CN105316724A - Electroplate liquid and electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy - Google Patents
Electroplate liquid and electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy Download PDFInfo
- Publication number
- CN105316724A CN105316724A CN201410373856.3A CN201410373856A CN105316724A CN 105316724 A CN105316724 A CN 105316724A CN 201410373856 A CN201410373856 A CN 201410373856A CN 105316724 A CN105316724 A CN 105316724A
- Authority
- CN
- China
- Prior art keywords
- pyrophosphate
- electroplate liquid
- content
- plating
- electroplate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Abstract
The invention discloses electroplate liquid and an electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy. The electroplate liquid is composed of 0.4-6 g/L of copper pyrophosphate in terms of copper, 8-36 g/L of stannous pyrophosphate in terms of tin, 72-189 g/L of alkali metal pyrophosphate in terms of pyrophosphate radicals, 0.36-0.72 g/L of brightening agents and 40-60 g/L of sulfosalicylic acid. The brightening agents are reaction products obtained through a reaction between piperazine and epoxy chloropropane which are equal in molar weight. According to the electroplate liquid, the copper pyrophosphate serves as main copper salt, the stannous pyrophosphate serves as main tin salt, the alkali metal pyrophosphate serves as coordination agents, the reaction products obtained through the reaction between the piperazine and the epoxy chloropropane which are equal in molar weight serve as the brightening agents, and the sulfosalicylic acid serves as electroplate liquid stabilizers, so that the obtained electroplate liquid is good in dispersion capacity and covering capacity, cathode currents are high in efficiency, and the electroplate liquid is excellent in performance. By the adoption of the electroplate liquid, plating obtained through electroplating under the alkaline condition is low in porosity, high in brightness and good in quality.
Description
Technical field
The present invention relates to electro-coppering tin technical field, particularly relate to a kind of non-cyanide plating Cu-Sn alloy pyrophosphate salt electroplate liquid and electro-plating method.
Background technology
Electroplating copper tin alloy develops one of alloy plating the earliest.Due to reasons such as nickel resources shortage, the price sustainable growth of nickel, more and more attracts much attention for nickel coating.Gunmetal is used for protection, decorative coating as nickel, both can meet service requirements, and also can reduce the use of nickel, and therefore have very high marketable value.The later stage eighties, research finds that the skin of metallic nickel contact people can cause nickel condition susceptible, thus in many countries, such as, EU member country drought is nickel content in just having made laws restriction jewelry the nineties, requires that the amount of precipitation every square centimeter of metallic nickel is no more than 0.5 microgram.Therefore study nickel substitute plating technique and have very large necessity.Following performance should be possessed: first the Surface flat of coating, luminance brightness will be got well, and have excellent decorative effect for nickel coating.Secondly, coating should be able to stop underlying metal to and the diffusion of layer, to prevent the variable color of precious metal plating.Moreover electroplating cost can not be too high.That commonly uses mainly contains electro-coppering alloy, plating palladium or Pd-Ni alloy, cobalt plating for nickel technique a few days ago.Cobalt plating and plating palladium all make their industrialization promotion be restricted because it is expensive.Plating Cu-Sn alloy, can obtain smooth and bright coating, the non-proliferation of gunmetal is functional, outbalance, and electroplating cost is ideal.Moreover, electroplating wastewater treatment technical requirements is not high.Based on this, plating Cu-Sn alloy obtains a wide range of applications in the plating of decoration protective, is most widely used generation one of nickel coating.
Because prussiate has severe toxicity, under the large historical background progressively strengthened of environmental consciousness, cyanide electroplating Cu-Sn alloy starts to be limited by legislation by national governments.The exploitation of cyanideless electro-plating highlights huge market outlook.The performance of existing cyanide electroplating Cu-Sn alloy ubiquity plating solution is not good, and the technological deficiency that quality of coating is not high, these seriously constrain non-cyanide copper electroplating tin further genralrlization industrially.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of electroplate liquid of non-cyanide plating Cu-Sn Alloy pyrophosphate salt, 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 non-cyanide plating Cu-Sn Alloy pyrophosphate salt, by content be 0.4 ~ 6g/L in copper cupric pyrophosphate, content be 8 ~ 36g/L be forming in the sulphosalicylic acid of pyrophosphate alkali metal pyrophosphate, content to be the brightening agent of 0.36 ~ 0.72g/L and content be 40 ~ 60g/L of 72 ~ 189g/L in tin stannous pyrophosphate, content; Described brightening agent is the reaction product obtained by the piperazine of equimolar amount and epichlorohydrin reaction.
Wherein, by content be 4g/L be 18g/L be 134g/L be 52g/L in pyrophosphate alkali metal pyrophosphate, the content brightening agent that is 0.50g/L and content in tin stannous pyrophosphate, content in copper cupric pyrophosphate, content sulphosalicylic acid forms.
In the technical scheme of above electroplate liquid, cupric pyrophosphate is selected to be the main salt of copper.Stannous pyrophosphate is selected to be the main salt of tin.。Pyrophosphate salt is selected to be coordination agent.Pyrophosphate salt is preferably alkali-metal pyrophosphate salt, such as trisodium phosphate or potassium.Alkali-metal pyrophosphate salt is soluble salt.Pyrophosphate can form complex compound with cupric ion and stannous ion, and the better simply bivalent cupric ion of the discharge potential of this complex compound when cathodic deposition is more negative, and namely degree of polarization is larger.Thus, complexing ion electric discharge is more steady, makes the more careful smooth of coating.Cupric pyrophosphate and the pyrophosphate contained by stannous pyrophosphate, as coordination agent negatively charged ion, can not cause the anionic impurity introducing other in plating solution.
Brightening agent be by the piperazine of equimolar amount and epoxy chloropropane at 50 ~ 70 DEG C by reaction product that condensation reaction 3 ~ 5h obtains.This reaction take water as reaction solvent.First by piperazine dissolved in water, when temperature is adjusted to 40 DEG C, epoxy chloropropane is added to above-mentioned solution under agitation, then constant temperature in 50 ~ 70 DEG C reaction the some time after, naturally cool to room temperature discharging.What deserves to be explained is, the isothermal reaction time is decided by feed time.The feed way of epoxy chloropropane can be intermittent type in batches, also can for drip formula continuously.But regardless of which kind of feed way, the rising degree of the temperature of reaction system should be brought control according to the release of reaction heat to reinforced speed.Specifically, for the epoxy chloropropane of 1mol, in step reinforced process in batches, often criticizing the timed interval that epoxy chloropropane feeds intake is 10 ~ 15min; In the process of continuous dropping formula, the overall time of dropping is advisable with 30 ~ 60min.
Select sulphosalicylic acid as bath stability agent.It can stop in plating solution because cupric is precipitated out from plating solution by the copper simple substance that stannous ion reduction produces.
In addition to the above additives, the present invention also can select suitable amounts other in this area the additive commonly used, these all can not damage the characteristic of coating.
The present invention provides on the other hand a kind of electro-plating method of non-cyanide plating Cu-Sn alloy pyrophosphate salt, 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) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains 0.4 ~ 6g and forms in pyrophosphate alkali metal pyrophosphate, 0.36 ~ 0.72g brightening agent and 40 ~ 60g sulphosalicylic acid in tin stannous pyrophosphate, 72 ~ 189g in copper cupric pyrophosphate, 8 ~ 36g; Described brightening agent is the reaction product obtained by the piperazine of equimolar amount and epichlorohydrin reaction;
(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 1 ~ 2A/dm
2.
Wherein, in described step (2), the pH of electroplate liquid is 8 ~ 10.
Wherein, the temperature of electroplate liquid is 30 ~ 50 DEG C.
Wherein, the time of plating is 25 ~ 50min.
Wherein, in described step (2), the area ratio of negative electrode and positive electrode is (1/2 ~ 2): 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 consumption.
Using the steel plate of low-carbon (LC) as negative electrode.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.
In step (2), the area ratio of negative electrode and positive electrode is preferably 1:1.5.Ratio of cathodic to anodic area is crossed conference and is made it more easily passivation occur, and even can produce mantoquita or cuprous oxide compound; Otherwise, then cathode copper sedimentation rate can be caused too small, thus reduce current efficiency.
Electroplate liquid of the present invention is slight alkalinity.If pH is too low, tetra-sodium is changed to positive phosphoric acid, thus produces adverse influence, such as, damage the homogeneity of galvanic deposit, also can make the shaggy coating of acquisition, and these all can not affect coating and occur abnormal.Otherwise current density narrows, the homogeneity of galvanic deposit and current efficiency reduce.Temperature also has a certain impact to plating solution, if such as temperature is too high, tetra-sodium is changed to positive phosphoric acid, thus causes coating to occur above-mentioned exception.
The present invention take cupric pyrophosphate as the main salt of copper, stannous pyrophosphate is the main salt of tin, using alkali-metal pyrophosphate salt as coordination agent, the reaction product obtained using the piperazine of equimolar amount and epichlorohydrin reaction is as brightening agent, using sulphosalicylic acid as bath stability agent, 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.
Prepare brightening agent in accordance with the following methods: 300ml water and 1mol (86g) piperazine are added in the there-necked flask with thermometer, serpentine condenser, whipping appts and thermostat water bath.Start stirrer, adjusting rotary speed is 200 ~ 500rpm, makes it stir and fully dissolves formation solution.Until by after this solution warms to 50 DEG C, the same time-division that 1mol (92g) epoxy chloropropane is stirring is added to above-mentioned solution 6 times, controlling the timed interval at every turn added between epoxy chloropropane is 10 ~ 15min, to ensure that the temperature of reaction soln is no more than 75 DEG C.After epoxy chloropropane is reinforced, constant temperature, in 50 ~ 70 DEG C, after total reaction time is 3 ~ 5h (total reaction time comprises aforesaid feed time), naturally cools to room temperature discharging, adds water and be settled to 1L, obtain brightening agent.
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 Q235 steel plate of 10mm × 10mm × 0.2mm 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 steel plate.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 copper sheet 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 30 ~ 50 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 1 ~ 2A/dm
2.After 25 ~ 50min 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 1A/dm
2; PH is 8, and temperature is 50 DEG C, and electroplating time is 50min.
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 1.2A/dm
2; PH is 8.5, and temperature is 45 DEG C, and electroplating time is 45min.
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 2A/dm
2; PH is 9, and temperature is 30 DEG C, and electroplating time is 40min.
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 1.8A/dm
2; PH is 10, and temperature is 35 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 1.6A/dm
2; PH is 9.5, and temperature is 45 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 1.5A/dm
2; PH is 9.8, and temperature is 40 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, monovalence Cu electrochemical equivalent is 2.372g.A
-1.h
-1, tetravalence Sn electrochemical equivalent is 1.107g.A
-1.h
-1.In embodiments of the invention, Sn mass percent/1.107 in Cu mass percent/2.372+ coating in the electrochemical equivalent=coating of cathodic deposition metal to be measured.
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 P content of PHI700SAM type Auger electron spectrometer to the coating of embodiment 1 ~ 6 and comparative example is adopted to test.
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 1.5A/dm
2; PH is 9.8, and temperature is 40 DEG C, and electroplating time is 35min, and negative and positive area ratio is 2:3.
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 non-cyanide plating Cu-Sn alloy pyrophosphate salt, it is characterized in that, by content be 0.4 ~ 6g/L in copper cupric pyrophosphate, content be 8 ~ 36g/L be forming in the sulphosalicylic acid of pyrophosphate alkali metal pyrophosphate, content to be the brightening agent of 0.36 ~ 0.72g/L and content be 40 ~ 60g/L of 72 ~ 189g/L in tin stannous pyrophosphate, content; Described brightening agent is the reaction product obtained by the piperazine of equimolar amount and epichlorohydrin reaction.
2. electroplate liquid according to claim 1, it is characterized in that, by content be 4g/L be 18g/L be 134g/L be 52g/L in pyrophosphate alkali metal pyrophosphate, the content brightening agent that is 0.50g/L and content in tin stannous pyrophosphate, content in copper cupric pyrophosphate, content sulphosalicylic acid forms.
3. electroplate liquid according to claim 1, is characterized in that, the temperature of described reaction is 50 ~ 70 DEG C.
4. electroplate liquid according to claim 1, is characterized in that, the time of described reaction is 3 ~ 5h.
5. use the electroplate liquid electric plating method described in claim 1, it is characterized in that, comprise the following steps:
(1) electroplate liquid is prepared: in water, dissolve each feed composition form electroplate liquid, described often liter of electroplate liquid contains 0.4 ~ 6g and forms in pyrophosphate alkali metal pyrophosphate, 0.36 ~ 0.72g brightening agent and 40 ~ 60g sulphosalicylic acid in tin stannous pyrophosphate, 72 ~ 189g in copper cupric pyrophosphate, 8 ~ 36g; Described brightening agent is the reaction product obtained by the piperazine of equimolar amount and epichlorohydrin reaction;
(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 1 ~ 2A/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 30 ~ 50 DEG C.
9. method according to claim 5, is characterized in that, the time of plating is 25 ~ 50min.
10. method according to claim 5, is characterized in that, in described step (2), the area ratio of negative electrode and positive electrode is (1/2 ~ 2): 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410373856.3A CN105316724A (en) | 2014-07-31 | 2014-07-31 | Electroplate liquid and electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410373856.3A CN105316724A (en) | 2014-07-31 | 2014-07-31 | Electroplate liquid and electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105316724A true CN105316724A (en) | 2016-02-10 |
Family
ID=55245007
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410373856.3A Pending CN105316724A (en) | 2014-07-31 | 2014-07-31 | Electroplate liquid and electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105316724A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA034147B1 (en) * | 2018-07-06 | 2020-01-09 | Белорусский Государственный Университет (Бгу) | Electrolyte for non-sublayer deposition of copper coatings on products of non-corrosion-resistant metals |
| CN113574211A (en) * | 2018-12-17 | 2021-10-29 | 赛峰飞机发动机公司 | Electrolyte for electrochemical machining of gamma-gamma' nickel-based superalloys |
-
2014
- 2014-07-31 CN CN201410373856.3A patent/CN105316724A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EA034147B1 (en) * | 2018-07-06 | 2020-01-09 | Белорусский Государственный Университет (Бгу) | Electrolyte for non-sublayer deposition of copper coatings on products of non-corrosion-resistant metals |
| CN113574211A (en) * | 2018-12-17 | 2021-10-29 | 赛峰飞机发动机公司 | Electrolyte for electrochemical machining of gamma-gamma' nickel-based superalloys |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104264195A (en) | Mercaptoiminazole cyanide-free gold-electroplating solution and electroplating method thereof | |
| CN105316724A (en) | Electroplate liquid and electroplate method for pyrophosphate used for cyanide-free plated Cu-Sn alloy | |
| CN105274589A (en) | Alkaline cyanogen-free copper plating electroplating liquid and electroplating method thereof | |
| CN105274588A (en) | Succinimide cyanogen-free monovalent copper plating electroplating liquid and electroplating method thereof | |
| CN105316728A (en) | Electroplate liquid and electroplate method for gelatin cyanide-free plated Cu-Sn alloy | |
| CN105316718A (en) | Electroplate liquid and electroplate method for cyanide-free gold electroplating of sulfite | |
| CN105297089A (en) | Arsenic-contained sulfite cyanide-free plated gold electroplating liquid and electroplating method | |
| CN104233385A (en) | Electroplating liquid for non-cyanide plating gold by thiazole and electroplating method thereof | |
| CN105316719A (en) | Electroplate liquid and electroplate method for cyanide-free gold plating of thallium-contained sulfite | |
| CN105316726A (en) | Electroplate liquid and electroplate method for pyrophosphate cyanide-free plated Cu-Sn alloy | |
| CN105200464A (en) | Hydrazine reducing agent cyanide-free cuprous electroplating solution and electroplating method | |
| CN105132961A (en) | Electroplating solution for hydroxymethyldimethyl cyanide-free monovalent copper plating, and electroplating method thereof | |
| CN104630843A (en) | Plating solution for acid copper plating by phenazine dye system and electroplating method thereof | |
| CN105316731A (en) | Electroplate liquid and electroplate method for benzaldehyde brightening agent cyanide plated Cu-Sn alloy | |
| CN105316723A (en) | Electroplate liquid and electroplate method for butynediol brightening agent cyanide-plated Cu-Sn alloy | |
| CN105316725A (en) | Electroplate liquid and electroplate method for composite additive cyanide-plated Cu-Sn alloy | |
| CN105463526A (en) | Plating solution for mercapto sulfonic acid non-cyanogen gold plating and plating method thereof | |
| CN105483768A (en) | Gluconic acid cyanide-free gold-electroplating solution and electroplating method thereof | |
| CN105316730A (en) | Electroplate liquid and electroplate method for diethylaminopropyne cyanide-plated Cu-Sn alloy | |
| CN105316720A (en) | Electroplate liquid and electroplate method for cyanide-free gold plating of antimony-contained sulfite | |
| CN105483770A (en) | Iodide-added thiosulfate cyanide-free gold-electroplating solution and electroplating method | |
| CN105401179A (en) | Thiosulfate cyanogens-free gold plating liquid added with phenol, and electroplating method | |
| CN105441996A (en) | Thiosulfate cyanide-free gold-plating electroplating liquid with added hydrazine hydrochloride and electroplating method | |
| CN105483769A (en) | Propylene-glycol-added thiosulfate cyanide-free gold-electroplating solution and electroplating method | |
| CN104630841A (en) | Electroplating liquid and electroplating method of biurea cyanide-free copper plating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20160210 |