CN104047037A - Hardener - Google Patents
Hardener Download PDFInfo
- Publication number
- CN104047037A CN104047037A CN201410268462.1A CN201410268462A CN104047037A CN 104047037 A CN104047037 A CN 104047037A CN 201410268462 A CN201410268462 A CN 201410268462A CN 104047037 A CN104047037 A CN 104047037A
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- CN
- China
- Prior art keywords
- gold
- salt
- stiffening agent
- product
- liquid
- 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.)
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Links
- 239000004848 polyfunctional curative Substances 0.000 title abstract 4
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- 125000003748 selenium group Chemical class *[Se]* 0.000 claims abstract description 15
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000008139 complexing agent Substances 0.000 claims abstract description 9
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 3
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- 239000003351 stiffener Substances 0.000 claims description 56
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical group [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 11
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- 239000011591 potassium Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 9
- 150000003016 phosphoric acids Chemical class 0.000 claims description 9
- 235000011009 potassium phosphates Nutrition 0.000 claims description 8
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 claims description 6
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 6
- 229940093916 potassium phosphate Drugs 0.000 claims description 6
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 6
- BVTBRVFYZUCAKH-UHFFFAOYSA-L disodium selenite Chemical compound [Na+].[Na+].[O-][Se]([O-])=O BVTBRVFYZUCAKH-UHFFFAOYSA-L 0.000 claims description 5
- 239000011781 sodium selenite Substances 0.000 claims description 5
- 229960001471 sodium selenite Drugs 0.000 claims description 5
- 235000015921 sodium selenite Nutrition 0.000 claims description 5
- AFWAHDXCIBPFNW-UHFFFAOYSA-J sodium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Na+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O AFWAHDXCIBPFNW-UHFFFAOYSA-J 0.000 claims description 5
- BEGBSFPALGFMJI-UHFFFAOYSA-N ethene;sodium Chemical group [Na].C=C BEGBSFPALGFMJI-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- 229940026189 antimony potassium tartrate Drugs 0.000 claims description 3
- WBTCZEPSIIFINA-MSFWTACDSA-J dipotassium;antimony(3+);(2r,3r)-2,3-dioxidobutanedioate;trihydrate Chemical compound O.O.O.[K+].[K+].[Sb+3].[Sb+3].[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O.[O-]C(=O)[C@H]([O-])[C@@H]([O-])C([O-])=O WBTCZEPSIIFINA-MSFWTACDSA-J 0.000 claims description 3
- RNGFNLJMTFPHBS-UHFFFAOYSA-L dipotassium;selenite Chemical compound [K+].[K+].[O-][Se]([O-])=O RNGFNLJMTFPHBS-UHFFFAOYSA-L 0.000 claims description 3
- BHZRJJOHZFYXTO-UHFFFAOYSA-L potassium sulfite Chemical group [K+].[K+].[O-]S([O-])=O BHZRJJOHZFYXTO-UHFFFAOYSA-L 0.000 claims description 3
- 235000019252 potassium sulphite Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 3
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 3
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 claims description 3
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- NSBGJRFJIJFMGW-UHFFFAOYSA-N trisodium;stiborate Chemical compound [Na+].[Na+].[Na+].[O-][Sb]([O-])([O-])=O NSBGJRFJIJFMGW-UHFFFAOYSA-N 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- 239000007788 liquid Substances 0.000 abstract description 132
- 239000010931 gold Substances 0.000 abstract description 115
- 229910052737 gold Inorganic materials 0.000 abstract description 115
- 238000009713 electroplating Methods 0.000 abstract description 109
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 100
- 238000000034 method Methods 0.000 abstract description 59
- 230000008569 process Effects 0.000 abstract description 15
- -1 hydrophosphate Chemical compound 0.000 abstract description 9
- 239000000126 substance Substances 0.000 abstract description 4
- 229910052783 alkali metal Inorganic materials 0.000 abstract 1
- 150000001340 alkali metals Chemical group 0.000 abstract 1
- 238000007747 plating Methods 0.000 description 58
- 229910000906 Bronze Inorganic materials 0.000 description 50
- 239000010974 bronze Substances 0.000 description 50
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 50
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 37
- 238000002844 melting Methods 0.000 description 27
- 230000008018 melting Effects 0.000 description 27
- 229910052802 copper Inorganic materials 0.000 description 25
- 239000010949 copper Substances 0.000 description 25
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 24
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 24
- 230000015572 biosynthetic process Effects 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 239000000463 material Substances 0.000 description 14
- JEOOVNWNJKBHRG-UHFFFAOYSA-N [Na+].[S--].[S--].[Au+3] Chemical compound [Na+].[S--].[S--].[Au+3] JEOOVNWNJKBHRG-UHFFFAOYSA-N 0.000 description 11
- JCDVTZPJEWWGHU-UHFFFAOYSA-N gold sulfurous acid Chemical compound [Au].S(O)(O)=O JCDVTZPJEWWGHU-UHFFFAOYSA-N 0.000 description 9
- 229910001152 Bi alloy Inorganic materials 0.000 description 8
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 8
- 150000002343 gold Chemical class 0.000 description 8
- 229910017604 nitric acid Inorganic materials 0.000 description 8
- FLBXDQRAKXWJSF-UHFFFAOYSA-N [K].[Au].S(O)(O)=O Chemical compound [K].[Au].S(O)(O)=O FLBXDQRAKXWJSF-UHFFFAOYSA-N 0.000 description 7
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 6
- 238000003556 assay Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 229920002379 silicone rubber Polymers 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- JWVAUCBYEDDGAD-UHFFFAOYSA-N bismuth tin Chemical compound [Sn].[Bi] JWVAUCBYEDDGAD-UHFFFAOYSA-N 0.000 description 4
- 238000010106 rotational casting Methods 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GKSYFVIEBZCLEQ-UHFFFAOYSA-N OS(O)=O.N.[Au+3] Chemical compound OS(O)=O.N.[Au+3] GKSYFVIEBZCLEQ-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910052797 bismuth Inorganic materials 0.000 description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 235000011008 sodium phosphates Nutrition 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- MKYLOMHWHWEFCT-UHFFFAOYSA-N Manthidine Natural products C1C2=CC=3OCOC=3C=C2C2C3=CC(OC)C(O)CC3N1C2 MKYLOMHWHWEFCT-UHFFFAOYSA-N 0.000 description 1
- SNFRINMTRPQQLE-JQWAAABSSA-N Montanin Chemical compound O[C@H]([C@@]1(CO)O[C@H]1[C@H]1[C@H]2O3)[C@]4(O)C(=O)C(C)=C[C@H]4[C@]11OC3(CCCCCCCCCCC)O[C@@]2(C(C)=C)C[C@H]1C SNFRINMTRPQQLE-JQWAAABSSA-N 0.000 description 1
- SNFRINMTRPQQLE-OFGNMXNXSA-N Montanin Natural products O=C1[C@@]2(O)[C@@H](O)[C@@]3(CO)O[C@H]3[C@@H]3[C@H]4[C@@]5(C(=C)C)O[C@](CCCCCCCCCCC)(O4)O[C@@]3([C@H](C)C5)[C@@H]2C=C1C SNFRINMTRPQQLE-OFGNMXNXSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- QTZPBQMTXNEKRX-UHFFFAOYSA-N Voacristine pseudoindoxyl Natural products N1C2=CC=C(OC)C=C2C(=O)C21CCN(C1)C3C(C(C)O)CC1CC32C(=O)OC QTZPBQMTXNEKRX-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 235000013871 bee wax Nutrition 0.000 description 1
- 239000012166 beeswax Substances 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 235000019994 cava Nutrition 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 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
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 229960005215 dichloroacetic acid Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000012184 mineral wax Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000012169 petroleum derived wax Substances 0.000 description 1
- 235000019381 petroleum wax Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Substances [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- LUPNKHXLFSSUGS-UHFFFAOYSA-M sodium;2,2-dichloroacetate Chemical compound [Na+].[O-]C(=O)C(Cl)Cl LUPNKHXLFSSUGS-UHFFFAOYSA-M 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Abstract
The invention provides a hardener which comprises phosphate, hydrophosphate, sulfite, antimonic salt and/or selenium salt and a complexing agent, wherein the sulfite is alkali metal sulfite. The hardener obtained by match of the substances for use in electroplating to prepare a gold product not only can remarkably improve the stability of the electroplate liquid so as to make the electroplating process be stably processed, but also further can improve the hardness of the gold product, so that the hardener has an extremely good industrial application prospect.
Description
Technical field
The present invention relates to a kind of stiffening agent.
Background technology
Along with the raising day by day of people's living standard, gold product is more and more subject to consumers in general's favor.At present, the gold product of producing by the mode of electroplating is more and more.Wherein, in electroplating process, electroplate liquid used is mainly the solution that contains potassium auric cyanide.Yet potassium auric cyanide belongs to highly toxic substance, not only in the production process of gold product, can to work the mischief to the healthy of producer, and to produce the pollution of waste liquid to environment in order reducing, also need to spend a large amount of expenses with process for producing waste liquid.
In order to overcome the above-mentioned defect that contains potassium auric cyanide electroplate liquid, in recent years, also the solution that has Some Enterprises to adopt to contain sulfurous acid gold liquid (sulfurous acid gold potassium and/or gold sodium sulfide) substitute contain potassium auric cyanide solution as electroplate liquid, to prepare gold product.Yet, due to the less stable of sulfurous acid gold potassium and gold sodium sulfide, in electroplating process, very easily separate out, thereby affected the stability of electroplating process and the performance of gold product.In addition, the hardness of the gold product that sulfurous acid gold potassium and/or gold sodium sulfide obtain as electroplate liquid of usining is lower, can make like this to make gold product that purity is higher particularly during thousand pure golds, easily deforms, caves in, and in use very easily damages.The hardness that how to improve gold product has become the technical problem that current yellow Manufacturing Technology is needed solution badly.
Summary of the invention
The object of the invention is provides a kind of stiffening agent that is conducive to improve gold product hardness in order to overcome existing gold product hardness compared with low defect.
Particularly, the invention provides a kind of stiffening agent, wherein, described stiffening agent contains phosphoric acid salt, hydrophosphate, sulphite, stiffening agent and complexing agent, and described sulphite is alkali sulfite metal-salt.
The present inventor finds by further investigation, above-mentioned several materials are used in conjunction with to the stiffening agent that obtains for electroplating the process of preparing gold product, not only can significantly improve the stability of electroplate liquid, electroplating process is steadily carried out, but also can improve the hardness of gold product, have prospects for commercial application.
A preferred embodiment of the invention, when described stiffening agent is the mixture of antimonic salt and selenium salt, and the weight ratio of described antimonic salt and selenium salt is while being 0.25-1:1, can further improve the hardness of gained gold product.
Other features and advantages of the present invention partly in detail are described the embodiment subsequently.
Accompanying drawing explanation
Accompanying drawing is to be used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is a kind of concrete preparation method of gold product provided by the invention.
Description of reference numerals
10-mandrel; 11-silicon rubber mould; 12-scavenging solution; 13-copper plating bath; 14-electroplate liquid; 15-nickel-plating liquid; 20-hanger.
Embodiment
Below the specific embodiment of the present invention is elaborated.Should be understood that, embodiment described herein only, for description and interpretation the present invention, is not limited to the present invention.
Stiffening agent provided by the invention contains phosphoric acid salt, hydrophosphate, sulphite, antimonic salt and/or selenium salt and complexing agent, and described sulphite is alkali sulfite metal-salt.
The present invention is not particularly limited the content of each component in above-mentioned stiffening agent, for example, the described phosphoric acid salt of relative 100-200 gram, the content of described hydrophosphate can be 50-200 gram, the content of described alkali sulfite metal-salt can be 30-120 gram, the total content of described antimonic salt and selenium salt can be 0.01-2 gram, and the content of described complexing agent can be 0.01-5 gram.Preferably, with respect to the described phosphoric acid salt of 150-200 gram, the content of described hydrophosphate is 80-120 gram, and the content of described alkali sulfite metal-salt is 40-100 gram, and the total content of described antimonic salt and selenium salt is 0.5-1.5 gram, and the content of described complexing agent is 2-5 gram.
According to the present invention, described phosphoric acid salt, hydrophosphate and alkali sulfite metal-salt all can be selected for the routine of this area.For example, described phosphoric acid salt can be potassiumphosphate and/or sodium phosphate.Described hydrophosphate can be selected from one or more in potassium phosphate,monobasic, potassium primary phosphate, disodium-hydrogen and SODIUM PHOSPHATE, MONOBASIC.Described alkali sulfite metal-salt can be potassium sulfite and/or S-WAT.
According to stiffening agent provided by the invention, preferably, described stiffening agent contains antimonic salt and selenium salt simultaneously, can further improve like this hardness of gold product.When described stiffening agent contains antimonic salt and selenium salt simultaneously, the weight ratio of described antimonic salt and selenium salt is particularly preferably 0.25-1:1.In addition, the example of described antimonic salt includes but not limited to: one or more in sodium antimony tartrate, antimonypotassium tartrate, sodium antimonate and potassium antimonate.The example of described selenium salt includes but not limited to: one or more in sodium thiosulfate, seleno potassium sulfate, Sodium Selenite and potassium selenite.
Described complexing agent can variously can form the compound of complexing ion for existing with gold ion, for example, can be selected from one or more in sodium ethylene diamine tetracetate, thiocarbamide and Sulfothiorine.
In concrete use procedure, above-mentioned stiffening agent is joined in the electroplate liquid of preparing gold product, then electroplate.Described electroplate liquid can, for containing cyanogen electroplate liquid (main component that is electroplate liquid is potassium auric cyanide), can be also cyanideless electro-plating liquid (main component that is electroplate liquid is sulfurous acid gold potassium and/or gold sodium sulfide) not only.In other words, stiffening agent provided by the invention not only can improve the hardness by the gold product preparing containing cyanogen electroplate liquid, but also can improve the hardness of the gold product being prepared by cyanideless electro-plating liquid.From the angle of environmental protection, consider, described electroplate liquid is cyanideless electro-plating liquid, wherein contains sulfurous acid gold liquid and above-mentioned stiffening agent.
Described sulfurous acid gold liquid can be for existing various without cyanogen and can electroplate the material that contains sulfite ion and gold ion that obtains gold product, and its specific examples includes but not limited to: one or more in sulfurous acid gold potassium, gold sodium sulfide and sulfurous acid gold ammonium.Yet because described sulfurous acid gold ammonium can produce poisonous ammonia in electroplating process, therefore, described sulfurous acid gold liquid is particularly preferably sulfurous acid gold potassium and/or gold sodium sulfide.
The present invention is not particularly limited the consumption of described cyanideless electro-plating liquid Central Asia auric sulfate liquid, for example, in described cyanideless electro-plating liquid, the weight ratio of phosphatic content in the content of described sulfurous acid gold liquid of gold element and described stiffening agent of take is 10:100-200, is preferably 10:150-200.
As a rule, described cyanideless electro-plating liquid also contains water.The consumption of described water can be selected for the routine of this area, as long as can guarantee electroplating process smoothly, for example, the consumption of described water can be benchmark so that take the described cyanideless electro-plating liquid of 1L, the content of described sulfurous acid gold liquid of gold element of take can be 8-20g, is preferably 9-12g.
Main improvements of the present invention have been to adopt a kind of new stiffening agent, can be same as the prior art and adopt the cyanideless electro-plating liquid that contains this stiffening agent and/or have cyanogen electroplate liquid to electroplate the concrete grammar of the described gold product of formation.
According to a kind of embodiment of the present invention, the preparation method of described gold product comprises:
In the mandrel being formed by the low melting material Gold plated Layer that powers on;
Formation arrives the hole of described mandrel through electrolytic coating, and described mandrel is melted to by described hole, discharge; Wherein, in the power on method of Gold plated Layer of described mandrel, comprise and take described mandrel as negative electrode, at the cyanideless electro-plating liquid that contains above-mentioned stiffening agent and/or in having cyanogen electroplate liquid, electroplate.
Described mandrel mainly plays the effect of forming mould, thereby not only can obtain the gold product of different shape, and the gold product obtaining after described mandrel is removed is hollow structure, thereby can show gold consumption used while reducing the gold product of producing same size, reduce production cost.In the present invention, described " low melting point " refers to that fusing point, not higher than 200 ℃, is preferably 60-130 ℃.The material of the mandrel of described low melting point can be sn-bi alloy and/or wax.Wherein, in described sn-bi alloy, the weight ratio of described tin and bismuth can be 0.5-1.5:1.The example of described wax includes but not limited to: one or more in beeswax, mineral wax (as montanin wax, ceresine, paraffin) and petroleum wax etc.The size and shape of the gold product that the size and shape of described mandrel can obtain as required carries out choose reasonable, and therefore not to repeat here.
In addition, because described sn-bi alloy is when the high temperature stripping, can corrode gold, therefore, before described mandrel powers on Gold plated Layer, preferably first on described mandrel, electroplate the first bronze medal layer, and then on described the first bronze medal layer, electroplate described gold layer, and after described mandrel being melted and discharge, remove described the first bronze medal layer.In addition,, as the optional mode of another kind, described mandrel also can be after electroplating the first bronze medal layer, before electrogilding layer, remove.While removing described mandrel, can adopt the discharge of the auxiliary described low melting material of vibration.
According to the present invention, when described mandrel or the first bronze medal layer power on Gold plated Layer, the condition of described plating can comprise conventionally: the temperature of electroplate liquid is 40-60 ℃, and the pH value of electroplate liquid is 6-8, and cathode current density is 0.1-1A/dm
2, electroplating time is 8-20 hour.In addition, the thickness of the described gold layer of formation can be 50-150 μ m, is preferably 100-130 μ m.The method that the pH value of described electroplate liquid is controlled in above-mentioned scope is known to the skilled person, and for example, adds acidic substance or alkaline matter in described electroplate liquid in the past.Described acidic substance are such as thinking one or more in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid etc.Described alkaline matter is such as thinking one or more in sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood, ammoniacal liquor etc.The consumption of above-mentioned acidic substance and alkaline matter is to be adjusted to the pH value of described electroplate liquid in above-mentioned scope and to be as the criterion, and therefore not to repeat here.
According to the present invention; before the preparation method of described hard gold is also included in and forms described hole; first on described gold layer, electroplate successively the second bronze medal layer and nickel dam; and after described mandrel being melted and discharge, remove described the second bronze medal layer and nickel dam; can prevent like this gold layer " dissolving ", thereby play a protective role.In the concrete preparation process of described hard gold, the method that forms described the first bronze medal layer generally includes described low melting material (as sn-bi alloy and/or wax, when being wax, conventionally need on the surface of wax, be coated with conductive oil) as negative electrode, using phosphorized copper as anode, in copper-contained electroplating liquid, electroplate.The method that forms described the second bronze medal layer generally includes using the goods that are electroplate with gold layer as negative electrode, using phosphorized copper as anode, containing in copper electrolyte, is electroplating.The copper-contained electroplating liquid adopting in the process of above-mentioned twice copper electroplating layer can be selected for the routine of this area, and therefore not to repeat here.
The plating condition that forms described the first bronze medal layer can be identical or different with the plating condition that forms described the second bronze medal layer, and comprise independently of one another: the temperature of electroplate liquid can be 15-35 ℃, the pH value of electroplate liquid can be 0.1-0.5, and cathode current density can be 0.5-5A/dm
2, electroplating time can be 30-60 minute.In addition, the thickness of the described first bronze medal layer of formation can be 40-60 micron, is preferably 45-55 micron; The thickness of described the second bronze medal layer forming can be 40-60 micron, is preferably 45-55 micron.Described the first bronze medal layer is preferably bright and smooth, and it is also bright and smooth can making so the follow-up gold layer obtaining.
According to the present invention, the method that forms described nickel dam generally includes using the goods that are electroplate with the second bronze medal layer as negative electrode, using metallic nickel as anode, containing in nickel electrolyte, is electroplating.Described can be the routine selection of this area containing nickel electrolyte, and therefore not to repeat here.The plating condition that forms described nickel dam can comprise conventionally: the temperature of electroplate liquid is 35-50 ℃, and the pH value of electroplate liquid is 3.5-5, and cathode current density is 2-4A/dm
2, electroplating time is 10-20 minute.In addition, the thickness of the described nickel dam of formation can be 5-20 micron, is preferably 5-10 micron.
In addition, can adopt existing the whole bag of tricks to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam, for example, can, after described mandrel is removed, the gold prefabricated component of acquisition be immersed in dilute nitric acid solution.The concentration of described dilute nitric acid solution can be for example 5-10mol/L.
According to a kind of embodiment of the present invention, as shown in Figure 1, the preparation method of described hard gold comprises: the mandrel 10 that rotational casting is formed by low melting point alloy in silicon rubber mould 11, again described mandrel 10 is placed in cylinder to remove thorn or any joint line, then mandrel 10 is connected on the hanger 20 of plating rack, and cleans in electrolysis and/or ultrasonic cleaning solution 12.If the fusing point of mandrel 10, lower than the temperature that forms the electroplate liquid of gold layer, need to form the first bronze medal layer on mandrel 10, that is, clean mandrel 10 is transferred to the electroplating of going forward side by side in copper plating bath 13, to form the first bronze medal layer on the surface at mandrel 10.Described the first bronze medal layer should be bright and smooth, thereby make the gold layer of follow-up formation, is also bright and smooth.(be electroplate with the first bronze medal layer or be not electroplate with the first bronze medal layer) mandrel 10 is placed in to have cyanogen or the cyanideless electro-plating liquid 14 that contain stiffening agent and electroplates, form gold layer, then the product obtaining is placed in to copper plating bath 13 and electroplates, to form the second bronze medal layer on gold layer.After forming the second bronze medal layer, the product obtaining is placed in to nickel-plating liquid 15 and electroplates, to form nickel dam on the second bronze medal layer.After completing plating, the product obtaining is removed from fixture 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 ℃, mandrel 10 fusings of low melting point are also flowed out from hole.Then by removing product after the mandrel 10 of low melting point, be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam again, only retain gold layer, thereby obtain gold product.
Above-mentioned each plating step all can be implemented by traditional way, for example, can will comprise that described mandrel 10 is electrically connected to the negative electrode of direct supply by hanger 20 and inserts in corresponding electroplate liquid with the product of the associated metal level forming afterwards, anode is connected to the positive terminal of direct supply and inserts in corresponding electroplate liquid.
In addition, the preparation method of described hard gold also comprises and adopts the modes such as welding, sandblast and polishing to process to become jewelry piece by removing residual low melting material and the gold product after the first bronze medal layer, the second bronze medal layer and nickel dam.
Below will describe the present invention by embodiment.
Embodiment 1
This embodiment is for illustrating the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
At 60 ℃, 200 grams of potassiumphosphates, 100 grams of potassium phosphate,monobasics, 50 grams of S-WATs, 0.5 gram of sodium antimony tartrate, 0.5 gram of Sodium Selenite and 5 grams of sodium ethylene diamine tetracetates are dissolved in 1L water, obtain stiffening agent Y1.At 60 ℃, by take the gold sodium sulfide that gold element consumption is 10 grams, mix with stiffening agent Y1, obtain cyanideless electro-plating liquid Z1.By cyclic voltammetry, cathodic polarization curve and cathode efficiency method, measure stability and the electroconductibility of cyanideless electro-plating liquid Z1.Result shows, the stability of cyanideless electro-plating liquid Z1 is high, only has very a small amount of gold ion automatic reduction, and electroconductibility is very good, and cathode efficiency maintains more than 90%.
Embodiment 2
This embodiment is for illustrating the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
At 40 ℃, 180 grams of sodium phosphates, 80 grams of disodium-hydrogens, 40 grams of potassium sulfites, 0.2 gram of antimonypotassium tartrate, 0.3 gram of sodium thiosulfate and 2 grams of thiocarbamides are dissolved in 1L water, obtain stiffening agent Y2.At 60 ℃, by take the sulfurous acid gold potassium that gold element consumption is 10 grams, mix with stiffening agent Y2, obtain cyanideless electro-plating liquid Z2.According to the method for embodiment 1, stability and the electroconductibility of cyanideless electro-plating liquid Z2 are tested.Result shows, the stability of cyanideless electro-plating liquid Z2 is high, there is no gold ion automatic reduction, and electroconductibility is better but lower than cyanideless electro-plating liquid Z1, and cathode efficiency maintains more than 90%.
Embodiment 3
This embodiment is for illustrating the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
At 45 ℃, 150 grams of potassiumphosphates, 120 grams of potassium primary phosphates, 100 grams of S-WATs, 0.5 gram of sodium antimonate, 1 gram of potassium selenite and 5 grams of Sulfothiorine are dissolved in 1L water, obtain stiffening agent Y3.At 60 ℃, by take the gold sodium sulfide that gold element consumption is 10 grams, mix with stiffening agent Y3, obtain cyanideless electro-plating liquid Z3.According to the method for embodiment 1, stability and the electroconductibility of cyanideless electro-plating liquid Z3 are tested.Result shows, cyanideless electro-plating liquid Z3 stability is very high, there is no gold ion automatic reduction, and electroconductibility is very good, and cathode efficiency maintains more than 90%.
Embodiment 4
This embodiment is for illustrating the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
According to the method for embodiment 1, prepare cyanideless electro-plating liquid, different, described sodium antimony tartrate substitutes with the Sodium Selenite of identical weight part, obtains stiffening agent Y4 and cyanideless electro-plating liquid Z4.According to the method for embodiment 1, stability and the electroconductibility of cyanideless electro-plating liquid Z4 are tested.Result shows, the stability of cyanideless electro-plating liquid Z4 is high, only has very a small amount of gold ion automatic reduction, and electroconductibility is better but lower than cyanideless electro-plating liquid Z1, and cathode efficiency maintains more than 90%.
Embodiment 5
This embodiment is for illustrating stiffening agent provided by the invention and the preparation method who has cyanogen electroplate liquid.
According to the method for embodiment 1, be prepared with cyanogen electroplate liquid, different, the potassium auric cyanide that the gold sodium sulfide that the gold element consumption of take is 10 grams is 10 grams in order to gold element meter consumption substitutes, and has obtained cyanogen electroplate liquid Z5.According to the method for embodiment 1 to having stability and the electroconductibility of cyanogen electroplate liquid Z5 to test.Result shows have the stability of cyanogen electroplate liquid Z5 high, there is no gold ion automatic reduction, and electroconductibility is better but higher than cyanideless electro-plating liquid Z1, and cathode efficiency maintains more than 95%.
Comparative example 1
This comparative example is for illustrating the preparation method of stiffening agent and the cyanideless electro-plating liquid of reference.
According to the method for embodiment 4, prepare stiffening agent and cyanideless electro-plating liquid, different, described potassiumphosphate substitutes with the potassium phosphate,monobasic of identical weight part, obtains reference stiffening agent DY1 and cyanideless electro-plating liquid DZ1.According to the method for embodiment 1, stability and the electroconductibility of reference cyanideless electro-plating liquid DZ1 are tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ1 is low, poorly conductive, and cathode current density only can reach 80%.
Comparative example 2
This comparative example is for illustrating the preparation method of stiffening agent and the cyanideless electro-plating liquid of reference.
According to the method for embodiment 4, prepare modification electroplate liquid and cyanideless electro-plating liquid, different, described potassium phosphate,monobasic substitutes with the potassiumphosphate of identical weight part, obtains reference stiffening agent DY2 and cyanideless electro-plating liquid DZ2.According to the method for embodiment 1, the stability of reference cyanideless electro-plating liquid DZ2 is tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ2 is low, poorly conductive, and cathode current density only can reach 80%.
Comparative example 3
This comparative example is for illustrating the preparation method of stiffening agent and the cyanideless electro-plating liquid of reference.
According to the method for comparative example 1, prepare stiffening agent and cyanideless electro-plating liquid, different, described potassium phosphate,monobasic substitutes with the gold sodium sulfide of identical weight part, obtains reference stiffening agent and cyanideless electro-plating liquid DZ3.According to the method for embodiment 1, stability and the electroconductibility of reference cyanideless electro-plating liquid DZ3 are tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ3 is low, poorly conductive, and cathode current density only can reach 75%.
Comparative example 4
This comparative example is for illustrating the preparation method of the cyanideless electro-plating liquid of reference.
According to the method for embodiment 1, prepare cyanideless electro-plating liquid, different is, potassiumphosphate in cyanideless electro-plating liquid, potassium phosphate,monobasic, S-WAT, sodium antimony tartrate, Sodium Selenite and sodium ethylene diamine tetracetate are all substituted with the gold sodium sulfide of identical weight part, obtain reference cyanideless electro-plating liquid DZ4.According to the method for embodiment 1, stability and the electroconductibility of reference cyanideless electro-plating liquid DZ4 are tested.Result shows, the stability extreme difference of reference cyanideless electro-plating liquid DZ4, and poorly conductive, cathode current density only can reach 60%.
Application Example 1
As shown in Figure 1, in silicon rubber mould 11, by low melting point tin bismuth alloy, (weight ratio of tin and bismuth is 52:48 to rotational casting, the mandrel 10 forming down together), again described mandrel 10 is placed in cylinder to remove thorn or any joint line, then mandrel 10 is connected on the hanger 20 of plating rack, and cleans in ultrasonic cleaning solution 12.Then clean mandrel 10 is transferred to the copper plating bath 13 (mixture of the copper sulfate of 200g/L and the sulfuric acid of 70g/L, lower with) in the electroplating of going forward side by side, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 ℃, the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the first bronze medal layer of 50 microns.Then the mandrel 10 that is electroplate with the first bronze medal layer is placed in to the cyanideless electro-plating liquid Z1 that contains sulfurous acid gold liquid and electroplates, wherein, plating condition comprises that the temperature of cyanideless electro-plating liquid Z1 is 60 ℃, and the pH value of cyanideless electro-plating liquid Z1 is 8, and cathode current density is 0.8A/dm
2, electroplating time is 8 hours, formation thickness is the gold layer of 130 microns.Then the product that is electroplate with gold layer is placed in to copper plating bath 13 and electroplates, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 ℃, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the second bronze medal layer of 50 microns.Then the product that is electroplate with the second bronze medal layer is placed in to the nickel-plating liquid 15 (mixture of the single nickel salt of the boric acid of 20g/L, the sodium sulfate of 100g/L and 100g/L, down together), electroplate, wherein, plating condition comprises that the temperature of nickel-plating liquid 15 is 45 ℃, the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, formation thickness is the nickel dam of 10 microns.After completing plating, the product obtaining is removed from hanger 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 ℃, axle center 10 fusings of low melting point are also flowed out from hole.Then by removing product after the axle center 10 of low melting point, be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam again, thereby obtain only retaining the gold product of gold layer.Through sclerometer calibrating, the hardness of this gold product is 130Hv, and golden purity is 99.96% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Application Example 2
As shown in Figure 1, the mandrel 10 that rotational casting is formed by low melting point tin bismuth alloy in silicon rubber mould 11, again described mandrel 10 is placed in cylinder and stings or any joint line to remove, then mandrel 10 is connected on the hanger 20 of plating rack, and clean in ultrasonic cleaning solution 12.Then clean mandrel 10 is transferred to the electroplating of going forward side by side in copper plating bath 13, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 ℃, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the first bronze medal layer of 50 microns.Then the mandrel 10 that is electroplate with the first bronze medal layer is placed in to the cyanideless electro-plating liquid Z2 that contains sulfurous acid gold liquid and electroplates, wherein, plating condition comprises that the temperature of cyanideless electro-plating liquid Z2 is 40 ℃, and the pH value of cyanideless electro-plating liquid Z2 is 6, and cathode current density is 0.2A/dm
2, electroplating time is 16 hours, formation thickness is the gold layer of 100 microns.Then the product that is electroplate with gold layer is placed in to copper plating bath 13 and electroplates, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 ℃, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the second bronze medal layer of 50 microns.Then the product that is electroplate with the second bronze medal layer is placed in to nickel-plating liquid 15 and electroplates, wherein, plating condition comprises that the temperature of nickel-plating liquid 15 is 45 ℃, and the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, formation thickness is the nickel dam of 10 microns.After completing plating, the product obtaining is removed from hanger 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 ℃, axle center 10 fusings of low melting point are also flowed out from hole.Then by removing product after the axle center 10 of low melting point, be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam again, thereby obtain only retaining the gold product of gold layer.Through sclerometer, assay, the hardness of this gold product is 135Hv, and golden purity is 99.92% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Application Example 3
As shown in Figure 1, the mandrel 10 that rotational casting is formed by low melting point tin bismuth alloy in silicon rubber mould 11, again described mandrel 10 is placed in cylinder and stings or any joint line to remove, then mandrel 10 is connected on the hanger 20 of plating rack, and clean in ultrasonic cleaning solution 12.Then clean mandrel 10 is transferred to the electroplating of going forward side by side in copper plating bath 13, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 ℃, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the first bronze medal layer of 50 microns.Then the mandrel 10 that is electroplate with the first bronze medal layer is placed in to the cyanideless electro-plating liquid Z3 that contains sulfurous acid gold liquid and electroplates, wherein, plating condition comprises that the temperature of cyanideless electro-plating liquid Z3 is 45 ℃, and the pH value of cyanideless electro-plating liquid Z3 is 7, and cathode current density is 0.3A/dm
2, electroplating time is 12 hours, formation thickness is the gold layer of 120 microns.Then the product that is electroplate with gold layer is placed in to copper plating bath 13 and electroplates, wherein, plating condition comprises that the temperature of copper plating bath 13 is 25 ℃, and the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, formation thickness is the second bronze medal layer of 50 microns.Then the product that is electroplate with the second bronze medal layer is placed in to nickel-plating liquid 15 and electroplates, wherein, plating condition comprises that the temperature of nickel-plating liquid 15 is 45 ℃, and the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, formation thickness is the nickel dam of 10 microns.After completing plating, the product obtaining is removed from hanger 20, and bored in place the plural hole that reaches mandrel 10 centers through each electrolytic coating.Then product is put into stove to be heated approximately 200 ℃, axle center 10 fusings of low melting point are also flowed out from hole.Then by removing product after the axle center 10 of low melting point, be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer, the second bronze medal layer and nickel dam again, thereby obtain only retaining the gold product of gold layer.Through sclerometer, assay, the hardness of this gold product is 145Hv, and golden purity is 99.95% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Application Example 4
According to the method for embodiment 1, electroplate gold and carry out the preparation of hard gold, different, described cyanideless electro-plating liquid Z1 substitutes with cyanideless electro-plating liquid Z4, obtains only retaining the gold product of gold layer.Through sclerometer calibrating, the hardness of this gold product is 102Hv, and golden purity is 99.94% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Application Example 5
According to the method for embodiment 4, electroplate gold and carry out the preparation of hard gold, different is, in preparation process, do not comprise the step that forms the second bronze medal layer and nickel dam, but directly the product forming after the first bronze medal layer and gold layer is bored a hole to remove low melting point axle center 10, and be immersed in dilute nitric acid solution to remove residual low melting material and the first bronze medal layer removing product after the axle center 10 of low melting point, thereby obtain only retaining the gold product of gold layer.Through sclerometer calibrating, the hardness of this gold product is 90Hv, and golden purity is 99.92% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Application Example 6
According to the method for embodiment 3, electroplate gold and carry out the preparation of hard gold, different, when forming mandrel 10, low melting point tin bismuth alloy is substituted by the paraffin of same volume, obtains gold product.Through sclerometer calibrating, the hardness of this gold product is 142Hv, and golden purity is 99.93% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Application Example 7
According to the method for Application Example 1, electroplate gold and carry out the preparation of hard gold, different, in electroplating process, cyanideless electro-plating liquid Z1 is substituted with the cyanogen electroplate liquid Z5 that has of identical weight part, obtain gold product.Through sclerometer calibrating, the hardness of this gold product is 125Hv, and golden purity is 99.97% through the calibrating of fire examination method, and smooth surface, meets product standard requirement.
Application comparative example 1
According to the method for Application Example 1, electroplate gold and carry out the preparation of hard gold, different, described cyanideless electro-plating liquid Z1 substitutes with reference cyanideless electro-plating liquid DZ1.Through sclerometer, assay, the hardness of the gold product that employing the method obtains is only 90Hv, and golden purity is 98.97% through the calibrating of fire examination method, rough, fails to meet product standard requirement.
Application comparative example 2
According to the method for Application Example 1, electroplate gold and carry out the preparation of hard gold, different, described cyanideless electro-plating liquid Z1 substitutes with reference cyanideless electro-plating liquid DZ2.Through sclerometer, assay, the hardness of the gold product that employing the method obtains is only 70Hv, and golden purity is 98.51% through the calibrating of fire examination method, rough, fails to meet product standard requirement.
Application comparative example 3
According to the method for Application Example 1, electroplate gold and carry out the preparation of hard gold, different, described cyanideless electro-plating liquid Z1 substitutes with reference cyanideless electro-plating liquid DZ3.Through sclerometer, assay, the hardness of the gold product that employing the method obtains is only 70Hv, and golden purity is 98.45% through the calibrating of fire examination method, and surface irregularity, fails to meet product standard requirement.
Application comparative example 4
According to the method for Application Example 1, electroplate gold and carry out the preparation of hard gold, different, described cyanideless electro-plating liquid Z1 substitutes with reference cyanideless electro-plating liquid DZ4.Through sclerometer, assay, the hardness of the gold product that employing the method obtains is only 60Hv, and golden purity is 99.8% through the calibrating of fire examination method, and surface irregularity, fails to meet product standard requirement.
As can be seen from the above results, above-mentioned several materials are used in conjunction with to the stiffening agent that obtains for electroplating the process of preparing gold product, can significantly improve the stability of electroplate liquid, electroplating process is steadily carried out.What is more important, from Application Example 1 and the contrast of application comparative example 4, can find out, add stiffening agent provided by the invention in the process of gold product is prepared in plating after, the hardness of gold product has been brought up to 130Hv by 60Hv, as can be seen here, stiffening agent provided by the invention can effectively improve the hardness of gold product, has prospects for commercial application.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition each the concrete technical characterictic described in above-mentioned embodiment, in reconcilable situation, can combine by any suitable mode.For fear of unnecessary repetition, the present invention is to the explanation no longer separately of various possible array modes.
In addition, between various embodiment of the present invention, also can carry out arbitrary combination, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. a stiffening agent, is characterized in that, described stiffening agent contains phosphoric acid salt, hydrophosphate, sulphite, antimonic salt and/or selenium salt and complexing agent, and described sulphite is alkali sulfite metal-salt.
2. stiffening agent according to claim 1, wherein, in described stiffening agent, described phosphoric acid salt with respect to 100-200 gram, the content of described hydrophosphate is 50-200 gram, the content of described alkali sulfite metal-salt is 30-120 gram, and the total content of described antimonic salt and selenium salt is 0.01-2 gram, and the content of described complexing agent is 0.01-5 gram.
3. stiffening agent according to claim 1 and 2, wherein, described phosphoric acid salt is potassiumphosphate and/or sodium phosphate.
4. stiffening agent according to claim 1 and 2, wherein, described hydrophosphate is selected from one or more in potassium phosphate,monobasic, potassium primary phosphate, disodium-hydrogen and SODIUM PHOSPHATE, MONOBASIC.
5. stiffening agent according to claim 1 and 2, wherein, described alkali sulfite metal-salt is potassium sulfite and/or S-WAT.
6. stiffening agent according to claim 1 and 2, wherein, described stiffening agent contains antimonic salt and selenium salt simultaneously.
7. stiffening agent according to claim 6, wherein, the weight ratio of described antimonic salt and selenium salt is 0.25-1:1.
8. stiffening agent according to claim 6, wherein, described antimonic salt is selected from one or more in sodium antimony tartrate, antimonypotassium tartrate, sodium antimonate and potassium antimonate; Described selenium salt is selected from one or more in sodium thiosulfate, seleno potassium sulfate, Sodium Selenite and potassium selenite.
9. stiffening agent according to claim 1 and 2, wherein, described complexing agent is selected from one or more in sodium ethylene diamine tetracetate, thiocarbamide and Sulfothiorine.
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| CN104862752A (en) * | 2015-06-12 | 2015-08-26 | 深圳市联合蓝海投资有限公司 | Modified cyanide-free gold plating solution and application thereof as well as preparation method of hard gold |
| WO2015131796A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and use therefor |
| WO2015131795A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海科技开发有限公司 | Gold electroplating method and hard gold preparation method |
| CN106929889A (en) * | 2017-05-09 | 2017-07-07 | 句容市博远电子有限公司 | A kind of cyanideless electro-plating liquid and preparation method thereof |
| CN110129843A (en) * | 2019-06-05 | 2019-08-16 | 深圳市华乐珠宝首饰有限公司 | A kind of hard golden mirror photoelectricity casting process of no cyanogen |
| CN110205654A (en) * | 2019-06-05 | 2019-09-06 | 深圳市尚美金品有限公司 | A kind of manufacture craft of hollow jewelry piece |
| CN110230079A (en) * | 2015-01-16 | 2019-09-13 | 哈钦森技术股份有限公司 | Golden electroplating solution and method |
| US20230070481A1 (en) * | 2021-09-08 | 2023-03-09 | Suzhou Ontap Precision Electronic Co., Ltd. | Method for preparing heat dissipation component with high flexibility made of graphite or graphene material |
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| WO2015131796A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and use therefor |
| WO2015131795A1 (en) * | 2014-03-04 | 2015-09-11 | 深圳市联合蓝海科技开发有限公司 | Gold electroplating method and hard gold preparation method |
| CN110230079A (en) * | 2015-01-16 | 2019-09-13 | 哈钦森技术股份有限公司 | Golden electroplating solution and method |
| CN110230079B (en) * | 2015-01-16 | 2022-03-11 | 哈钦森技术股份有限公司 | Gold plating solution and method |
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| CN110129843A (en) * | 2019-06-05 | 2019-08-16 | 深圳市华乐珠宝首饰有限公司 | A kind of hard golden mirror photoelectricity casting process of no cyanogen |
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