dissolved;
D. slowly adding a small amount of stannous sulfate into the electrolytic bath for many times, stirring while adding, and finally, using water to fix the volume to a target volume, and adjusting the PH to 9;
E. the metered 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole, HBOPS-Na, diethylenetriamine and tetraethylenepentamine are respectively dissolved in water and respectively added into an electrolytic tank, and low-density current is used for electrolysis to remove impurities.
The prepared cyanide-free plating solution was allowed to stand for 24 hours, 48 hours, and 96 hours, and the presence or absence of precipitation was observed by visual inspection.
(3) The zipper puller has smaller volume and needs batch electroplating, so the embodiment adopts a barrel plating process
Barrel plating is carried out on the zipper head pretreated in the step (1) by using the cyanide-free electroplating solution which is kept stand for 96 hours in the step (2), the pH is controlled to be 8.8-9.3, the concentration of the copper sulfate pentahydrate is controlled to be 0.15-0.25mol/L based on the copper content, the concentration of the stannous sulfate is controlled to be 0.04-0.08mol/L based on the tin content, the dynamically-changed pH and the main salt concentration are monitored in real time, if the pH exceeds a limiting range, the electroplating temperature is adjusted in time to be 35 ℃, and the cathode current density is set to be 0.9A/dm 2 The anode is electrolytic copper, the rotating speed is 8r/min, and the barrel plating time is 15min.
(4) And cleaning the barrel-plated zipper head, and drying to obtain the finished product shown in figure 8.
The surface of the electroplated zipper puller in the embodiment is covered with an imitation shallow gold composite plating layer, and referring to fig. 5, a bottoming alkaline copper plating layer 3, a brightening acid copper plating layer 2 and an imitation shallow gold plating layer 1 are sequentially arranged from the surface of the zipper puller 4 outwards.
Example 4
(1) Removing oil and activating the zipper head (zinc alloy zipper head blank) to be electroplated, preplating alkaline copper for priming, and then plating acid copper for increasing brightness.
(2) Preparation of cyanide-free electroplating solution
The cyanide-free electroplating solution comprises the following raw materials:
configuration operation:
A. weighing and pouring metered potassium pyrophosphate into a plating bath according to the concentration of a cylinder and the size of the bath volume, adding water to 1/2 of the bath volume, and fully stirring until the potassium pyrophosphate is completely dissolved for standby;
B. and additionally preparing an auxiliary complexing agent: dissolving the metered ammonium citrate, nitrilotriacetic acid, EDTMPA and KOH by using water with the volume of 1/4 of the tank, regulating the PH to about 9 by KOH, slowly pouring into the electrolytic tank in the step A, and uniformly stirring;
C. slowly pouring the metered copper pyrophosphate into an electrolytic tank, and stirring until the copper pyrophosphate is completely dissolved;
D. slowly adding stannous pyrophosphate into the electrolytic bath for a plurality of times, stirring while adding, and finally, fixing the volume to a target volume by using water, and adjusting the PH to 9;
E. the metered 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole and HOP-A modified methyl trigonelline are respectively dissolved in water and respectively added into an electrolytic tank, and low-density current electrolysis is carried out to remove impurities.
The prepared cyanide-free plating solution was allowed to stand for 24 hours, 48 hours, and 96 hours, and the presence or absence of precipitation was observed by visual inspection.
(3) The zipper puller has smaller volume and needs batch electroplating, so the embodiment adopts a barrel plating process
Barrel plating the zipper head pretreated in the step (1) by using the cyanide-free electroplating solution which is subjected to standing for 96 hours in the step (2), controlling the pH value to be 8.5-9.5, controlling the copper pyrophosphate concentration to be 0.15-0.25mol/L based on the copper content, controlling the stannous pyrophosphate concentration to be 0.04-0.08mol/L based on the tin content, monitoring the dynamically-changed pH value and main salt concentration in real time, and if the pH value exceeds a limiting range, timely adjusting the electroplating temperature to be 40 ℃, and controlling the negative temperature to be negativeThe polar current density was set to 1.2A/dm 2 The anode is electrolytic copper, the rotating speed is 10r/min, and the barrel plating time is 25min.
(4) And cleaning the barrel-plated zipper head, and drying.
The surface of the electroplated zipper puller in the embodiment is covered with an imitation shallow gold composite plating layer, and referring to fig. 5, a bottoming alkaline copper plating layer 3, a brightening acid copper plating layer 2 and an imitation shallow gold plating layer 1 are sequentially arranged from the surface of the zipper puller 4 outwards.
Example 5
(1) Removing oil and activating the zipper head (zinc alloy zipper head blank) to be electroplated, preplating alkaline copper for priming, and then plating acid copper for increasing brightness.
(2) Preparation of cyanide-free electroplating solution
The cyanide-free electroplating solution comprises the following raw materials:
configuration operation:
A. weighing and pouring metered potassium pyrophosphate into a plating bath according to the concentration of a cylinder and the size of the bath volume, adding water to 1/2 of the bath volume, and fully stirring until the potassium pyrophosphate is completely dissolved for standby;
B. and additionally preparing an auxiliary complexing agent: dissolving the metered ammonium citrate, nitrilotriacetic acid, EDTMPA and KOH by using water with the volume of 1/4 of the tank, regulating the PH to about 9 by using KOH, slowly pouring into the electrolytic tank in the step A, and uniformly stirring;
C. slowly pouring the metered copper pyrophosphate into an electrolytic tank, and stirring until the copper pyrophosphate is completely dissolved;
D. slowly adding stannous pyrophosphate into the electrolytic bath for a plurality of times, stirring while adding, and finally, fixing the volume to a target volume by using water, and adjusting the PH to 9;
E. the metered 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole, PEA and HOP-A modified methyl trigonelline are respectively dissolved in water and respectively added into an electrolytic tank, and low-density current is used for electrolysis to remove impurities.
The prepared cyanide-free plating solution was allowed to stand for 24 hours, 48 hours, and 96 hours, and the presence or absence of precipitation was observed by visual inspection.
(3) The zipper puller has smaller volume and needs batch electroplating, so the embodiment adopts a barrel plating process
Barrel plating the zipper head pretreated in the step (1) by using the cyanide-free electroplating solution which is subjected to standing for 96 hours in the step (2), controlling the pH value to be 8.5-9.5, controlling the copper pyrophosphate concentration to be 0.15-0.25mol/L based on the copper content, controlling the stannous pyrophosphate concentration to be 0.04-0.08mol/L based on the tin content, monitoring the dynamically-changed pH value and main salt concentration in real time, and if the pH value and the main salt concentration are out of a limiting range, timely adjusting the electroplating temperature to be 40 ℃ and setting the cathode current density to be 1.2A/dm 2 The anode is electrolytic copper, the rotating speed is 10r/min, and the barrel plating time is 25min.
(4) And cleaning the barrel-plated zipper head, and drying.
The surface of the electroplated zipper puller in the embodiment is covered with an imitation shallow gold composite plating layer, and referring to fig. 5, a bottoming alkaline copper plating layer 3, a brightening acid copper plating layer 2 and an imitation shallow gold plating layer 1 are sequentially arranged from the surface of the zipper puller 4 outwards.
Comparative example 1
(1) Removing oil and activating the zipper head (zinc alloy zipper head blank) to be electroplated, preplating alkaline copper for priming, and then plating acid copper for increasing brightness.
(2) Performing electroplating solution configuration
The electroplating solution comprises the following raw materials:
configuration operation:
A. weighing and pouring metered potassium pyrophosphate into a plating bath according to the concentration of a cylinder and the size of the bath volume, adding water to 1/2 of the bath volume, and fully stirring until the potassium pyrophosphate is completely dissolved for standby;
B. and additionally preparing an auxiliary complexing agent: dissolving the measured potassium citrate, nitrilotriacetic acid, EDTMPA and KOH with water with the volume of 1/4 of the tank volume, adjusting the PH of the KOH to about 8.0, slowly pouring the solution into the electrolytic tank in the step A, and uniformly stirring;
C. slowly pouring the measured copper sulfate pentahydrate into an electrolytic tank, and stirring until the copper sulfate pentahydrate is completely dissolved;
D. slowly adding a small amount of stannous sulfate into the electrolytic bath for many times, stirring while adding, and finally, using water to fix the volume to a target volume, and adjusting the PH to 8.0;
E. the metered 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole is dissolved in water and then added into an electrolytic tank, and low-density current is used for electrolysis to remove impurities.
(3) The zipper puller has smaller volume and needs batch electroplating, so the embodiment adopts a barrel plating process
Barrel plating the zipper head pretreated in the step (1) by using the electroplating solution in the step (2), controlling the pH value to be 8.0-8.5, controlling the concentration of copper sulfate pentahydrate to be 0.05-0.15mol/L based on the copper content, controlling the concentration of stannous sulfate to be 0.02-0.04mol/L based on the tin content, monitoring the dynamically-changed pH value and main salt concentration in real time, and if the pH value and the main salt concentration are out of a limited range, adjusting the electroplating temperature to be 35 ℃ in time, and setting the cathode current density to be 0.1A/dm 2 The anode is electrolytic copper, the rotating speed is 8r/min, and the barrel plating time is 15min.
(4) The zipper head after barrel plating is cleaned and dried, and the finished product is shown in figure 9, and the coating is reddish yellow and does not accord with the light gold imitation pursued by the invention.
Comparative example 2
(1) Removing oil and activating the zipper head (zinc alloy zipper head blank) to be electroplated, preplating alkaline copper for priming, and then plating acid copper for increasing brightness.
(2) Performing electroplating solution configuration
The electroplating solution comprises the following raw materials:
configuration operation:
A. weighing and pouring metered potassium pyrophosphate into a plating bath according to the concentration of a cylinder and the size of the bath volume, adding water to 1/2 of the bath volume, and fully stirring until the potassium pyrophosphate is completely dissolved for standby;
B. and additionally preparing an auxiliary complexing agent: dissolving the measured potassium citrate, nitrilotriacetic acid, EDTMPA and KOH with water with the volume of 1/4 of the tank volume, regulating the PH to about 9.0 with KOH, slowly pouring into the electrolytic tank in the step A, and uniformly stirring;
C. slowly pouring the measured copper sulfate pentahydrate into an electrolytic tank, and stirring until the copper sulfate pentahydrate is completely dissolved;
D. slowly adding a small amount of stannous sulfate into the electrolytic bath for many times, stirring while adding, and finally, using water to fix the volume to a target volume, and adjusting the PH to 8.5-9.5;
E. the metered 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole is dissolved in water and then added into an electrolytic tank, and low-density current is used for electrolysis to remove impurities.
(3) The zipper puller has smaller volume and needs batch electroplating, so the embodiment adopts a barrel plating process
Barrel plating the zipper head pretreated in the step (1) by using the electroplating solution in the step (2), controlling the pH value to be 8.5-9.5, controlling the concentration of copper sulfate pentahydrate to be 0.25-0.35mol/L based on the copper content, controlling the concentration of stannous sulfate to be 0.08-0.12mol/L based on the tin content, monitoring the dynamically-changed pH value and main salt concentration in real time, and if the pH value and the main salt concentration are out of a limited range, adjusting the electroplating temperature in time to be 50 ℃, and setting the cathode current density to be 1.8A/dm 2 The anode is electrolytic copper, the rotating speed is 8r/min, and the barrel plating time is 15min.
(4) The zipper head after barrel plating is cleaned and dried, and the finished product is shown in figure 10, and the coating is silvery white and does not accord with the light gold imitation pursued by the invention.
Performance testing
Since the solutions of comparative examples 1 and 2 failed to achieve the light gold-like color pursued by the present invention, as shown in fig. 9 and 10, they were removed. The performance test was performed on examples 1 to 5 below.
(1) The stability of the plating solutions and the surface quality of the plating layers of examples 1 to 5 were tested
Standing the cyanide-free electroplating solutions prepared in examples 1 to 5 for 24 hours, 48 hours and 96 hours respectively, and observing whether a precipitate is separated out or not by a visual inspection method; meanwhile, the color, texture and surface morphology of the plating layer plated by the plating solution after standing for 96 hours are observed.
In each of examples 1 to 5, the slide fastener slider was barrel-plated with the plating solution after standing for 96 hours, and a sample was shown in example 3, as shown in fig. 8.
From the above results, it can be seen that: the electroplating solution system has good stability, no precipitation occurs after standing, good electroplating quality is maintained, and the service life is longer; meanwhile, the cyanide-free electroplating solution and the electroplating method can form a bright and flat imitation shallow gold plating layer on the surface of the zipper head.
In addition, as can be seen from comparative examples 1 and 3, HBOPS-Na, diethylenetriamine and tetraethylenepentamine have the effect of improving the surface quality of the imitation shallow gold plating layer, so that the plating layer is smoother and brighter; as can be seen from comparative examples 4 and 5, PEA also has the effect of improving the surface quality of the imitation shallow gold plating.
(2) The surface of example 3 was observed under a scanning electron microscope and subjected to qualitative and semi-quantitative analysis of chemical components
Fig. 1 and 3 are electron microscope scans of two samples of the slider of the slide fastener of example 3, and it can be seen that the coating is flat and smooth, the structure is compact, and the gaps are very few.
FIG. 2 is a graph of the square micro-region of FIG. 1, with the composition scan results shown in the following table:
| Element | Line Type | Weight％ | Weight％Sigma | Atmoic％ |
| C | K series | 3.18 | 0.22 | 15.55 |
| Cu | L series | 84.85 | 0.26 | 78.52 |
| Sn | L series | 11.97 | 0.18 | 5.93 |
| Total | - | 100.00 | - | 100.00 |
FIG. 4 is a graph of the square micro-region of FIG. 3, with the composition scan results shown in the following table:
| Element | Line Type | Weight％ | Weight％Sigma | Atmoic％ |
| C | K series | 3.49 | 0.23 | 16.83 |
| Cu | L series | 84.85 | 0.27 | 77.47 |
| Sn | L series | 11.66 | 0.19 | 5.70 |
| Total | - | 100.00 | - | 100.00 |
(3) Metallographic section analysis of the coatings of example 4 and example 5
Fig. 7 shows a 200-fold magnification of the section of example 4 under a microscope, and fig. 6 shows a 200-fold magnification of the section of example 5 under a microscope, it being seen that the coating of example 5 with PEA added is very flat, whereas the coating of example 4 without PEA added is relatively rough.
(4) The following abrasion resistance test, salt spray test and aging test were performed on the pseudo-light gold slider prepared in example 1 and example 3.
A. Abrasion resistance test: the abrasion resistance was measured by referring to the AATCC 135 American standard washer water wash test and the AATCC-612A steel ball abrasion resistance water wash test.
The results of example 1 are as follows:
Appearance Durability to Laundering(American standard)
Appearance Durability to Washing
the results of example 3 are as follows:
Appearance Durability to Laundering(American standard)
/>
Appearance Durability to Washing
Note：
scale of 1to 5，where 1is bad and 5 is good.
5-----Negligible or no change.
4-----Slight changed
3------Noticeable changed
2------Considerable changed
1------Heavy changed
* And (3) standard judgment: 1 to 3 are disqualified; and 4 to 5 are qualified.
B. Salt spray test: corrosion resistance was measured by referring to ASTM B368 acid salt spray test standard.
The test results of example 1 are as follows:
Acid Salt Spray(CASS Test)
the test results of example 3 are as follows:
Acid Salt Spray(CASS Test)
Note：
Rating coated metal color change：
10-no change
9-very slight changed
8-slightly changed
6-moderate changed
4-Noticeable changed
2-severe changed
C. aging test: the mixture was left for 72 hours at a temperature of 135F (about 57 degrees) in a humidity chamber with 95% humidity.
The test results of example 1 are as follows:
Wet Environmental Super Accelarated Aging Test
the test results of example 3 are as follows:
Wet Environmental Super Accelarated Aging Test
Note：
Rating coated metal color change：
10-----No Change
9-----Very slight changed
8-----Slight changed
6-----Moderate changed
4-----Noticeable changed
2-----Severe changed
from the results, the example 1 has good wear resistance and corrosion resistance, but the example 3 has better performance, which shows that the HBOPS-Na, diethylenetriamine and tetraethylenepentamine can further improve the performance of the imitation shallow gold plating layer, and also proves that the cyanide-free electroplating solution has ideal coloring effect, high color fastness, corrosion resistance, friction resistance and better plating layer performance.
Variations and modifications to the above would be obvious to persons skilled in the art to which the invention pertains from the foregoing description and teachings. Therefore, the invention is not limited to the specific embodiments disclosed and described above, but some modifications and changes of the invention should be also included in the scope of the claims of the invention. In addition, although specific terms are used in the present specification, these terms are for convenience of description only and do not limit the present invention in any way.
Claims (10)
1. An electroless cyanide plating solution for preparing a shallow gold-imitated slide fastener, characterized in that only copper salt and tin salt are used as main salts, comprising:
copper salt of 0.15-0.3mol/L in terms of copper content and tin salt of 0.04-0.1mol/L in terms of tin content;
potassium pyrophosphate is used as a main complexing agent, and the concentration is 250-350g/L;
the auxiliary complexing agents are first auxiliary complexing agents, second auxiliary complexing agents and third auxiliary complexing agents, wherein the first auxiliary complexing agents are citrate, the second auxiliary complexing agents are nitrilotriacetic acid, and the third auxiliary complexing agents are one or more of ethylenediamine, ethylenediamine tetraacetic acid disodium salt, ethylenediamine tetraacetic acid tetrasodium salt and ethylenediamine tetramethylene phosphonic acid;
at least one brightening agent is set as a first brightening agent, and the first brightening agent is a mercaptoazole organic matter.
2. The cyanide-free plating bath according to claim 1, further comprising a second brightening agent and a third brightening agent,
the second brightening agent is butynol ether propane sulfonate, the CAS number is 90268-78-3, and the concentration is 15-25ppm;
the third brightening agent is one or more than two polyethylene polyamines.
3. The cyanide-free plating bath according to claim 2, wherein the third brightening agent is a combination of diethylenetriamine and tetraethylenepentamine, the concentration of diethylenetriamine is 0.01-0.03ml/L, and the concentration of tetraethylenepentamine is 0.03-0.05ml/L.
4. The cyanide-free plating bath according to claim 1, further comprising a second brightening agent and a third brightening agent,
the second brightening agent is diethyl propioamine and diphenyl sulphonimide addition product with the concentration of 50-80ppm, and the diethyl propioamine and diphenyl sulphonimide addition product adopts PEA diethyl propioamine and diphenyl sulphonimide addition product produced by Shanghai Shanxin chemical technology Co., ltd;
the third brightening agent is modified methyl trigonelline with the concentration of 5-20ppm, and the modified methyl trigonelline adopts HOP-A modified methyl trigonelline produced by Shanghai Shanxin chemical technology Co., ltd.
5. The cyanide-free plating bath according to claim 3 or 4, wherein the mercaptoazole organic compound is 1- (2-dimethylaminoethyl) -1H-5-mercapto-tetrazole, CAS No. 61607 to 68 to 9, and the concentration is 0.05 to 0.1g/L.
6. The cyanide-free plating bath according to claim 5, wherein the citrate is potassium citrate or ammonium citrate at a concentration of 10 to 50g/L;
the concentration of the nitrilotriacetic acid is 5-10g/L;
the third auxiliary complexing agent is ethylenediamine tetramethylene phosphonic acid, and the concentration is 2-5g/L.
7. An electroplating method for preparing a shallow gold-imitated slide fastener, which is characterized in that the electroplating is carried out by adopting the cyanide-free electroplating solution according to any one of claims 1 to 6, the pH is controlled to be 8.5-9.5, and the electroplating temperature is 25-45 ℃.
8. The method according to claim 7, wherein the main salts are copper salts of 0.15 to 0.25mol/L in terms of copper content and tin salts of 0.04 to 0.08mol/L in terms of tin content, the pH is controlled to 8.8 to 9.3, and the current density is set to 0.2 to 1.5A/dm when the plating is performed by the barrel plating process 2 The rotating speed is 6-10r/min, and the barrel plating time is 5-60min;
or, when plating is carried out by adopting the hanging plating process, the main salt is copper salt with the copper content of 0.2-0.3mol/L and tin salt with the tin content of 0.05-0.1mol/L, the pH is controlled to 8.8-9.3, and the current density is set to 0.1-2A/dm 2 The duration of the plating is 5-30min.
9. An imitation shallow gold composite plating layer, characterized in that an alkali copper plating layer, an acid copper plating layer and an imitation shallow gold plating layer are sequentially arranged outwards from the surface of a substrate to be plated, and the imitation shallow gold plating layer is formed by electroplating the cyanide-free electroplating solution according to any one of claims 1 to 6.
10. The imitation shallow gold composite plating layer of claim 9, wherein the imitation shallow gold plating layer comprises the following components in percentage by weight:
Cu 83-87wt％
Sn 10-14wt％
C 2-4wt％。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310997574.XA CN116988110A (en) | 2023-08-09 | 2023-08-09 | Cyanide-free electroplating solution for preparing imitated shallow gold zipper, electroplating method and composite coating thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310997574.XA CN116988110A (en) | 2023-08-09 | 2023-08-09 | Cyanide-free electroplating solution for preparing imitated shallow gold zipper, electroplating method and composite coating thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116988110A true CN116988110A (en) | 2023-11-03 |
Family
ID=88524542
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310997574.XA Pending CN116988110A (en) | 2023-08-09 | 2023-08-09 | Cyanide-free electroplating solution for preparing imitated shallow gold zipper, electroplating method and composite coating thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116988110A (en) |
-
2023
- 2023-08-09 CN CN202310997574.XA patent/CN116988110A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CA2159268C (en) | Alkaline zinc and zinc alloy electroplating baths and processes | |
| CA2883815C (en) | Plating solution and plating process for multi-layer cyanide-free plating copper-tin alloy coating, and coins made by the process | |
| JPH05271980A (en) | Palladium-nickel alloy plating liquid | |
| CN102953094B (en) | Semi-bright nickel electroplating solution additive, semi-bright nickel electroplating solution and semi-bright nickel electroplating method | |
| US2686756A (en) | Chromium plating | |
| US4299671A (en) | Bath composition and method for electrodepositing cobalt-zinc alloys simulating a chromium plating | |
| CN116988110A (en) | Cyanide-free electroplating solution for preparing imitated shallow gold zipper, electroplating method and composite coating thereof | |
| CN112410833B (en) | Cyanide-free copper plating brightener and preparation method and application thereof | |
| Narasimhamurthy et al. | Electrodeposition of Zn-Ni Alloy from an alkaline sulphate bath containing triethanolamine and mercaptopyridine | |
| CN110785516A (en) | Nickel electroplating bath for depositing decorative nickel coatings on substrates | |
| CA1062649A (en) | Electrodeposition of tin-containing alloys and bath therefor | |
| CN104233401A (en) | Electroplating preparation method for Cu-Co alloy | |
| CN117512715A (en) | Cyanide-free electroplating solution capable of forming tea golden coating, electroplating method thereof and composite coating | |
| CN111270276A (en) | Flash galvanizing plating solution and preparation method thereof and flash galvanizing method | |
| CN118256971A (en) | Cyanide-free silver-imitation electroplating solution, electroplating method thereof and composite plating layer | |
| CN110129842A (en) | A kind of compound cyanide-free gold electroplating plating solution preparation and gold process is electroplated using its | |
| CN114836801B (en) | Multilayer electroplating process of beryllium bronze elastic device | |
| RU2377344C1 (en) | Electrolyte and method to apply tin-cobalt alloy coats | |
| CN115747903B (en) | Corrosion self-adaptive gradient coating and preparation method thereof | |
| JPH06240490A (en) | Corrosion resistant chromium plating | |
| CN115182009B (en) | Bright nickel-tungsten alloy plating solution and preparation process of corrosion-resistant multilayer plating layer | |
| CN107630240A (en) | Electroplate liquid of steel and iron parts cyanideless electro-plating tin bronze and preparation method thereof and electro-plating method | |
| US2799633A (en) | Method and electrolyte for producing bright gold | |
| Zhu | Study on the electrodeposited Au-Co alloy coating | |
| CN106521579A (en) | Cyanide-free alkaline low-tin copper-tin alloy electroplating liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |