CN106637307A - Additive for cyanide-free electroforming technology of gold - Google Patents
Additive for cyanide-free electroforming technology of gold Download PDFInfo
- Publication number
- CN106637307A CN106637307A CN201710004079.9A CN201710004079A CN106637307A CN 106637307 A CN106637307 A CN 106637307A CN 201710004079 A CN201710004079 A CN 201710004079A CN 106637307 A CN106637307 A CN 106637307A
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- CN
- China
- Prior art keywords
- gold
- additive
- trivalent
- chromium
- aluminium
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- 239000010931 gold Substances 0.000 title claims abstract description 68
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 68
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 238000005323 electroforming Methods 0.000 title claims abstract description 50
- 239000000654 additive Substances 0.000 title claims abstract description 43
- 230000000996 additive effect Effects 0.000 title claims abstract description 42
- 239000003792 electrolyte Substances 0.000 claims abstract description 21
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims abstract description 12
- 239000004411 aluminium Substances 0.000 claims abstract description 7
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 7
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 7
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 239000011651 chromium Substances 0.000 claims abstract description 6
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims abstract description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims abstract description 5
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims abstract description 5
- 229960000359 chromic chloride Drugs 0.000 claims abstract description 5
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims abstract description 5
- 239000008367 deionised water Substances 0.000 claims abstract description 5
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 5
- 239000005955 Ferric phosphate Substances 0.000 claims abstract description 4
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims abstract description 4
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims abstract description 4
- 229940032958 ferric phosphate Drugs 0.000 claims abstract description 4
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 claims abstract description 4
- 229910000399 iron(III) phosphate Inorganic materials 0.000 claims abstract description 4
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims abstract description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims abstract description 3
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims description 46
- 238000000034 method Methods 0.000 claims description 34
- 150000001767 cationic compounds Chemical class 0.000 claims description 5
- 241000370738 Chlorion Species 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 150000001450 anions Chemical class 0.000 claims description 2
- 238000005868 electrolysis reaction Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000007747 plating Methods 0.000 abstract description 8
- -1 ion compounds Chemical class 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 abstract description 4
- 229910019142 PO4 Inorganic materials 0.000 abstract description 2
- 239000010452 phosphate Substances 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 abstract 1
- 229940001007 aluminium phosphate Drugs 0.000 abstract 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000000151 deposition Methods 0.000 description 8
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229910000402 monopotassium phosphate Inorganic materials 0.000 description 5
- 235000019796 monopotassium phosphate Nutrition 0.000 description 5
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 5
- 235000011164 potassium chloride Nutrition 0.000 description 5
- 239000001103 potassium chloride Substances 0.000 description 5
- 230000008021 deposition Effects 0.000 description 4
- 229910052742 iron Inorganic materials 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- NWXQHQALYYJTEH-UHFFFAOYSA-K [Au](Cl)(Cl)Cl.N#CC#N Chemical compound [Au](Cl)(Cl)Cl.N#CC#N NWXQHQALYYJTEH-UHFFFAOYSA-K 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241001354491 Lasthenia californica Species 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GSOLWAFGMNOBSY-UHFFFAOYSA-N cobalt Chemical compound [Co][Co][Co][Co][Co][Co][Co][Co] GSOLWAFGMNOBSY-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000005494 tarnishing Methods 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to an additive for a cyanide-free electroforming technology of gold. The additive comprises trivalent position ion compounds. The additive is characterized in that the trivalent position ion compounds comprise ferric iron positive ions, trivalent aluminium positive ions and trivalent chromium positive ions; negative ions are chloride ions, sulfate radicals and phosphate radicals; ferric iron is one or more in ferric chloride, ferric phosphate or ferric sulfate; trivalent aluminium is one or more in aluminium chloride, aluminium phosphate or aluminum sulfate; trivalent chromium is one or more in chromium trichloride, chromium phosphate or chromium sulfate; the mass concentration of the components is 0.2 g/L to 5 g/L; and the components are prepared through deionized water and are fully stirred for 3 to 5 minutes through ultrasonic waves. The additive is inorganic salt, can dissolve in water, does not react with other components in an electrolyte, does not volatilize, and is small in dosage, free of toxicity and easy to store; and through the addition of the additive, the deep plating capability of the electrolyte can be improved, the hardness of an electroformed layer is obviously improved as well, and a compact, flat thick gold layer which is low in porosity and not liable to deform and achieves the mass fraction of 99.9% can be obtained.
Description
Technical field
The present invention relates to it is a kind of for additive of the gold without cyanogen electroforming process, it is specifically a kind of to be used to improve without cyanogen
Additive formulations used in the gold electroforming process of electroforming gold solution covering power and hardness.
Background technology
Very well, it is unique metal not reacted with oxygen under high temperature to the chemical stability of gold, with various acid, alkali nearly all
Do not have an effect.The bright of gold is honorable, and corrosion resistance and anti-tarnishing ability are strong, and billon is presented not because of the addition of alloying element
Same tone, therefore enjoy the favor of people.Gold electroforming process is a kind of electro-deposition forming technique, is that a kind of special of plating should
With its principle is identical with plating.Cyaniding electroforming gold solution, the solution is adopted to have good dispersion in electroforming gold process mostly in the early time
Ability and covering power, coating crystallization is careful.But cyanide is constituted very big as the chemicals of severe toxicity to environment and operating personnel
Threat.Country has promulgated related command, eliminates application of the cyanide in plating, electroforming process.
For a long time, Chinese scholars are to being capable of having carried out extensively without cyanogen electroforming gold process for substitute electroforming gold process
General research, current mainstream research is concentrated mainly on sulfurous acid system, and the major defect of the system is the sulphite in solution
It is unstable, its concentration is reduced by the oxidation of the oxygen in the oxygen or air of generation on anode, cause the decomposition of plating solution.
And sulphite system needs in process of production the supplement of extra gold salt, and electrolyte to use aging phenomenon after a period of time
Than more serious.Therefore, solving problem present in gold electroforming process is one that related personnel is inquiring into always in industry and asks
Topic.Problem present in gold electroforming process is concentrated mainly on that electrolyte covering power is poor, and stability is poor, and the electroformed layer for obtaining is hard
Spend the aspect such as inadequate.
For the problems referred to above, Chinese scholars have carried out the exploration of correlation, and by metal co-deposition two phase alloys are formed
Method improves the hardness of electroformed layer, such as the co-deposition of gold/cobalt, the co-deposition of gold/carbon, the co-deposition of gold/nickel.But these yuan
While being added on reduction current efficiency of element, can also make deposition layer have at a relatively high internal stress, and deposition layer occurs
The phenomenon of stress cracking, so that electroformed layer fragility is larger.
China discloses the application for a patent for invention of " a kind of technique of double-pulse plating gold ", application on May 21st, 2014
Number be 201210451481.9, wherein, the technique for describing cyanide-free gold electroplating, the technology be mainly primarily adapted for use in plating golden collar
Domain, it is relatively low using sedimentation rate in electroforming gold field, it is impossible to meet industrial requirement well.Also at 2015 2
" one kind is without cyanogen electroforming gold solution and the electroforming gold method " of China Geological Univ. Wuhan's application disclosed in the moon 18, Patent No.
201410667310.9, the patent also describes the electroforming gold solution and technique of cyanide-free gold electroplating, is related in the patented technology
The casting gold solution without cyanogen gold chloride system, without in cyanogen gold chloride system with gold chloride as gold salt, complex ion based on chlorion.Should
System can obtain the higher thick layer gold of Vickers hardness, and making direct current into pulse current can make deposition layer crystal grains fine,
Cast layer thickeies, and intensity becomes big.It is deep but the system yet suffers from some needs the aspect of optimization, such as only rely on basic bath
Degree ability is not ideal enough, and the deposition layer covering power for obtaining is poor, and electroformed layer is in uneven thickness, so as to bulk strength still not
It is well positioned to meet the requirement of product.
The content of the invention
The invention aims to the deficiency that the prior art for solving is present, and one kind is provided and specially solves current gold electricity
The problems such as cast layer hardness is not enough, deep plating property is poor for additive of the gold without cyanogen electroforming process, in the base of basic electrolyte
By adding this additive on plinth, can obtain electroforming it is smooth it is fine and close, porosity is low, hardness is high, thickness is uniform and is unlikely to deform
Thick layer gold.
For achieving the above object, the technical measures taken of the present invention be to provide it is a kind of for gold without cyanogen electroforming process
Additive, the cationic compound containing trivalent in additive component, described cationic compound includes ferric iron, trivalent
Aluminium, trivalent chromium, anion is chlorion, sulfate radical, phosphate radical；
Described ferric iron is one or more in iron chloride or ferric phosphate, ferric sulfate, trivalent aluminium be aluminium chloride or
One or more in person's aluminum phosphate, aluminum sulfate, trivalent chromium is chromium trichloride or the one kind or several in chromium phosphate, chromium sulfate
Kind, the mass concentration of each component is 0.2～5g/L, and deionized water is prepared, and is sufficiently stirred for 3～5 minutes with ultrasonic wave.
Described additive is added to gold without in cyanogen electroforming Gold electrolysis liquid according to required dosage, and electroforming process condition is,
The electrolyte pH of electroforming gold is 2～6, and temperature is 20～40 DEG C；Electric pulse parameter is direct impulse 200～2000Hz of frequency, just
It is 10～200ms to pulse ON time, positive dutycycle is 10%～70%, and reverse impulse frequency is 200～2000Hz, instead
It is 5～100ms to pulse ON time, reverse dutycycle is 10%～90%.
Electroforming gold system of the gold used in the present invention without cyanogen electroforming gold is gold chloride system, is matched somebody with somebody in basic electrolyte
Add this additive on the basis of side, operating condition is：The electrolyte pH scopes of electroforming gold are 2～6, and temperature is 20～40 DEG C.
After adding this additive, the thickness gold of 200 μm of thickness, mass fraction more than 99.9%, microhardness 100HV0.2/15 can be obtained
Layer.
The present invention has an advantageous effect in that compared with prior art for additive of the gold without cyanogen electroforming process：
(1), the present invention add this additive on the basis of former electrolyte prescription, solve basic bath covering power compared with
Difference, the relatively low problem of the product electroformed layer hardness that electroforming is obtained, while the additive of the present invention during electroforming without mending again
Other additives are filled, the industrialization demand of electroforming industry can be met.
(2), additive physicochemical properties of the invention are stablized, and good conductivity is non-volatile, and get along well in electrolyte into
Distribute biochemical reaction.
(3), additive formulations of the invention are simple, easy to maintain without extremely toxic substance, not volatile, and pH value is neutrality, makes
With conveniently, consumption is few and simple to operate.
(4), using the additive low cost of the present invention, the covering power and hardness of electrolyte can be significantly improved, addition is originally
The gold product electroformed layer hardness that electroforming is obtained after the additive of invention is significantly improved, and Vickers hardness number can reach
100HV0.2/15, and product crystallization is careful, corrosion resistance is strong, and porosity is low.
Specific embodiment
With reference to specific embodiment, the invention will be further described, but the enforcement not limited to this of the present invention.
The basic electrolyte of predetermined is prepared, it is each according to the additive that basic electrolyte concentration known is calculated required
The quality of component, additive is added in electrolyte according to required dosage.Cationization containing trivalent in additive component
Compound, additive each component is analyzes pure, and deionized water is prepared, and is sufficiently stirred for 3～5 minutes with ultrasonic wave, you can opened
Beginning carries out gold electroforming.Following examples are currently preferred case study on implementation.
Embodiment 1：The present invention provides a kind of for additive of the gold without cyanogen electroforming process, and three are contained in additive component
The cationic compound of valency, is ferric phosphate 0.2g/L, aluminium chloride 5g/L, chromium trichloride 1g/L, and deionized water is prepared, and with surpassing
Sound wave is sufficiently stirred for 3 minutes, in being added to basic electrolyte.Basis includes without cyanogen electroforming gold solution：Gold chloride (gold ion concentration
Meter) 10g/L, potassium chloride 80g/L, potassium dihydrogen phosphate 20g/L, pH2,40 DEG C of temperature.According to the formula as electrolyte, technique
Condition is that electric pulse parameter is direct impulse frequency 200Hz, and direct impulse ON time is 50ms, and positive dutycycle is 50%,
Reverse impulse frequency is 1000Hz, and reverse impulse ON time is 25ms, and reverse dutycycle is 10%.Thickness can be obtained with electroforming
200 μm, mass fraction more than 99.9%, micro-vickers hardness 105HV0.2/15 thick layer gold products in uniform thickness.
Embodiment 2：The present invention provides a kind of for additive of the gold without cyanogen electroforming process, and phosphorus is contained in additive component
Sour iron 5g/L, aluminium chloride 0.2g/L, aluminum sulfate 0.2g/L, chromium sulfate 0.5g/L.Basis includes without cyanogen electroforming gold solution：Gold chloride
(gold ion densimeter) 20g/L, potassium chloride 100g/L, potassium dihydrogen phosphate 15g/L, pH6,20 DEG C of temperature.Make according to the formula
For electrolyte, process conditions are that electric pulse parameter is direct impulse frequency 1000Hz, and direct impulse ON time is 200ms, just
It is 20% to dutycycle, reverse impulse frequency is 800Hz, reverse impulse ON time is 100ms, and reverse dutycycle is 90%.
200 μm of thickness, mass fraction more than 99.9%, micro-vickers hardness 102HV0.2/15 thick layer gold in uniform thickness can be obtained.
Embodiment 3：The present invention provides a kind of for additive of the gold without cyanogen electroforming process, and chlorine is contained in additive component
Change iron 0.5g/L, aluminum sulfate 0.2g/L, aluminum phosphate 0.2g/L, chromium trichloride 4g/L, chromium sulfate 1g/L.Basis is molten without cyanogen electroforming gold
Liquid includes：Gold chloride (gold ion densimeter) 15g/L, potassium chloride 120g/L, potassium dihydrogen phosphate 20g/L, pH5,30 DEG C of temperature.Press
According to the formula as electrolyte, process conditions are that electric pulse parameter is direct impulse frequency 2000Hz, when direct impulse is turned on
Between be 120ms, positive dutycycle be 10%, reverse impulse frequency be 2000Hz, reverse impulse ON time be 60ms, reversely account for
Sky is than being 40%.200 μm of thickness, mass fraction more than 99.9%, micro-vickers hardness 110HV0.2/15 thickness can be obtained equal
Even thick layer gold.
Embodiment 4：The present invention provides a kind of for additive of the gold without cyanogen electroforming process, and chlorine is contained in additive component
Change iron 3g/L, aluminium chloride 1g/L, chromium phosphate 2g/L.Basis includes without cyanogen electroforming gold solution：Gold chloride (gold ion densimeter)
25g/L, potassium chloride 140g/L, potassium dihydrogen phosphate 30g/L, pH4,40 DEG C of temperature.According to the formula as electrolyte, technique bar
Part is that electric pulse parameter is direct impulse frequency 500Hz, and direct impulse ON time is 10ms, and positive dutycycle is 30%, instead
It is 200Hz to pulse frequency, reverse impulse ON time is 5ms, and reverse dutycycle is 20%.200 μm of thickness, matter can be obtained
Amount fraction more than 99.9%, micro-vickers hardness 100HV0.2/15 thick layer gold in uniform thickness.
Embodiment 5：The present invention provides a kind of for additive of the gold without cyanogen electroforming process, and sulphur is contained in additive component
Sour iron 3g/L, aluminum phosphate 0.2g/L, chromium sulfate 3g/L.Basis includes without cyanogen electroforming gold solution：Gold chloride (gold ion densimeter)
30g/L, potassium chloride 150g/L, potassium dihydrogen phosphate 35g/L, pH3,20 DEG C of temperature.According to the formula as electrolyte, technique bar
Part is that electric pulse parameter is direct impulse frequency 333Hz, and direct impulse ON time is 40ms, and positive dutycycle is 70%, instead
It is 800Hz to pulse frequency, reverse impulse ON time is 20ms, and reverse dutycycle is 30%.Can obtain 200 μm of thickness,
Mass fraction more than 99.9%, micro-vickers hardness 106HV0.2/15 thick layer gold in uniform thickness.
The additive formulations of the present invention are simple, and consumption is few, low cost, easy to use, and simple to operate.The addition present invention's
The gold product Vickers hardness number that electroforming is obtained after additive can reach 100HV0.2/15, and product crystallizes careful, corrosion resistance
By force, porosity is low.
Claims (2)
1. a kind of for additive of the gold without cyanogen electroforming process, the cationic compound containing trivalent in additive component, its
It is characterised by：Described cationic compound includes ferric iron, trivalent aluminium, trivalent chromium, and anion is chlorion, sulfate radical, phosphorus
Acid group；
Described ferric iron is one or more in iron chloride or ferric phosphate, ferric sulfate, and trivalent aluminium is aluminium chloride or phosphorus
One or more in sour aluminium, aluminum sulfate, trivalent chromium is one or more in chromium trichloride or chromium phosphate, chromium sulfate, respectively
The mass concentration of component is 0.2～5g/L, and deionized water is prepared, and is sufficiently stirred for 3～5 minutes with ultrasonic wave.
2. according to claim 1 a kind of for additive of the gold without cyanogen electroforming process, it is characterised in that：Described adds
Plus agent is added to gold without in cyanogen electroforming Gold electrolysis liquid according to required dosage, electroforming process condition is, the electrolyte pH of electroforming gold
For 2～6, temperature is 20～40 DEG C；Electric pulse parameter is direct impulse 200～2000Hz of frequency, and direct impulse ON time is
10～200ms, positive dutycycle is 10%～70%, and reverse impulse frequency is 200～2000Hz, and reverse impulse ON time is
5～100ms, reverse dutycycle is 10%～90%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710004079.9A CN106637307B (en) | 2017-01-04 | 2017-01-04 | A kind of additive for gold without cyanogen electroforming process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710004079.9A CN106637307B (en) | 2017-01-04 | 2017-01-04 | A kind of additive for gold without cyanogen electroforming process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106637307A true CN106637307A (en) | 2017-05-10 |
| CN106637307B CN106637307B (en) | 2019-01-01 |
Family
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107227469A (en) * | 2017-06-26 | 2017-10-03 | 南京市产品质量监督检验院 | A kind of hard golden electroforming solutions of 3D, its preparation method and its application |
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| CN106637307B (en) | 2019-01-01 |
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