CN105332017A - Disulfide heterocyclic compound cyanide-free gilding electroplating solution and method - Google Patents
Disulfide heterocyclic compound cyanide-free gilding electroplating solution and method Download PDFInfo
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- CN105332017A CN105332017A CN201410396253.5A CN201410396253A CN105332017A CN 105332017 A CN105332017 A CN 105332017A CN 201410396253 A CN201410396253 A CN 201410396253A CN 105332017 A CN105332017 A CN 105332017A
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Abstract
The invention discloses a disulfide heterocyclic compound cyanide-free gilding electroplating solution and method. The electroplating solution comprises, 10 g/L to 15 g/L of auric chloride by gold, 72 g/L to 108 g/L of a disulfide heterocyclic compound by disulfide group, 1 g/L to 4 g/L of glycerol, 0.30 g/L to 0.65 g/L of an organic phosphorus compound and 0.05 g/L to 0.14 g/L of thallous salt by thallium. The disulfide heterocyclic compound serves as a main coordination agent, the glycerol serves as a stabilizing agent, the organic phosphorus compound serves as an electron acceleration agent, the thallous salt serves as a brightening agent, and the auric chloride serves as main auric salt, so that the obtained electroplating solution has the good dispersion force and the deep-plating capacity, the cathode current efficiency is high, and the performance of the electroplating solution is excellent. The electroplating solution is adopted for electroplating under the alkaline condition, so that an obtained plated layer is low in porosity, high in brightness and good in quality.
Description
Technical field
The present invention relates to electrogilding technical field, particularly relate to a kind of electroplate liquid and electro-plating method of dithia cyclic cpds cyanogen-less gold.
Background technology
Gold ductility is good, is easy to polishing, has lower contact resistance, and conductivity, welding property are good, are widely used in the electronics industry as solderable coating.Gold is high temperature resistant, and hard gold is also more wear-resisting, and therefore gold plate is widely used in the part that precision instrument, instrument, printed-wiring board (PWB), unicircuit, shell, electric contact etc. require electrical parameter performance long-term stability.The chemical stability of gold is very high, and be only dissolved in chloroazotic acid and be insoluble to other acid, thus gold plate solidity to corrosion is very strong, and have good discoloration-resisting, meanwhile, au-alloy coating has multiple color tones, therefore is commonly used for famous and precious decorative coating, as jewelry, wrist-watch, artwork etc.
Gold-plated and the cyanogen-less gold of cyanogen is had according to whether being divided into containing prussiate in gold-plated plating solution.Because prussiate has severe toxicity, under the large historical background progressively strengthened of environmental consciousness, cyanide electroplating gold starts to be limited by legislation by national governments.The exploitation of cyanogen-less gold highlights huge market outlook.The performance of existing cyanide electroplating gold ubiquity plating solution is not good, and the technological deficiency that quality of coating is not high, these seriously constrain cyanide-free gold electroplating further genralrlization industrially.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of electroplate liquid of dithia cyclic cpds cyanogen-less gold, and the plating solution performance of this electroplate liquid is better, and the quality of coating using this plating solution to obtain is higher.
An electroplate liquid for dithia cyclic cpds cyanogen-less gold, comprise in the gold perchloride of gold 10 ~ 15g/L, in the dithia cyclic cpds of disulfide group 72 ~ 108g/L, the glycerine of 1 ~ 4g/L, the organo phosphorous compounds of 0.30 ~ 0.65g/L and 0.05 ~ 0.14g/L in the sub-thallium salt of thallium.
Wherein, comprise in the gold perchloride of gold 12g/L, in the dithia cyclic cpds of disulfide group 88g/L, the glycerine of 3g/L, the organo phosphorous compounds of 0.45g/L and 0.08g/L in the sub-thallium salt of thallium.
Wherein, described dithia cyclic cpds is two (2-thienyl) disulfide, 2,2'-bis-sulphur two pyridines or 4,4'-bis-sulphur two pyridines
Wherein, described organo phosphorous compounds is ketone group phosphorus compound or aminoalkyl phosphide, and described sub-thallium salt is Thallous iodide.
In the technical scheme of above electroplate liquid, select as gold perchloride is main salt.In the present invention, gold ion content can make that cathode current density is higher and sedimentation velocity is very fast.If golden salts contg is too high, not only can increase electroplating cost, and coating can be made to produce the phenomenon of fragility increase; If content is too low, tint is poor, and cathode current density is lower, and sedimentation velocity is slower.
Select as the main coordination agent of dithia cyclic cpds.The molecular structure of dithia cyclic cpds is that the two ends of disulfide group (-S-S-) connect two heterocyclic groups, and two heterocyclic groups can be identical, also can not be identical.Heterocyclic group can be five yuan or hexa-atomic heterocyclic group, such as, be thienyl, pyridyl.-S-S-in dithia cyclic cpds and gold ion form comparatively stable complex compound.
Select glycerine as stablizer, inferior sulfate radical can be prevented oxidized.
Select sub-thallium salt to be brightening agent, improve the luminance brightness of coating.Because sub-thallium ion occurs to owe electromotive force deposition in gold surface, thus improve the deposition potential of gold, make coating crystallization careful.
Select organo phosphorous compounds to contain unpaired electron, it can have the effect accelerating electron transmission, is conducive to the additive of the quickening of sedimentation velocity.These additives have hydrophilic group, to raising complex ion spread coefficient, reduce thickness of diffusion layer all favourable, thus accelerate the mobility of solution, improve the current density of plating solution.
Except mentioned component, the present invention also can select suitable amounts other in this area the additive commonly used, such as conductive agent salt of wormwood, auxiliary complexing agent such as citric acid or its salt etc., these all can not damage the characteristic of coating.
The present invention provides on the other hand a kind of electro-plating method of dithia cyclic cpds cyanogen-less gold, the method the better performances of electroplate liquid that is suitable for, higher according to quality of coating prepared by the method.
Use an above-mentioned electroplate liquid electric plating method, comprise the following steps:
(1) prepare electroplate liquid: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains counts the dithia cyclic cpds 7 of 72 ~ 108g, 1 ~ 4g glycerine, 0.30 ~ 0.65g organo phosphorous compounds and 0.05 ~ 0.14g in the sub-thallium salt of thallium in gold 10 ~ 15g gold perchloride, disulfide group;
(2) insert with pretreated negative electrode and anode and pass into electric current in described electroplate liquid and electroplate.
Wherein, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 0.5 ~ 1ms, and dutycycle is 5 ~ 30%, and average current density is 0.5 ~ 1A/dm
2.
Wherein, in described step (2), the pH of electroplate liquid is 8 ~ 10.
Wherein, the temperature of electroplate liquid is 50 ~ 60 DEG C.
Wherein, the time of plating is 20 ~ 40min.
Wherein, the area ratio of described step (2) Anodic and negative electrode is (1 ~ 4): 1.
In the technical scheme of above electro-plating method, monopulse rectangular wave current is defined as at t
1passing into current density in time is J
pelectric current, at t
2without passing into electric current in time, it is a kind of intermittent pulse current.Dutycycle is defined as t
1/ (t
1+ t
2), frequency is 1/ (t
1+ t
2), mean current is defined as J
pt
1/ (t
1+ t
2).Compare with DC electrodeposition, thickness and the ion concentration distribution of electrostatic double layer all change; While adding electrochemical polarization, reduce concentration polarization, the direct effect of generation is, the coating that pulse plating obtains than DC electrodeposition coating evenly, crystallization is finer and closely woven.Moreover, pulse plating also has: hardness and the wear resistance of (1) coating are all high; (2) solution dispersibility and covering power good; (3) decrease the super plating of part edge, coating distributing homogeneity is good, can save plating solution usage quantity.
Using Copper Foil as negative electrode, take platinized platinum as anode.Anticathode pre-treatment is by comprising anticathode sand papering, oil removing, pickling, preimpregnation copper after elder generation successively.This use sand papering can polish twice, and first time with flint paper such as 200 object sand paperings, can be used fine sandpaper, such as, can use WC28 abrasive paper for metallograph for the second time.This oil removing can first adopt chemical alkali liquor oil removing then to adopt the dehydrated alcohol oil removing of 95%.Wherein, chemical alkali lye consists of: 50 ~ 80g/LNaOH, 15 ~ 20g/LNa
3pO
4, 15 ~ 20g/LNa
2cO
3and 5g/LNa
2siO
3with 1 ~ 2g/LOP-10.Electrochemical deoiling detailed process is through treating oil removing negative electrode 15 ~ 40 DEG C of dipping 30s in chemical alkali lye.The pickling time is 1 ~ 2min, and the object of pickling is activation, specifically, removes the oxide film on plating piece top layer, makes the lattice of matrix completely exposed, be in active state.Pickling solution composition used is: 100g/L sulfuric acid and 0.15 ~ 0.20g/L thiocarbamide.The preimpregnation copper time is 1 ~ 2min, and solution composition used is: 100g/L sulfuric acid, 50g/L anhydrous cupric sulfate and 0.20g/L thiocarbamide.
The area ratio of step (2) Anodic and negative electrode is preferably 3:1.Ratio of cathodic to anodic area is crossed conference and is made it more easily passivation occur; Otherwise, then cathode copper sedimentation rate can be caused too small, thus reduce current efficiency.
The pH of electroplate liquid is 8 ~ 10.PH is less than 8, and the sulphur atom that gold ion can be caused to be oxidized in disulfide group produces sulphur simple substance.If be greater than 10, plating solution can become dun, affects the gloss of final coating.
The present invention with dithia cyclic cpds for main coordination agent, take glycerine as stablizer, take organo phosphorous compounds as Accelerating electron agent, with sub-thallium salt for brightening agent, take gold perchloride as the main salt of gold, make the plating solution of acquisition have good dispersion force and covering power thus, cathode efficiency is high, and plating solution performance is excellent.The porosity that employing electroplates the coating of acquisition in the basic conditions at plating solution is low, and luminance brightness is high, and quality of coating is good.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with embodiment.
According to formulated electroplate liquid described in embodiment 1 ~ 6, specific as follows: the quality taking each feed composition according to formula electronic balance.Fully mix then after each feed composition is dissolved in appropriate deionized water respectively, add water move to pre-determined volume, adding caustic soda adjust ph is 8 ~ 10.
The electroplate liquid of formulated described in embodiment 1 ~ 6 and comparative example is used to carry out electric plating method:
(1) negative electrode adopts the Copper Foil of 10mm × 10mm × 0.1mm specification.Metalluster is exposed with the polishing of WC28 abrasive paper for metallograph to surface again after first tentatively being polished with 200 order waterproof abrasive papers by Copper Foil.Successively through temperature be 50 ~ 70 DEG C chemical alkali liquor oil removing, distilled water flushing, 95% dehydrated alcohol oil removing, distilled water flushing, pickling 1 ~ 2min, preimpregnation copper 1 ~ 2min, redistilled water rinse.Wherein, the formula of chemical alkali lye is 50 ~ 80g/LNaOH, 15 ~ 20g/LNa
3pO
4, 15 ~ 20g/LNa
2cO
3and 5g/LNa
2siO
3with 1 ~ 2g/LOP-10.Pickling solution composition used is: 100g/L sulfuric acid and 0.15 ~ 0.20g/L thiocarbamide.The solution composition used of preimpregnation copper is: 100g/L sulfuric acid, 50g/L anhydrous cupric sulfate and 0.20g/L thiocarbamide.
(2) with the platinum plate of 15mm × 10mm × 0.2mm specification for anode, by level and smooth for sand papering, deionized water rinsing and oven dry before plating.
(3) by the electroplate liquid in pretreated anode and negative electrode immersion plating groove, just plating tank is placed in thermostat water bath, and is plating tank installation electric blender, the stirring rod of electric blender is inserted in electroplate liquid.Bath temperature to be regulated makes temperature of electroplating solution maintain 50 ~ 60 DEG C, and after mechanical stirring rotating speed is adjusted to 100 ~ 250rpm, make pulse power supply, the pulsewidth of pulsed current is 0.5 ~ 1ms, and dutycycle is 5 ~ 30%, and average current density is 0.5 ~ 1A/dm
2.After 20 ~ 40min to be energised, cut off the power supply of electroplanting device.Take out steel plate, use distilled water cleaning, drying.
Embodiment 1
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.5ms, and dutycycle is 30%, and average current density is 0.5A/dm
2; PH is 8, and temperature is 60 DEG C, and electroplating time is 40min.
Embodiment 2
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.6ms, and dutycycle is 25%, and average current density is 0.6A/dm
2; PH is 8.5, and temperature is 60 DEG C, and electroplating time is 35min.
Embodiment 3
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.8ms, and dutycycle is 20%, and average current density is 1A/dm
2; PH is 9, and temperature is 50 DEG C, and electroplating time is 20min.
Embodiment 4
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 1ms, and dutycycle is 15%, and average current density is 0.9A/dm
2; PH is 10, and temperature is 50 DEG C, and electroplating time is 25min.
Embodiment 5
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.9ms, and dutycycle is 5%, and average current density is 0.8A/dm
2; PH is 9.5, and temperature is 55 DEG C, and electroplating time is 30min.
Embodiment 6
The formula of electroplate liquid is as follows:
Plating technology condition: the pulsewidth of monopulse rectangular wave current is 0.7ms, and dutycycle is 10%, and average current density is 0.7A/dm
2; PH is 9.2, and temperature is 55 DEG C, and electroplating time is 35min.
With reference to following methods, dispersive ability test is carried out to the plating solution of embodiment 1 ~ 6:
The dispersive ability of plating solution adopts far and near cathode method (Haring-Blue method) to measure.Measure the Hull groove that groove adopts the HullCell267ml model of Kocour company of the U.S., interior dimensions is 150mm × 50mm × 70mm.Negative electrode selects thickness to be the copper sheet of 0.5mm, and working face is of a size of 50mm × 50mm; Anode is plating nickel plate with holes; Plating electric current 1A, electroplating time 30min.
The dispersive ability calculation formula of plating solution is:
Dispersive ability=[K-(the Δ M of plating solution
1/ Δ M
2)]/(K-1) (result represents with percentage);
In formula, K is negative electrode far away to the distance of anode and nearly negative electrode to the ratio of distances constant of anode, and in this test, K gets 2; Δ M
1for the increment (g) after plating on nearly negative electrode; Δ M
2for the increment (g) after plating on negative electrode far away.
With reference to following methods, covering power test is carried out to the plating solution of embodiment 1 ~ 6:
Endoporus method is adopted to measure.Negative electrode selects internal diameter l10mm, and pipe range is the copper pipe of 50mm, and one end is closed.During test, the distance of the mouth of pipe and anode is fixed on 80mm, test current 0.2A, electroplating time 30min.According to following formulae discovery:
Covering power=endoporus coating length/pipe range (result represents with percentage).
With reference to following methods, current efficiency test is carried out to the plating solution of embodiment 1 ~ 6:
Copper voltameter method is adopted to measure.Negative electrode to be tested and copper voltameter cleaned and dry up rear electronic scale weighing, then insert in electrodeposit groove by two negative electrodes simultaneously, be energized 10 ~ 30min, take out and clean dry up after use electronic scale weighing.According to following formulae discovery:
Current efficiency=(1.186 × cathode quality to be measured)/(electrochemical equivalent of copper voltameter quality × cathodic deposition metal to be measured) × 100%.Here, electrochemical equivalent=molar mass ÷ (depositing ions valency × 26.8), unit is g.A
-1.h
-1.In this test, trivalent Au electrochemical equivalent is 2.453g.A
-1.h
-1.
Speed test is plated with reference to the plating solution of following methods to embodiment 1 ~ 6:
Mass method is adopted to measure sedimentation rate.Be 10 with sensitivity
-4electronic balance weighing sample plating before and after quality.By the acquisition sedimentation rate of poor quality of unit time, unit surface, press formulae discovery below:
Plating speed=(after plating before sample mass-plating sample mass)/(specimen surface to be plated long-pending × plating time).Each Data duplication is measured three times and is got its mean value.
Test with reference to the bonding force of following methods to the coating of embodiment 1 ~ 6:
The method adopting line to draw lattice measures the bonding force of coating, is specially: being 30 degree with one cutting edge by electrodeposition cladding, converted steel draws parallel lines or the 1mm that 2mm of being separated by drawn by cutter
2square lattice.Whether the coating observing line tilts or peels off.Should master the dynamics during line, a cutter just can scratch coating, arrives matrix metal.Adopt quench to measure the bonding force of coating, be specially: the test piece of having plated is placed in retort furnace quenching in the cold water being heated to 300 DEG C of insulation 30min taking-up immersion 10 DEG C immediately, observe coating and whether occur bubble and decortication phenomenon.
With reference to following methods, toughness test is carried out to the coating of embodiment 1 ~ 6:
Coating is stripped down, is bent to 180 °, and extrudes knee, observe coating and whether occur fracture.
With reference to following methods, porosity test is carried out to the coating of embodiment 1 ~ 6:
The large young pathbreaker of porosity is directly connected to the corrosion resisting property of coating, adopts paster method to press GB5935-86 standard detection.The etchant solution that the potassium ferricyanide solution of 10g/L and the sodium chloride solution of 20g/L are tested as porosity.Operation steps is: after wiped clean of being deoiled by coating surface, is close to coating surface with the filter paper soaking into etchant solution, and the two can not have gap.Buy the fully wetting filter paper of etchant solution solution by glass stick or degreasing swab stick, supplement a solution at interval of 1min, taken off by filter paper after 5min, dry after clean with distilled water flushing, record hole is counted.Be placed on cleaned glass plate and dry, the number of number Bluepoint.Substitute into formulae discovery voidage below:
Number/tested area (individual/the cm of porosity=spot
2);
When calculating number of apertures, do following calculating by spot diameter size: hot spot diameter is less than 1mm, and with a porosimeter at often; Be greater than 1mm and be less than 3mm often o'clock with three porosimeters; Be greater than 3mm and be less than 5mm, often with ten porosimeters.
With reference to following methods, Surface flat test is carried out to the coating of embodiment 1 ~ 6:
By the Hull groove of the HullCell267ml model with the Kocour company of the test piece U.S. after 200 order sand paperings evenly at 3A/dm
2dC current density carries out plating 10min at 25 DEG C of temperature, and whether then observe test piece has scratch.
To expose aptitude tests with reference to the coating of following methods to embodiment 1 ~ 6:
Adopt the Hull groove of the HullCell267ml model of Kocour company of the U.S. at 3A/dm
2after DC current density carries out plating 10min at 25 DEG C of temperature, observe the surface luminous intensity of coating.
The test result of the coating of embodiment 1 ~ 6 and comparative example and the performance of plating solution is as follows:
As can be seen from the above table, in embodiment 1 ~ 6, consider from the integration test effect of plating solution and coating, the dispersive ability of the formula plating solution of embodiment 6, covering power, current efficiency and plating speed, the porosity of coating and bonding force will be got well compared with other embodiment.Thus, this formula is screening formulation of the present invention, and the preferred plating conditions of its correspondence is the pulsewidth of monopulse rectangular wave current is 0.7ms, and dutycycle is 10%, and average current density is 0.7A/dm
2; PH is 9.2, and temperature is 55 DEG C, and electroplating time is 35min, and male and femal face is long-pending than being 3:1.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, various amendment and improvement can be made to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not by the restriction of given any specific exemplary teachings.
Below know-why of the present invention is described in conjunction with specific embodiments.These describe just in order to explain principle of the present invention, and can not be interpreted as limiting the scope of the invention by any way.Based on explanation herein, those skilled in the art does not need to pay performing creative labour can associate other embodiment of the present invention, and these modes all will fall within protection scope of the present invention.
Claims (10)
1. the electroplate liquid of a dithia cyclic cpds cyanogen-less gold, it is characterized in that, comprise in the gold perchloride of gold 10 ~ 15g/L, in the dithia cyclic cpds of disulfide group 72 ~ 108g/L, the glycerine of 1 ~ 4g/L, the organo phosphorous compounds of 0.30 ~ 0.65g/L and 0.05 ~ 0.14g/L in the sub-thallium salt of thallium.
2. electroplate liquid according to claim 1, is characterized in that, comprise in the gold perchloride of gold 12g/L, in the dithia cyclic cpds of disulfide group 88g/L, the glycerine of 3g/L, the organo phosphorous compounds of 0.45g/L and 0.08g/L in the sub-thallium salt of thallium.
3. electroplate liquid according to claim 1, is characterized in that, described dithia cyclic cpds is two (2-thienyl) disulfide, 2,2'-bis-sulphur two pyridines or 4,4'-bis-sulphur two pyridines.
4. electroplate liquid according to claim 1, is characterized in that, described organo phosphorous compounds is ketone group phosphorus compound or aminoalkyl phosphide, and described sub-thallium salt is Thallous iodide.
5. use the electroplate liquid electric plating method described in claim 1, it is characterized in that, comprise the following steps:
(1) prepare electroplate liquid: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains counts the dithia cyclic cpds 7 of 72 ~ 108g, 1 ~ 4g glycerine, 0.30 ~ 0.65g organo phosphorous compounds and 0.05 ~ 0.14g in the sub-thallium salt of thallium in gold 10 ~ 15g gold perchloride, disulfide group;
(2) insert with pretreated negative electrode and anode and pass into electric current in described electroplate liquid and electroplate.
6. want the method described in 5 according to right, it is characterized in that, described electric current is monopulse rectangular wave current; The pulsewidth of described monopulse rectangular wave current is 0.5 ~ 1ms, and dutycycle is 5 ~ 30%, and average current density is 0.5 ~ 1A/dm
2.
7. method according to claim 5, is characterized in that, in described step (2), the pH of electroplate liquid is 8 ~ 10.
8. method according to claim 5, is characterized in that, the temperature of electroplate liquid is 50 ~ 60 DEG C.
9. method according to claim 5, is characterized in that, the time of plating is 20 ~ 40min.
10. method according to claim 5, is characterized in that, the area ratio of described step (2) Anodic and negative electrode is (1 ~ 4): 1.
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|---|---|---|---|---|
| CN109972180A (en) * | 2019-04-12 | 2019-07-05 | 博敏电子股份有限公司 | The new application of 2,2 '-dithiodipyridine and the electro-plating method that filling perforation additive is electroplated and uses the additive for using it |
-
2014
- 2014-08-12 CN CN201410396253.5A patent/CN105332017A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109972180A (en) * | 2019-04-12 | 2019-07-05 | 博敏电子股份有限公司 | The new application of 2,2 '-dithiodipyridine and the electro-plating method that filling perforation additive is electroplated and uses the additive for using it |
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