CN104047037B - Hardener - Google Patents
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- CN104047037B CN104047037B CN201410268462.1A CN201410268462A CN104047037B CN 104047037 B CN104047037 B CN 104047037B CN 201410268462 A CN201410268462 A CN 201410268462A CN 104047037 B CN104047037 B CN 104047037B
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- China
- Prior art keywords
- gold
- salt
- stiffening agent
- copper
- liquid
- Prior art date
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- 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 13
- 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 114
- 229910052737 gold Inorganic materials 0.000 abstract description 114
- 238000009713 electroplating Methods 0.000 abstract description 103
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 100
- 238000000034 method Methods 0.000 abstract description 60
- 230000008569 process Effects 0.000 abstract description 15
- -1 hydrophosphate Chemical compound 0.000 abstract description 8
- 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
- 229910052802 copper Inorganic materials 0.000 description 75
- 239000010949 copper Substances 0.000 description 75
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 74
- 238000007747 plating Methods 0.000 description 61
- 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
- 238000002360 preparation method Methods 0.000 description 25
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 24
- 229910052759 nickel Inorganic materials 0.000 description 18
- 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
- 230000000052 comparative effect Effects 0.000 description 9
- 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
- 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
- 230000015572 biosynthetic process Effects 0.000 description 7
- 150000002343 gold Chemical class 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
- 230000009467 reduction Effects 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
- 230000000717 retained effect 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
- 238000004519 manufacturing process Methods 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
- 239000000203 mixture Substances 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
- 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 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
- GKSYFVIEBZCLEQ-UHFFFAOYSA-N OS(O)=O.N.[Au+3] Chemical compound OS(O)=O.N.[Au+3] GKSYFVIEBZCLEQ-UHFFFAOYSA-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
- 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
- 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
- QUCZBHXJAUTYHE-UHFFFAOYSA-N gold Chemical compound [Au].[Au] QUCZBHXJAUTYHE-UHFFFAOYSA-N 0.000 description 1
- SRCZENKQCOSNAI-UHFFFAOYSA-H gold(3+);trisulfite Chemical compound [Au+3].[Au+3].[O-]S([O-])=O.[O-]S([O-])=O.[O-]S([O-])=O SRCZENKQCOSNAI-UHFFFAOYSA-H 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000000155 melt Substances 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
- 238000005488 sandblasting Methods 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
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
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 the favor of consumers in general.At present, get more and more with the gold product that the mode of plating is produced.Wherein, electroplate liquid used in electroplating process is mainly the solution containing potassium auric cyanide.But potassium auric cyanide belongs to highly toxic substance, not only can work the mischief to the healthy of producer in the production process of gold product, and produce waste liquid to the pollution of environment to reduce, also need to spend a large amount of expenses with process for producing waste liquid.
In order to overcome the above-mentioned defect containing potassium auric cyanide electroplate liquid, in recent years, also Some Enterprises is had to adopt the solution containing sulfurous acid gold liquid (sulfurous acid gold potassium and/or gold sodium sulfide) to substitute solution containing potassium auric cyanide as electroplate liquid, to prepare gold product.But, due to sulfurous acid gold potassium and the less stable of gold sodium sulfide, very easily separate out in electroplating process, thus have impact on the stability of electroplating process and the performance of gold product.In addition, lower using the hardness of gold product that sulfurous acid gold potassium and/or gold sodium sulfide obtain as electroplate liquid, can make like this to make the higher gold product of purity particularly thousand pure golds time, easily deform, cave in, in use very easily damage.The hardness how improving gold product has become the technical problem that current yellow Manufacturing Technology needs solution badly.
Summary of the invention
The object of the invention is to provide a kind of stiffening agent being conducive to improving gold product hardness to overcome the lower defect of existing gold product hardness.
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 is found by further investigation, being used for electroplating with the use of the stiffening agent obtained by above-mentioned several material prepares in the process of gold product, the stability of electroplate liquid can not only be significantly improved, electroplating process is steadily carried out, but also the hardness of gold product can be improved, 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 when the weight ratio of described antimonic salt and selenium salt is 0.25-1:1, can improve the hardness of gained gold product further.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is 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 the concrete preparation method of one 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 described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of 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 content of the present invention to component each in above-mentioned stiffening agent is not particularly limited, such as, 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, the described phosphoric acid salt relative to 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 can be all that the routine of this area is selected.Such as, described phosphoric acid salt can be potassiumphosphate and/or sodium phosphate.Described hydrophosphate can be selected from potassium phosphate,monobasic, potassium primary phosphate, disodium-hydrogen and SODIUM PHOSPHATE, MONOBASIC one or more.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 containing antimonic salt and selenium salt, can improve the hardness of gold product simultaneously so further.When described stiffening agent is simultaneously containing antimonic salt and selenium salt, 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 variously can form the compound of complexing ion with gold ion for existing, such as, can be selected from sodium ethylene diamine tetracetate, thiocarbamide and Sulfothiorine one or more.
In concrete use procedure, above-mentioned stiffening agent is joined and prepares in the electroplate liquid of gold product, then electroplate.Described electroplate liquid can, for containing cyanogen electroplate liquid (namely the main component of electroplate liquid is potassium auric cyanide), also can be cyanideless electro-plating liquid (namely the main component of 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 prepared containing cyanogen electroplate liquid, but also can improve the hardness of the gold product prepared by cyanideless electro-plating liquid.Consider from the angle of environmental protection, described electroplate liquid is cyanideless electro-plating liquid, wherein containing sulfurous acid gold liquid and above-mentioned stiffening agent.
Described sulfurous acid gold liquid variously can electroplate without cyanogen the material containing sulfite ion and gold ion obtaining gold product for existing, and its specific examples includes but not limited to: one or more in the golden ammonium of sulfurous acid gold potassium, gold sodium sulfide and sulfurous acid.But 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 consumption of the present invention to described cyanideless electro-plating liquid sulfite gold liquid is not particularly limited, such as, in described cyanideless electro-plating liquid, in the weight ratio of phosphatic content in the content of the described sulfurous acid gold liquid of gold element and described stiffening agent for 10:100-200, be preferably 10:150-200.
As a rule, described cyanideless electro-plating liquid is also containing water.The consumption of described water can be the routine selection of this area, as long as can guarantee that electroplating process carries out smoothly, such as, the consumption of described water can make with the described cyanideless electro-plating liquid of 1L as benchmark, for 8-20g, 9-12g can be preferably in the content of the described sulfurous acid gold liquid of gold element.
Main improvements of the present invention are to have employed a kind of new stiffening agent, and adopt the cyanideless electro-plating liquid containing this stiffening agent and/or have cyanogen electroplate liquid to electroplate form the concrete grammar of described gold product can be same as the prior art.
According to a kind of embodiment of the present invention, the preparation method of described gold product comprises:
To power on Gold plated Layer at the mandrel formed by low melting material;
Form the hole arriving described mandrel through electrolytic coating, and by described mandrel fusing to be discharged by described hole; Wherein, comprise with described mandrel for negative electrode in the power on method of Gold plated Layer of described mandrel, electroplate at the cyanideless electro-plating liquid containing above-mentioned stiffening agent and/or have in cyanogen electroplate liquid.
Described mandrel mainly plays the effect of forming mould, thus the gold product of different shape can not only be obtained, and the gold product obtained after being removed by described mandrel is hollow structure, thus gold consumption used when can show the gold product of the same size of reduction production, reduce production cost.In the present invention, described " low melting point " refers to fusing point not higher than 200 DEG C, is preferably 60-130 DEG C.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 high temperature stripping, gold can be corroded, therefore, before described mandrel powers on Gold plated Layer, the first layers of copper is electroplated on described mandrel by preferred elder generation, and then electroplates described layer gold in described first layers of copper, and removes described first layers of copper after being melted by described mandrel and discharge.In addition, as the optional mode of another kind, described mandrel also can be removed after plating first layers of copper, before plating layer gold.When removing described mandrel, the discharge of the auxiliary described low melting material of vibration can be adopted.
According to the present invention, when described mandrel or the first layers of copper power on Gold plated Layer, the condition of described plating can comprise usually: the temperature of electroplate liquid is 40-60 DEG C, 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 layer gold of formation can be 50-150 μm, is preferably 100-130 μm.The method that the pH value of described electroplate liquid controls in above-mentioned scope is known to the skilled person, such as, acidic substance or alkaline matter can be added in described electroplate liquid in the past.Described acidic substance can be such as one or more in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid etc.Described alkaline matter can be such as 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 as the criterion the pH value of described electroplate liquid to be adjusted in above-mentioned scope, 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 in described layer gold, electroplate the second layers of copper and nickel dam successively; and after being melted by described mandrel and discharge, remove described second layers of copper and nickel dam; layer gold " dissolving " can be prevented like this, thus play a protective role.In the concrete preparation process of described hard gold, the method forming described first layers of copper generally includes described low melting material (as sn-bi alloy and/or wax, when for wax, usual needs are applying conductive oil on the surface of wax) as negative electrode, using phosphorized copper as anode, electroplate in copper-contained electroplating liquid.The method forming described second layers of copper generally includes being electroplate with the goods of layer gold as negative electrode, using phosphorized copper as anode, is electroplating containing in copper electrolyte.The copper-contained electroplating liquid adopted 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 conditions forming described first layers of copper can be identical or different with the plating conditions forming described second layers of copper, and comprise independently of one another: the temperature of electroplate liquid can be 15-35 DEG C, 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 described first layers of copper of formation can be 40-60 micron, is preferably 45-55 micron; The thickness of described second layers of copper formed can be 40-60 micron, is preferably 45-55 micron.Described first layers of copper is preferably bright and smooth, and the follow-up layer gold obtained can be made so to be also bright and smooth.
According to the present invention, the method forming described nickel dam generally includes being electroplate with the goods of the second layers of copper as negative electrode, using metallic nickel as anode, is electroplating containing in nickel electrolyte.Described containing nickel electrolyte can be this area routine selection, therefore not to repeat here.The plating conditions forming described nickel dam can comprise usually: the temperature of electroplate liquid is 35-50 DEG C, 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, existing various method can be adopted to remove residual low melting material and the first layers of copper, the second layers of copper and nickel dam, such as, after described mandrel is removed, the gold prefabricated component of acquisition can be immersed in dilute nitric acid solution.The concentration of described dilute nitric acid solution can be such as 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 is lower than the temperature of electroplate liquid forming layer gold, then need to form the first layers of copper on mandrel 10, that is, clean mandrel 10 to be transferred in copper plating bath 13 and to electroplate, to form the first layers of copper on the surface of mandrel 10.Described first layers of copper should be bright and smooth, thus makes the layer gold of follow-up formation also be bright and smooth.(be electroplate with the first layers of copper or be not electroplate with the first layers of copper) mandrel 10 have cyanogen or the cyanideless electro-plating liquid 14 that are placed in containing stiffening agent are electroplated, form layer gold, then the product obtained is placed in copper plating bath 13 to electroplate, to form the second layers of copper in layer gold.After formation second layers of copper, the product obtained is placed in nickel-plating liquid 15 and electroplates, to form nickel dam in the second layers of copper.After completing plating, the product obtained is removed from fixture 20, and bore the plural hole reaching mandrel 10 center through each electrolytic coating in place.Then product is put into stove to be heated about 200 DEG C, the mandrel 10 of low melting point melts and flows out from hole.Then again the product after the mandrel 10 removing low melting point to be immersed in dilute nitric acid solution to remove residual low melting material and the first layers of copper, the second layers of copper and nickel dam, only to retain layer gold, thus obtain gold product.
Above-mentioned each plating step all can be implemented by traditional way, such as, can be electrically connected to the negative electrode of direct supply by comprising described mandrel 10 and the product associating metal level formed afterwards by hanger 20 and insert in corresponding electroplate liquid, anode be then connected to the positive terminal of direct supply and inserts in corresponding electroplate liquid.
In addition, the preparation method of the described hard gold gold product also comprised after the low melting material and the first layers of copper, the second layers of copper and nickel dam removal remained adopts the mode process such as welding, sandblasting and polishing to become jewelry piece.
Below will be described the present invention by embodiment.
Embodiment 1
This embodiment is for illustration of the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
At 60 DEG C, 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 DEG C, the gold sodium sulfide in gold element consumption being 10 grams is mixed with stiffening agent Y1, obtain cyanideless electro-plating liquid Z1.Stability and the electroconductibility of cyanideless electro-plating liquid Z1 is measured by cyclic voltammetry, cathodic polarization curve and cathode efficiency method.Result shows, the stability of cyanideless electro-plating liquid Z1 is high, only has very low amount gold ion automatic reduction, and electroconductibility is very good, and cathode efficiency maintains more than 90%.
Embodiment 2
This embodiment is for illustration of the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
At 40 DEG C, 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 DEG C, the sulfurous acid gold potassium being 10 grams is mixed with stiffening agent Y2, obtain cyanideless electro-plating liquid Z2 in gold element consumption.According to the method for embodiment 1, the stability of cyanideless electro-plating liquid Z2 and electroconductibility are tested.Result shows, the stability of cyanideless electro-plating liquid Z2 is high, does not have 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 illustration of the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
At 45 DEG C, 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 DEG C, the gold sodium sulfide in gold element consumption being 10 grams is mixed with stiffening agent Y3, obtain cyanideless electro-plating liquid Z3.According to the method for embodiment 1, the stability of cyanideless electro-plating liquid Z3 and electroconductibility are tested.Result shows, cyanideless electro-plating liquid Z3 stability is very high, does not have gold ion automatic reduction, and electroconductibility is very good, and cathode efficiency maintains more than 90%.
Embodiment 4
This embodiment is for illustration of the preparation method of stiffening agent provided by the invention and cyanideless electro-plating liquid.
Cyanideless electro-plating liquid is prepared according to the method for embodiment 1, unlike, the Sodium Selenite of described sodium antimony tartrate identical weight part substitutes, and obtains stiffening agent Y4 and cyanideless electro-plating liquid Z4.According to the method for embodiment 1, the stability of cyanideless electro-plating liquid Z4 and electroconductibility are tested.Result shows, the stability of cyanideless electro-plating liquid Z4 is high, only has very low amount 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 illustration of stiffening agent provided by the invention and the preparation method having cyanogen electroplate liquid.
Cyanogen electroplate liquid is had according to the method preparation of embodiment 1, unlike, be that the gold sodium sulfide of 10 grams substitutes in order to the potassium auric cyanide that gold element meter consumption is 10 grams in gold element consumption, obtained cyanogen electroplate liquid Z5.According to the method for embodiment 1, the stability and electroconductibility that have cyanogen electroplate liquid Z5 are tested.Result shows, has the stability of cyanogen electroplate liquid Z5 high, does not have 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
The stiffening agent of this comparative example for illustration of reference and the preparation method of cyanideless electro-plating liquid.
Stiffening agent and cyanideless electro-plating liquid is prepared according to the method for embodiment 4, unlike, the potassium phosphate,monobasic of described potassiumphosphate identical weight part substitutes, and obtains reference stiffening agent DY1 and cyanideless electro-plating liquid DZ1.According to the method for embodiment 1, the stability of reference cyanideless electro-plating liquid DZ1 and electroconductibility are tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ1 is low, and poorly conductive, cathode current density only can reach 80%.
Comparative example 2
The stiffening agent of this comparative example for illustration of reference and the preparation method of cyanideless electro-plating liquid.
Modification electroplate liquid and cyanideless electro-plating liquid is prepared according to the method for embodiment 4, unlike, the potassiumphosphate of described potassium phosphate,monobasic identical weight part substitutes, and obtains reference stiffening agent DY2 and cyanideless electro-plating liquid DZ2.Test according to the stability of method to reference cyanideless electro-plating liquid DZ2 of embodiment 1.Result shows, the stability of reference cyanideless electro-plating liquid DZ2 is low, and poorly conductive, cathode current density only can reach 80%.
Comparative example 3
The stiffening agent of this comparative example for illustration of reference and the preparation method of cyanideless electro-plating liquid.
Stiffening agent and cyanideless electro-plating liquid is prepared according to the method for comparative example 1, unlike, the gold sodium sulfide of described potassium phosphate,monobasic identical weight part substitutes, and obtains reference stiffening agent and cyanideless electro-plating liquid DZ3.According to the method for embodiment 1, the stability of reference cyanideless electro-plating liquid DZ3 and electroconductibility are tested.Result shows, the stability of reference cyanideless electro-plating liquid DZ3 is low, and poorly conductive, cathode current density only can reach 75%.
Comparative example 4
This comparative example is for illustration of the preparation method of the cyanideless electro-plating liquid of reference.
Cyanideless electro-plating liquid is prepared according to the method for embodiment 1, unlike, 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, obtains reference cyanideless electro-plating liquid DZ4.According to the method for embodiment 1, the stability of reference cyanideless electro-plating liquid DZ4 and electroconductibility are tested.Result shows, the stability extreme difference of reference cyanideless electro-plating liquid DZ4, 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 formed 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 and electroplate, wherein, the temperature that plating conditions comprises copper plating bath 13 is 25 DEG C, the pH value of copper plating bath 13 is 0.1, and cathode current density is 4A/dm
2, electroplating time is 1 hour, forms the first layers of copper that thickness is 50 microns.Then the cyanideless electro-plating liquid Z1 be placed in by the mandrel 10 being electroplate with the first layers of copper containing sulfurous acid gold liquid electroplates, and wherein, the temperature that plating conditions comprises cyanideless electro-plating liquid Z1 is 60 DEG C, 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, forms the layer gold that thickness is 130 microns.Then the product being electroplate with layer gold is placed in copper plating bath 13 to electroplate, wherein, the temperature that plating conditions comprises copper plating bath 13 is 25 DEG C, 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, forms the second layers of copper that thickness is 50 microns.Then the product being electroplate with the second layers of copper is placed in 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, electroplate down together), wherein, the temperature that plating conditions comprises nickel-plating liquid 15 is 45 DEG C, the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, forms the nickel dam that thickness is 10 microns.After completing plating, the product obtained is removed from hanger 20, and bore the plural hole reaching mandrel 10 center through each electrolytic coating in place.Then product is put into stove to be heated about 200 DEG C, the axle center 10 of low melting point is melted and is flowed out from hole.Then again the product after the axle center 10 of removal low melting point is immersed in remove residual low melting material and the first layers of copper, the second layers of copper and nickel dam in dilute nitric acid solution, thus is only retained the gold product of layer gold.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 being transferred to by clean mandrel 10 in copper plating bath 13 and to electroplate, wherein, the temperature that plating conditions comprises copper plating bath 13 is 25 DEG C, 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, forms the first layers of copper that thickness is 50 microns.Then the cyanideless electro-plating liquid Z2 be placed in by the mandrel 10 being electroplate with the first layers of copper containing sulfurous acid gold liquid electroplates, and wherein, the temperature that plating conditions comprises cyanideless electro-plating liquid Z2 is 40 DEG C, 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, forms the layer gold that thickness is 100 microns.Then the product being electroplate with layer gold is placed in copper plating bath 13 to electroplate, wherein, the temperature that plating conditions comprises copper plating bath 13 is 25 DEG C, 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, forms the second layers of copper that thickness is 50 microns.Then the product being electroplate with the second layers of copper is placed in nickel-plating liquid 15 to electroplate, wherein, the temperature that plating conditions comprises nickel-plating liquid 15 is 45 DEG C, and the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, forms the nickel dam that thickness is 10 microns.After completing plating, the product obtained is removed from hanger 20, and bore the plural hole reaching mandrel 10 center through each electrolytic coating in place.Then product is put into stove to be heated about 200 DEG C, the axle center 10 of low melting point is melted and is flowed out from hole.Then again the product after the axle center 10 of removal low melting point is immersed in remove residual low melting material and the first layers of copper, the second layers of copper and nickel dam in dilute nitric acid solution, thus is only retained the gold product of layer gold.Assay through sclerometer, 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 being transferred to by clean mandrel 10 in copper plating bath 13 and to electroplate, wherein, the temperature that plating conditions comprises copper plating bath 13 is 25 DEG C, 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, forms the first layers of copper that thickness is 50 microns.Then the cyanideless electro-plating liquid Z3 be placed in by the mandrel 10 being electroplate with the first layers of copper containing sulfurous acid gold liquid electroplates, and wherein, the temperature that plating conditions comprises cyanideless electro-plating liquid Z3 is 45 DEG C, 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, forms the layer gold that thickness is 120 microns.Then the product being electroplate with layer gold is placed in copper plating bath 13 to electroplate, wherein, the temperature that plating conditions comprises copper plating bath 13 is 25 DEG C, 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, forms the second layers of copper that thickness is 50 microns.Then the product being electroplate with the second layers of copper is placed in nickel-plating liquid 15 to electroplate, wherein, the temperature that plating conditions comprises nickel-plating liquid 15 is 45 DEG C, and the pH value of nickel-plating liquid 15 is 4, and cathode current density is 2A/dm
2, electroplating time is 20 minutes, forms the nickel dam that thickness is 10 microns.After completing plating, the product obtained is removed from hanger 20, and bore the plural hole reaching mandrel 10 center through each electrolytic coating in place.Then product is put into stove to be heated about 200 DEG C, the axle center 10 of low melting point is melted and is flowed out from hole.Then again the product after the axle center 10 of removal low melting point is immersed in remove residual low melting material and the first layers of copper, the second layers of copper and nickel dam in dilute nitric acid solution, thus is only retained the gold product of layer gold.Assay through sclerometer, 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
Electroplate gold according to the method for embodiment 1 and carry out the preparation of hard gold, unlike, described cyanideless electro-plating liquid Z1 cyanideless electro-plating liquid Z4 substitutes, and is only retained the gold product of layer gold.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
Electroplate gold according to the method for embodiment 4 and carry out the preparation of hard gold, unlike, in preparation process, do not comprise the step of formation second layers of copper and nickel dam, but directly the product after formation first layers of copper and layer gold is bored a hole to remove low melting point axle center 10, and be immersed in the product after the axle center 10 of removal low melting point to remove residual low melting material and the first layers of copper in dilute nitric acid solution, thus only retained the gold product of layer gold.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
Electroplate gold according to the method for embodiment 3 and carry out the preparation of hard gold, unlike, 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
Electroplate gold according to the method for Application Example 1 and carry out the preparation of hard gold, unlike, in electroplating process, the cyanogen electroplate liquid Z5 that has of cyanideless electro-plating liquid Z1 identical weight part is substituted, obtains 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.
Comparison study example 1
Electroplate gold according to the method for Application Example 1 and carry out the preparation of hard gold, unlike, described cyanideless electro-plating liquid Z1 reference cyanideless electro-plating liquid DZ1 substitutes.Assay through sclerometer, the hardness of the gold product adopting the method to obtain is only 90Hv, and golden purity is 98.97% through the calibrating of fire examination method, rough, fails to meet product standard requirement.
Comparison study example 2
Electroplate gold according to the method for Application Example 1 and carry out the preparation of hard gold, unlike, described cyanideless electro-plating liquid Z1 reference cyanideless electro-plating liquid DZ2 substitutes.Assay through sclerometer, the hardness of the gold product adopting the method to obtain is only 70Hv, and golden purity is 98.51% through the calibrating of fire examination method, rough, fails to meet product standard requirement.
Comparison study example 3
Electroplate gold according to the method for Application Example 1 and carry out the preparation of hard gold, unlike, described cyanideless electro-plating liquid Z1 reference cyanideless electro-plating liquid DZ3 substitutes.Assay through sclerometer, the hardness of the gold product adopting the method to obtain 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.
Comparison study example 4
Electroplate gold according to the method for Application Example 1 and carry out the preparation of hard gold, unlike, described cyanideless electro-plating liquid Z1 reference cyanideless electro-plating liquid DZ4 substitutes.Assay through sclerometer, the hardness of the gold product adopting the method to obtain 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 material is used for electroplating with the use of the stiffening agent obtained and prepares in the process of gold product, the stability of electroplate liquid can be significantly improved, electroplating process is steadily carried out.What is more important, as can be seen from contrast with Comparison study example 4 of Application Example 1, after plating is prepared in the process of gold product and is added stiffening agent provided by the invention, the hardness of gold product has brought up to 130Hv by 60Hv, as can be seen here, stiffening agent provided by the invention effectively can 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 characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode.In order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, 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 relative 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 be selected from potassium phosphate,monobasic, potassium primary phosphate, disodium-hydrogen and SODIUM PHOSPHATE, MONOBASIC one or more.
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 is simultaneously containing antimonic salt and selenium salt.
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 be selected from sodium antimony tartrate, antimonypotassium tartrate, sodium antimonate and potassium antimonate one or more; Described selenium salt be selected from sodium thiosulfate, seleno potassium sulfate, Sodium Selenite and potassium selenite one or more.
9. stiffening agent according to claim 1 and 2, wherein, described complexing agent be selected from sodium ethylene diamine tetracetate, thiocarbamide and Sulfothiorine one or more.
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| CN103938231B (en) * | 2014-03-04 | 2015-04-01 | 深圳市联合蓝海科技开发有限公司 | Gold electroplating method and hard gold preparation method |
| CN103938232B (en) * | 2014-03-04 | 2015-04-01 | 深圳市联合蓝海新技术有限公司 | Cyanide-free electroplating solution and application thereof |
| CN107250440B (en) * | 2015-01-16 | 2019-07-30 | 哈钦森技术股份有限公司 | Golden electroplating solution and method |
| CN104862752B (en) * | 2015-06-12 | 2016-02-17 | 深圳市联合蓝海投资控股集团有限公司 | The preparation method of modification cyanogen-less gold liquid and application and hard gold |
| 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 |
| 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 |
| 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 |
| CN113622007A (en) * | 2021-09-08 | 2021-11-09 | 苏州市安派精密电子有限公司 | Preparation method of high-flexibility graphite or graphene heat dissipation component |
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| CN1109517A (en) * | 1995-02-24 | 1995-10-04 | 清华大学 | Electromoulding liquid for cyanogen-free electromoulding K gold product |
| CN1494606A (en) * | 2001-02-28 | 2004-05-05 | ƽ | Bath for galvanic deposition of gold and gold alloys, and use thereof |
| JP2008115449A (en) * | 2006-11-07 | 2008-05-22 | Ne Chemcat Corp | Non-cyanogen-based gold electroplating bath for forming gold bump or gold wiring |
| CN101560676A (en) * | 2009-04-24 | 2009-10-21 | 武汉金凰珠宝股份有限公司 | Method for electroforming hard gold product |
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| CN104047037A (en) | 2014-09-17 |
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