CN106637307B - A kind of additive for gold without cyanogen electroforming process - Google Patents
A kind of additive for gold without cyanogen electroforming process Download PDFInfo
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- CN106637307B CN106637307B CN201710004079.9A CN201710004079A CN106637307B CN 106637307 B CN106637307 B CN 106637307B CN 201710004079 A CN201710004079 A CN 201710004079A CN 106637307 B CN106637307 B CN 106637307B
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- Prior art keywords
- gold
- additive
- chromium
- trivalent
- phosphate
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- 239000010931 gold Substances 0.000 title claims abstract description 63
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 63
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 238000005323 electroforming Methods 0.000 title claims abstract description 48
- 239000000654 additive Substances 0.000 title claims abstract description 44
- 230000000996 additive effect Effects 0.000 title claims abstract description 42
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 35
- 239000003792 electrolyte Substances 0.000 claims abstract description 23
- 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 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 150000001767 cationic compounds Chemical class 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
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910021556 Chromium(III) chloride Inorganic materials 0.000 claims abstract description 5
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims abstract description 5
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 4
- 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
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 3
- 150000001450 anions Chemical class 0.000 claims abstract description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims abstract description 3
- 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
- 239000010452 phosphate Substances 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 5
- BDGYOXLDSUTJGA-UHFFFAOYSA-N gold;oxalonitrile Chemical compound [Au].N#CC#N BDGYOXLDSUTJGA-UHFFFAOYSA-N 0.000 claims description 4
- 238000005266 casting Methods 0.000 claims description 2
- 230000005611 electricity Effects 0.000 claims description 2
- -1 chromium cation Chemical class 0.000 abstract description 6
- 239000004615 ingredient Substances 0.000 abstract 2
- 231100000252 nontoxic Toxicity 0.000 abstract 1
- 230000003000 nontoxic effect Effects 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 10
- 238000000151 deposition Methods 0.000 description 9
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 7
- 238000007747 plating Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 5
- 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
- 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
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process 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
- 241001354491 Lasthenia californica Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- 239000002253 acid 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
- 238000004458 analytical method Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 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
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 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
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000004 severe toxicity Toxicity 0.000 description 1
- 238000003756 stirring Methods 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 present invention relates to a kind of additive for gold without cyanogen electroforming process, the cationic compound containing trivalent in ingredient, including ferric iron, trivalent aluminium and trivalent chromium cation, anion are chloride ion, sulfate radical and phosphate radical；Ferric iron is one or more of iron chloride or ferric phosphate, ferric sulfate, trivalent aluminium is one or more of aluminium chloride or aluminum phosphate, aluminum sulfate, trivalent chromium is one or more of chromium trichloride or chromium phosphate, chromium sulfate, each component mass concentration is 0.2~5g/L, it is prepared with deionized water, and is sufficiently stirred 3~5 minutes with ultrasonic wave.It is water-soluble that this additive is that inorganic salts are in neutrality, and does not react with ingredients other in electrolyte.This additive is non-volatile, and dosage is few, non-toxic easy to maintain.Add the covering power that electrolyte can be improved after this additive, electroformed layer hardness is also significantly improved, can be obtained it is fine and close it is smooth, porosity is low, be unlikely to deform and mass fraction reach 99.9% thick layer gold.
Description
Technical field
The present invention relates to a kind of additives for gold without cyanogen electroforming process, specifically a kind of for improving without cyanogen
Additive formulations used in electroforming gold solution covering power and the gold electroforming process of hardness.
Background technique
The chemical stability of gold is fine, it is the metal not reacted with oxygen uniquely under high temperature, nearly all with various acid, alkali
It does 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 by the favor of people.Gold electroforming process is a kind of electro-deposition forming technique, is that one kind of plating special is answered
With principle is identical as plating.Mostly use cyaniding electroforming gold solution in electroforming gold process greatly in the early time, which has good dispersion
Ability and covering power, coating crystallization are careful.But chemicals of the cyanide as severe toxicity is constituted environment and operator very big
Threat.Country has promulgated related command, eliminates application of the cyanide in plating, electroforming process.
For a long time, domestic and foreign scholars are to capableing of having carried out extensively without cyanogen electroforming gold process for substitute electroforming gold process
General research, mainstream research is concentrated mainly on sulfurous acid system at present, 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 that generate on anode, causes the decomposition of plating solution.
And sulphite system needs the supplement of additional gold salt and electrolyte to use aging phenomenon after a period of time in process of production
Than more serious.Therefore, solve the problems, such as that gold electroforming process is that related personnel asks at the one of discussion always in industry
Topic.It is concentrated mainly on that electrolyte covering power is poor, and stability is poor the problem of gold electroforming process, obtained electroformed layer is hard
It spends inadequate etc..
In view of the above-mentioned problems, domestic and foreign scholars have carried out relevant exploration, two phase alloys are formed by metal co-deposition
Method improves the hardness of electroformed layer, such as gold/cobalt co-deposition, gold/carbon co-deposition, gold/nickel co-deposition.But these yuan
The addition of element can also make deposition layer have quite high internal stress, make deposition layer while reducing current efficiency
The phenomenon that stress cracking, so that electroformed layer brittleness is larger.
China discloses the application for a patent for invention of " a kind of technique of double-pulse plating gold " on May 21st, 2014, application
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 lower using deposition rate in electroforming gold field, it is not well positioned to meet industrial requirement.There are also at 2015 2
" a kind of no cyanogen electroforming gold solution and gold electroforming method " of the application of China Geological Univ. Wuhan disclosed in months 18 days, Patent No.
201410667310.9, which also describes the electroforming gold solution and technique of cyanide-free gold electroplating, involved in the patented technology
It is the casting gold solution of no cyanogen gold chloride system, using gold chloride as gold salt in no cyanogen gold chloride system, chloride ion is main complex ion.It should
The higher thick layer gold of the available Vickers hardness of system, direct current, which is changed to pulse current, can make deposition layer crystal grains fine,
Cast layer thickeies, and intensity becomes larger.But the system still has some aspects for needing to optimize, for example only relies on basic bath, it is deep
Degree ability is not ideal enough, and obtained deposition layer covering power is poor, and electroformed layer is in uneven thickness, so that integral strength is still not
It is well positioned to meet the requirement of product.
Summary of the invention
The invention aims to the shortcomings of the prior art of solution, and provide one kind and specially solve current gold electricity
The problems such as cast layer hardness is not enough, deep plating property is poor is used for additive of the gold without cyanogen electroforming process, in the base of basic electrolyte
By adding this additive on plinth, available 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.
To achieve the above object, the technical measures that the present invention takes be to provide it is a kind of for gold without cyanogen electroforming process
Additive, the cationic compound containing trivalent in additive component, the cationic compound be ferric iron, trivalent aluminium,
Trivalent chromium, anion are chloride ion, sulfate radical, phosphate radical；The ferric iron is in iron chloride or ferric phosphate, ferric sulfate
One or more, trivalent aluminium be aluminium chloride perhaps one or more of aluminum phosphate, aluminum sulfate trivalent chromium be chromium trichloride or
One or more of chromium phosphate, chromium sulfate；
The mass concentration of the additive each component is 0.2~5g/L, is prepared with deionized water, and filled with ultrasonic wave
Divide stirring 3~5 minutes；
The additive is added to gold without in cyanogen gold electroforming electrolyte according to required dosage, electroforming process condition
For the electrolyte pH of gold electroforming is 2~6, and temperature is 20~40 DEG C；Electric pulse parameter is 200~2000Hz of positive pulse frequency,
Direct impulse turn-on time is 10~200ms, and positive duty ratio is 10%~70%, and reverse impulse frequency is 200~2000Hz,
Reverse impulse turn-on time is 5~100ms, and reversed duty ratio is 10%~90%.
Gold electroforming system of the gold used in the present invention without cyanogen gold electroforming is gold chloride system, is matched in basic electrolyte
This additive, operating condition are added on the basis of side are as follows: the electrolyte pH range of gold electroforming is 2~6, and temperature is 20~40 DEG C.
After adding this additive, the thickness gold of 200 μm of thickness, 99.9% or more mass fraction, microhardness 100HV0.2/15 can get
Layer.
The present invention has the beneficial effect 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 lower problem of the product electroformed layer hardness that electroforming obtains, while additive of the invention do not have to mend again during electroforming
Other additives are filled, the industrialization demand of electroforming industry is able to satisfy.
(2), additive physicochemical properties of the invention are stablized, and good conductivity is non-volatile, and in electrolyte of getting along well at
Distribute biochemical reaction.
(3), additive formulations of the invention are simple, are free of extremely toxic substance, easy to maintain, and not volatile, pH value is neutrality, make
With conveniently, dosage is few, and easy to operate.
(4), at low cost using additive of the invention, the covering power and hardness of electrolyte can be significantly improved, addition is originally
The gold product electroformed layer hardness that electroforming obtains after the additive of invention is significantly improved, and Vickers hardness number can achieve
100HV0.2/15, and product crystallization is careful, corrosion resistance is strong, and porosity is low.
Specific embodiment
The present invention is further explained in the light of specific embodiments, but implementation of the invention is without being limited thereto.
The basic electrolyte of predetermined volume is prepared, the additive for calculating required according to basic electrolyte known concentration is each
Additive is added in electrolyte by the quality of component according to required dosage.Contain the cationization of trivalent in additive component
Object is closed, additive each component is that analysis is pure, is prepared with deionized water, and be sufficiently stirred 3~5 minutes with ultrasonic wave, Ji Kekai
Begin to carry out gold electroforming.Following embodiment is currently preferred case study on implementation.
Embodiment 1: the present invention provides a kind of additive for gold without cyanogen electroforming process, contains three in additive component
The cationic compound of valence is ferric phosphate 0.2g/L, and aluminium chloride 5g/L, chromium trichloride 1g/L prepare with deionized water, and with surpassing
Sound wave is sufficiently stirred 3 minutes, is added in basic electrolyte.Basis includes: gold chloride (gold ion concentration without cyanogen electroforming gold solution
Meter) 10g/L, potassium chloride 80g/L, potassium dihydrogen phosphate 20g/L, pH2,40 DEG C of temperature.Electrolyte, technique are used as according to the formula
Condition is that electric pulse parameter is positive pulse frequency 200Hz, and direct impulse turn-on time is 50ms, and positive duty ratio is 50%,
Reverse impulse frequency is 1000Hz, and reverse impulse turn-on time is 25ms, and reversed duty ratio is 10%.Thickness can be obtained with electroforming
200 μm, 99.9% or more mass fraction, micro-vickers hardness 105HV0.2/15 thick layer gold product in homogeneous thickness.
Embodiment 2: the present invention provides a kind of additive for gold without cyanogen electroforming process, contains phosphorus in additive component
Sour iron 5g/L, aluminium chloride 0.2g/L, aluminum sulfate 0.2g/L, chromium sulfate 0.5g/L.Basis includes: gold chloride without cyanogen electroforming gold solution
(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 positive pulse frequency 1000Hz, and direct impulse turn-on time is 200ms, just
It is 20% to duty ratio, reverse impulse frequency is 800Hz, and reverse impulse turn-on time is 100ms, and reversed duty ratio is 90%.
200 μm of available thickness, 99.9% or more mass fraction, micro-vickers hardness 102HV0.2/15 thick layer gold in homogeneous thickness.
Embodiment 3: the present invention provides a kind of additive for gold without cyanogen electroforming process, contains chlorine 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 gold electroforming
Liquid includes: gold chloride (gold ion densimeter) 15g/L, potassium chloride 120g/L, potassium dihydrogen phosphate 20g/L, pH5, and 30 DEG C of temperature.It presses
It is used as electrolyte according to the formula, process conditions are that electric pulse parameter is positive pulse frequency 2000Hz, when direct impulse is connected
Between be 120ms, positive duty ratio be 10%, reverse impulse frequency be 2000Hz, reverse impulse turn-on time be 60ms, reversely account for
Sky is than being 40%.200 μm of available thickness, 99.9% or more mass fraction, micro-vickers hardness 110HV0.2/15 thickness are equal
Even thick layer gold.
Embodiment 4: the present invention provides a kind of additive for gold without cyanogen electroforming process, contains chlorine in additive component
Change iron 3g/L, aluminium chloride 1g/L, chromium phosphate 2g/L.Basis includes: gold chloride (gold ion densimeter) without cyanogen electroforming gold solution
25g/L, potassium chloride 140g/L, potassium dihydrogen phosphate 30g/L, pH4,40 DEG C of temperature.Electrolyte, technique item are used as according to the formula
Part is that electric pulse parameter is positive pulse frequency 500Hz, and direct impulse turn-on time is 10ms, and positive duty ratio is 30%, instead
It is 200Hz to pulse frequency, reverse impulse turn-on time is 5ms, and reversed duty ratio is 20%.200 μm of available thickness, matter
Measure 99.9% or more score, micro-vickers hardness 100HV0.2/15 thick layer gold in homogeneous thickness.
Embodiment 5: the present invention provides a kind of additive for gold without cyanogen electroforming process, contains sulphur in additive component
Sour iron 3g/L, aluminum phosphate 0.2g/L, chromium sulfate 3g/L.Basis includes: gold chloride (gold ion densimeter) without cyanogen electroforming gold solution
30g/L, potassium chloride 150g/L, potassium dihydrogen phosphate 35g/L, pH3,20 DEG C of temperature.Electrolyte, technique item are used as according to the formula
Part is that electric pulse parameter is positive pulse frequency 333Hz, and direct impulse turn-on time is 40ms, and positive duty ratio is 70%, instead
It is 800Hz to pulse frequency, reverse impulse turn-on time is 20ms, and reversed duty ratio is 30%.200 μm of available thickness,
99.9% or more mass fraction, micro-vickers hardness 106HV0.2/15 thick layer gold in homogeneous thickness.
Additive formulations of the invention are simple, and dosage is few, at low cost, easy to use, and easy to operate.It adds of the invention
The gold product Vickers hardness number that electroforming obtains after additive can achieve 100HV0.2/15, and product crystallizes careful, corrosion resistance
By force, porosity is low.
Claims (1)
1. a kind of additive for gold without cyanogen electroforming process, the cationic compound containing trivalent in additive component, institute
The cationic compound stated is ferric iron, trivalent aluminium, trivalent chromium, and anion is chloride ion, sulfate radical, phosphate radical；Described three
Valence iron is that perhaps one or more of ferric phosphate, ferric sulfate trivalent aluminium are in aluminium chloride or aluminum phosphate, aluminum sulfate to iron chloride
One or more, trivalent chromium be one or more of chromium trichloride or chromium phosphate, chromium sulfate；It is characterized by: described
The mass concentration of additive each component be 0.2~5g/L, prepared with deionized water, and be sufficiently stirred 3~5 points with ultrasonic wave
Clock；
The additive is added to gold without in cyanogen gold electroforming electrolyte according to required dosage, electroforming process condition is electricity
The electrolyte pH of casting gold is 2~6, and temperature is 20~40 DEG C；Electric pulse parameter is 200~2000Hz of positive pulse frequency, positive
Pulse turn-on time is 10~200ms, and positive duty ratio is 10%~70%, and reverse impulse frequency is 200~2000Hz, reversely
Pulse turn-on time is 5~100ms, and reversed duty ratio is 10%~90%.
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| 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 |
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| 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 |
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| CN106637307A CN106637307A (en) | 2017-05-10 |
| CN106637307B true CN106637307B (en) | 2019-01-01 |
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|---|---|---|---|---|
| GB1251593A (en) * | 1969-01-10 | 1971-10-27 | ||
| US4310391A (en) * | 1979-12-21 | 1982-01-12 | Bell Telephone Laboratories, Incorporated | Electrolytic gold plating |
| GB2242200B (en) * | 1990-02-20 | 1993-11-17 | Omi International | Plating compositions and processes |
| ATE220736T1 (en) * | 1995-11-03 | 2002-08-15 | Enthone Omi Inc | ELECTROPLATTING METHODS, COMPOSITIONS AND COATINGS |
| CN101240436B (en) * | 2007-04-06 | 2010-12-22 | 中山火炬职业技术学院 | Gold electroforming technique |
| CN102105623B (en) * | 2008-06-11 | 2013-10-02 | 日本高纯度化学株式会社 | Electrolytic gold plating solution and gold film obtained using same |
| CN101392392A (en) * | 2008-10-22 | 2009-03-25 | 山东招金万足金珠宝有限公司 | Rigid pure gold ornamental article processing technology |
| CN101828799A (en) * | 2009-03-11 | 2010-09-15 | 栢莱化工有限公司 | Method for manufacturing hard gold jewelry |
| CN101560676B (en) * | 2009-04-24 | 2011-09-28 | 武汉金凰珠宝股份有限公司 | Method for electroforming hard gold product |
| CN102591134B (en) * | 2012-03-15 | 2015-05-13 | 昆山维信诺显示技术有限公司 | Mask plate and preparing method thereof |
| CN102758230B (en) * | 2012-07-11 | 2015-04-08 | 东莞市闻誉实业有限公司 | Gold electroplating solution and gold electroplating method |
| CN103741180B (en) * | 2014-01-10 | 2015-11-25 | 哈尔滨工业大学 | Non-cyanide bright electrogilding additive and application thereof |
| 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 |
| CN104357883B (en) * | 2014-11-20 | 2016-09-14 | 中国地质大学（武汉） | A kind of without cyanogen electroforming gold solution and electroforming gold method |
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2017
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