CN101899664A - Electroplating method - Google Patents
Electroplating method Download PDFInfo
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- CN101899664A CN101899664A CN2009101076524A CN200910107652A CN101899664A CN 101899664 A CN101899664 A CN 101899664A CN 2009101076524 A CN2009101076524 A CN 2009101076524A CN 200910107652 A CN200910107652 A CN 200910107652A CN 101899664 A CN101899664 A CN 101899664A
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Abstract
The invention relates to an electroplating method, which belongs to the field of electroplating, and the method comprises the following steps: (a) copper preplating; (b) acid bright copper plating; (c) chemical immersion tin; and (d) white copper tin electroplating. An electroplated product obtained by using the electroplating method with concentration can well solve the phenomena of greater stress of an electroplated white copper tin layer and easy production of dynamic embrittlement, and effectively improve the wear resistance and the anti-salt spray corrosion performance of the plated layer. The electroplating method can be widely applied in decoration of surfaces of metal products.
Description
Technical field
The present invention relates to a kind of surface treatment method, relate in particular to a kind of electro-plating method.
Background technology
The bright nickel plating layer is because its good ornamental and protective, in decorating the protection industry, obtained to use widely, no matter the bright nickel plating layer is as intermediate deposit or decorative coating, very high use value is all arranged, be widely used in industries such as haberdashery and hardware, lamp decoration dress ornament, instrument, glasses, the bright nickel plating layer still is good non-proliferation coating simultaneously, is able to widespread use in the jewellery production.
But directly contacting people's skin, metallic nickel can cause the responsive symptom of nickel, the existing clearly regulation in developed country such as America and Europe and area particularly in the world, the metal of decoration that contacts with human body skin such as wrist-watch, glasses, pen even dress ornament etc. does not allow nickel plating.
On the other hand, metallic nickel and its esters price are ascended to heaven in recent years, estimate that imbalance between supply and demand is still outstanding in the long duration, and the nickel price still presents high-order vibration situation, makes the Electroplate Factory that adopts nickel plating be in the boundary of difficulty.Therefore, seek that a kind of to replace the electroplating technology of bright nickel plating be very necessary.Useful plating copper-nickel alloy tin technology generation is for the bright nickel plating technology in the prior art.This plating copper-nickel alloy tin technology can obtain smooth and bright coating, and solidity to corrosion is good, and it is silvery white that outward appearance is light, the coating crystallization is careful, and flexibility was good when coating was thin, and good solderability and electroconductibility are arranged, the dispersive ability of plating bath and covering power are good, and bath stability is easy to operate, be easy to management, the non-proliferation performance of copper-nickel alloy tin is good, and electroplating cost is lower, and wastewater treatment is easy, thereby in many plating Application Areass, electroplating copper-nickel alloy tin technology is the optimal selection that replaces the bright nickel plating technology.
But electroplate copper-nickel alloy tin layer dynamic embrittlement taking place easily under action of compressive stress, makes the coating surface hot tearing.
Summary of the invention
The technical problem to be solved in the present invention is that dynamic embrittlement takes place under action of compressive stress product easily that electroplate copper-nickel alloy tin, makes the defective of coating surface hot tearing, thereby a kind of difficult generation embrittlement is provided, and coating surface does not produce the electro-plating method of hot tearing.
The invention provides a kind of electro-plating method, this method comprises the following steps: pre-copper facing: carry out pre-copper facing at substrate surface; Acid bright copper plating: the substrate surface after pre-copper facing carries out acid bright copper plating; Electroplate copper-nickel alloy tin: the substrate surface at acid bright copper plating is electroplated copper-nickel alloy tin again; Wherein, also comprise the heavy tin of chemistry between described acid bright copper plating and described plating copper-nickel alloy tin, described electroless plating tin is deposit tin on the substrate surface at acid bright copper plating.
It is bigger to the invention solves plating copper-nickel alloy tin ply stress, and the technical problem of dynamic embrittlement easily takes place, and effectively raises the anti-wear-resisting and salt spray corrosion resistance of coating.The decoration that can be widely used in the surface of metal product.
Embodiment
The invention provides a kind of electro-plating method, this method comprises the following steps: pre-copper facing: carry out pre-copper facing at substrate surface; Acid bright copper plating: the substrate surface after pre-copper facing carries out acid bright copper plating; Electroplate copper-nickel alloy tin: the substrate surface at acid bright copper plating is electroplated copper-nickel alloy tin again; Wherein, also comprise the heavy tin of chemistry between described acid bright copper plating and described plating copper-nickel alloy tin, described electroless plating tin is deposit tin on the substrate surface at acid bright copper plating.
According to electro-plating method provided by the invention, under situation preferably, the plating bath of the heavy tin of described chemistry is
SnCl
2·2H
2O 20-40g/L，
NaH
2PO
2·H
2O 15-30g/L，
CS(NH
2)
2 50-70g/L，
HCl(37％) 60-100mL/L，
Dodecyl chloropyridine 0.5-4g/L.
According to electro-plating method provided by the invention, under situation preferably, the condition of the heavy tin of described chemistry is working temperature 40-60 ℃, working hour 3-10min.
According to electro-plating method provided by the invention, under situation preferably, described pre-copper facing is the neutral pre-copper facing of no cyanogen, described pre-copper-plated plating bath is the aqueous solution that contains cupric salt and complexing agent, described electroplate liquid also contains auxiliary agent, described auxiliary agent is at least two kinds in an alkali metal salt of an alkali metal salt, allyl group sulphonamide, vinyl sulfonic acid of an alkali metal salt, the allyl sulphonic acid of an alkali metal salt, the dithiocarbonic acid of thionamic acid and the asccharin, and the pH value of described electroplate liquid is 6.5-7.5.According to non-cyanide pre-plating copper plating solution provided by the invention, owing to adopted described auxiliary agent, and the pH value of electroplate liquid is 6.5-7.5 for neutrality, make by the bonding force of resulting pre-copper plate of pre-plating copper plating solution provided by the invention and base material fine, when especially being applied to zinc, magnesium, aluminium or their alloy, can prevent the corrosion of non-cyanide alkali preplating electroplate liquid of the prior art, therefore more can obtain and the well pre-copper plate of the bonding force of base material them.Simultaneously, the flat appearance light of the product behind the plating, heatproof degree impact property and high-temperature baking resistant performance are all fine.And, adopt non-cyanide pre-plating copper plating solution provided by the invention that metal is carried out preplating and can effectively electroplate at normal temperatures, avoided the volatilization and the bigger problem of energy consumption of composition in the high temperature groove electroplate liquid.
According to electro-plating method provided by the invention, under situation preferably, the content of described cupric salt is the 15-25 grams per liter, and the content of described complexing agent is the 2-10 grams per liter, and the content of described auxiliary agent is the 0.06-0.21 grams per liter.
According to electro-plating method provided by the invention, under situation preferably, wherein, described cupric salt is one or more in cupric pyrophosphate, cupric ethylene diamine tetraacetate, Cuprocitrol, hydroxy ethylidene-diphosphate copper or the biuret copper; Described complexing agent is one or more in tetra-sodium, tartrate, citric acid, gluconic acid, ethylenediamine tetraacetic acid (EDTA) and hydroxy ethylene diphosphonic acid and their an alkali metal salt and the ammonium salt.According to non-cyanide pre-plating copper plating solution provided by the invention, under the preferable case, described pre-copper-plated plating bath also contains the additional salt of an alkali metal salt of tetra-sodium as plating bath of the present invention, and the content of an alkali metal salt of described tetra-sodium is the 220-380 grams per liter.In plating bath of the present invention, in plating bath of the present invention, can play the effect of the electroconductibility that improves plating bath as an alkali metal salt of the described tetra-sodium of additional salt.An alkali metal salt of described tetra-sodium can be potassium pyrophosphate or trisodium phosphate, as for the sylvite or the sodium salt that adopt tetra-sodium, depend primarily on bath system, usually keep consistent with bath system, that is, if bath system is a potassium salt system, then each composition of plating bath all adopts sylvite, if bath system is a sodium salt, then each composition of plating bath all adopts sodium salt.
According to electro-plating method provided by the invention, described acid bright copper plating can improve the workpiece surface luminance brightness and improve outward appearance.The plating bath of described acid bright copper plating is a technology as well known to those skilled in the art, and in the preferred case, the plating bath of described acid bright copper plating contains CuSO
4, H
2SO
4, chlorion, open the cylinder agent, fill and lead up the aqueous solution of agent and brightening agent.Described CuSO
4Content be 180-250g/l, preferred 220g/L; Described H
2SO
4Content be 50-70g/l, preferred 50g/L; The content of described chlorion is 40-100mg/L, described preferred 100mg/L; The described content of opening the cylinder agent is 8-10ml/L, preferred 8ml/L; The described content of filling and leading up agent is 0.4-0.6ml/L, preferred 0.5ml/L; The content of described brightening agent is 0.4-0.6ml/L, preferred 0.5ml/L.But the used plating bath of acid bright copper plating of the present invention can oneself be prepared the also product of commodity in useization, the UB-X series acid bright copper plating electroplating technology of the Chemical Manufacture of star forever of As used herein.The cathode current density of described acid bright copper plating is 3-5A/dm
2, temperature is 20-30 ℃, the time is 15-40min.Described acid bright copper plating is included in the galvanized process and stirs and filter.Stirring can make plating bath even, and filtration is to filter the impurity that produces in the plating bath, eliminates contaminating impurity, keeps the purity of plating bath.
According to electro-plating method provided by the invention, the plating bath of described plating copper-nickel alloy tin contains the aqueous solution of potassium pyrophosphate, cupric pyrophosphate, stannous pyrophosphate, complexing agent, stablizer and brightening agent.The content of described potassium pyrophosphate is 250-350g/L, preferred 320g/L; The content of described cupric pyrophosphate is 5-12g/L, preferred 10g/L; The content of described stannous pyrophosphate is 15-35g/L, and the content of described complexing agent is 80-120ml/L; The content of described stablizer is 10-30ml/L; The content of described brightening agent is 10-20ml/L.The cathode current density of described plating copper-nickel alloy tin is 0.5-1A/dm
2, temperature is 15-30 ℃, and pH value is 8.0-8.8, and the time is 5-15min.What the present invention was used is to reach the CS-138 plating copper-nickel alloy process of tin that will science and technology is produced.
According to electro-plating method provided by the invention, under situation preferably, before carrying out pre-copper facing, also to carry out pre-treatment, the method of metal being carried out pre-treatment can adopt the pre-treating process that is not quite similar at different metals, but it is known in those skilled in the art that these methods are, and for example the pre-treatment for magnesium alloy can comprise polishing, paraffin removal, oil removing, acid etching, activates and soak zinc.
Adopt polishing step certain ablation to be arranged to metal base, the defective with burr, oxide skin and the scuffing of removing product surface to reduce the roughness of metallic substrate surface, obtains the outward appearance of light.The method of polishing for example adopts mechanical polishing, chemical rightenning or electropolishing for well known to a person skilled in the art.
Adopting the paraffin removal step is in order to remove the buffing wax on the product, thereby makes coating and metal base generation good bonding force.The method of paraffin removal for example adopts Wax removal water to carry out paraffin removal under 70-80 ℃ temperature for well known to a person skilled in the art, Wax removal water can be selected commercially available various Wax removal waters (for example the Procleaner BR#1 general-purpose Wax removal water of star chemical company) forever for use.In the preferred case, can adopt ultrasonic wave to strengthen the effect of paraffin removal.
Adopt deoiling step can remove the grease of product surface, the dirty and clean buffing wax that do not eliminate, make follow-up galvanized coating that the good surface appearance effect can be arranged and make coating and the bonding force of metal base better.The method of oil removing can adopt and well known to a person skilled in the art the whole bag of tricks, for example can adopt electrochemical deoiling or electrolytic degreasing to carry out.Degreasing fluid can adopt one or more the aqueous solution that contains in yellow soda ash, sodium hydroxide, water glass, sodium phosphate and the sodium bicarbonate.
Adopt the acid etching step can remove oxide film, oxide skin and the corrosion product of metallic substrate surface.Generally speaking, pickling solution usually adopts one or more the aqueous solution that contains in sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid and the hydrofluoric acid.Thereby can improve the bonding force of pre-copper plate and metallic substrate surface.
Adopt activation step can remove the oxide film of substrate surface.
The reaction that the zinc step can cause the hole part is fast soaked in employing, can improve the covering power and the dispersive ability of plating bath, and improves the bonding force of coating and base material.In general, zincate solution adopts the aqueous solution that contains as the additional salt in the plating bath, the i.e. an alkali metal salt of the tetra-sodium among the present invention usually.
For attractive in appearance and to the further protection and the decoration of metal base, usually also will be after electroplating copper-nickel alloy tin re-plating one deck coating, for example electroplating gun color coating, trivalent chromium coating or rose gold coating.
Described rifle look electric plating method adopts the no nickel rifle look electroplating technology of the SCA-422 model of international Chemical Manufacture.Described rifle look galvanized working temperature is 40-50 ℃, and the working hour is 10min, and current density is 0.7A/dm
2
The plating bath of the white chromium of described plating trivalent is for opening cylinder agent, stablizer, wetting agent, complexing agent and the chromic aqueous solution.The described content of opening the cylinder agent is 400-450g/L, preferred 420g/L; The content of described stablizer is 55-75g/L, preferred 65g/L; The content of described wetting agent is 2-5ml/L, preferred 3ml/L; The content of described complexing agent is 1-3ml/L, preferred 2ml/L; Described chromic content is 20-25g/L, preferred 22g/L.The plating bath that the present invention electroplates the white chromium of trivalent can own preparation also can adopt the white chromium plating bath of TVC-trivalent of the company that starts.The temperature of the white chromium of described plating trivalent is 28-35 ℃; The pH value is 2.8-3.3; Cathode current density is 8-30A/dm
2Time is 1-5min, and anode is that the special-purpose anode of trivalent chromium can be an insoluble anode, a kind of in titanium alloy sheet and the graphite.
Described rose gold is electroplated, electroplate liquid formulation is gold sodium sulfide 5g/L, sodium sulphite anhydrous 99.3 130g/L, dipotassium hydrogen phosphate 40g/L, Tripotassium Citrate 90g/L, Repone K 110g/L, brightening agent 1g/L, stablizer 0.2g/L, adopt the graphite cake anode, experimental temperature is 50-60 ℃, the pH value is 8.5-9.0, and current density is 0.3A/dm
2, electroplating time is 40s.
After above-mentioned each stage, electro-plating method of the present invention can also comprise washing and exsiccant step, to remove the residual solution of substrate material surface; The used water of described water-washing step is various water of the prior art, as deionized water, distilled water, pure water or their mixture, is preferably deionized water.Can adopt the method for well known to a person skilled in the art to carry out drying, for example forced air drying, natural air drying or oven dry under 40-100 ℃.
Described base material of the present invention can be various metals and alloy thereof, be preferably magnesium alloy, aluminium alloy, for example, can be that magnesium alloy or the model of AZ91D, AM60B, AM50A is the aluminium alloy of AC8A, ZL303, YL117, KS282 or ZL102 for model, what embodiments of the invention were used is AZ91D type magnesium alloy die casting, but this method also is suitable for other magnesium alloy and aluminium alloy.
According to electro-plating method provided by the invention, effectively solved the situation of traditional copper-nickel alloy process of tin coating generation crackle.The present invention adopts and electroplates the technology of copper-nickel alloy tin for nickel, has effectively stopped the allergic symptom of human body skin to nickel, has reduced because the international nickel valency is high the impact that brings to nickel plating technology.
Below will the invention will be further described by embodiment.
Embodiment 1
(1) polishing
AZ91D type magnesium alloy die casting is buckled the cloth wheel with 1*10 cun carry out mechanical polishing in conjunction with 1*10 cun lamb hair buff polishing method, remove burr that former material itself produces, oxide skin etc. in press casting procedure, reduce the roughness on surface, improve the minute surface brightness effect and strengthen follow-up galvanized bonding force.
(2) paraffin removal
Adopt the magnesium alloy die casting after the above-mentioned polishing forever that the Procleaner BR#1 of star chemical company general-purpose Wax removal water carries out paraffin removal, opening the cylinder amount is 30ml/L, and working temperature is 80 ℃, paraffin removal 5min under ultrasonic environment.
(3) oil removing:
Magnesium alloy die casting behind the above-mentioned paraffin removal is carried out the catholyte oil removing, and electrolytic solution is: sodium phosphate 30g/L, yellow soda ash 30g/L; Removing oil temperature is 60 ℃, and the oil removing time is 1min, and current density is 5A/dm
2
(4) acid etching:
With the soak at room temperature 30s in hydrofluoric acid 10ml/L of the magnesium alloy die casting after the above-mentioned oil removing.
(5) activation:
Magnesium alloy die casting behind the above-mentioned acid etching is immersed soak at room temperature 2min among ammonium bifluoride 90g/L and the phosphatase 11 50ml/L.
(6) soak zinc
Magnesium alloy die casting after above-mentioned activation temperature in zinc sulfate 20g/L, potassium pyrophosphate 160g/L, Sodium Fluoride 5g/L and yellow soda ash 5g/L is flooded 3min down for 80 ℃.
(7) pre-copper facing
The above-mentioned magnesium alloy die casting that soaks behind the zinc is carried out pre-copper facing, pre-copper-plated plating bath is: cupric pyrophosphate 25 grams per liters, trisodium phosphate 220 grams per liters, disodium ethylene diamine tetraacetate 0.8 grams per liter, Trisodium Citrate 1.2 grams per liters, thionamic acid potassium 0.05 grams per liter and potassium dithiocarbonate 0.01 grams per liter.With the pH value of phosphoric acid adjustment plating bath, making pH is 6.5, and electroplating time is 5min, and current density is 1A/dm
2
(8) acid bright copper plating:
Magnesium alloy die casting after the above-mentioned pre-copper facing is carried out acid bright copper plating, and this process using is the UB-X series acid bright copper plating electroplating technology of star Chemical Manufacture forever.The working temperature of acid bright copper plating is 30 ℃, and the working hour is 30min, and current density is 4A/dm
2
(9) the heavy tin of chemistry
Magnesium alloy die casting behind the above-mentioned acid bright copper plating is carried out the heavy tin of chemistry, and the plating bath of the heavy tin of chemistry is SnCl
22H
2O 30g/L, NaH
2PO
2H
2O 25g/L, CS (NH
2)
260g/L, HCl (37%) 80mL/L, dodecyl chloropyridine 2g/L.The working temperature of the heavy tin of chemistry is 50 ℃, and the working hour is 5min.
(10) electroplate copper-nickel alloy tin
Magnesium alloy die casting behind the heavy tin of above-mentioned chemistry is electroplated copper-nickel alloy tin, and this process using reaches the CS-138 plating copper-nickel alloy process of tin that will science and technology is produced.The working temperature of electroplating copper-nickel alloy tin is 30 ℃, and the working hour is 15min, and current density is 1A/dm
2
(11) electroplate the white chromium of trivalent
Magnesium alloy die casting behind the above-mentioned plating copper-nickel alloy tin is electroplated the white chromium of trivalent, this process using white chromium plating bath of scientific and technological TVC series trivalent that starts.The working temperature of electroplating the white chromium of trivalent is 30 ℃, and pH is 3.0, and the working hour is 2min, and current density is 20A/dm
2
Embodiment 2
Step (1)-(6) are identical with embodiment 1.
(7) pre-copper facing:
The above-mentioned magnesium alloy die casting that soaks behind the zinc is carried out pre-copper facing, pre-copper-plated plating bath is: cupric pyrophosphate 15 grams per liters, potassium pyrophosphate 380 grams per liters, ethylenediamine tetraacetic acid (EDTA) 3 grams per liters, Tripotassium Citrate 7 grams per liters, thionamic acid potassium 0.6 grams per liter and potassium dithiocarbonate 0.15 grams per liter.With the pH value of phosphoric acid adjustment plating bath, making pH is 7.5, and electroplating time is 5min, and current density is 1A/dm
2
(8) acid bright copper:
Magnesium alloy die casting after the above-mentioned pre-copper facing is carried out bright copper plating, and this process using is the UB-X series acid bright copper plating electroplating technology of star Chemical Manufacture forever.The working temperature of acid bright copper plating is 30 ℃, and the working hour is 30min, and current density is 4A/dm
2
(9) the heavy tin of chemistry
Magnesium alloy die casting behind the above-mentioned acid bright copper plating is carried out the heavy tin of chemistry, SnCl
22H
2O20g/L, NaH
2PO
2H
2O 15g/L, CS (NH
2)
2, 50g/LHCl (37%) 60mL/L, dodecyl chloropyridine 0.5g/L.The working temperature of the heavy tin of chemistry is 40 ℃, and the working hour is 10min.
(10) electroplate copper-nickel alloy tin:
Magnesium alloy die casting behind the heavy tin of above-mentioned chemistry is electroplated copper-nickel alloy tin, and this process using reaches the CS-138 plating copper-nickel alloy process of tin that will science and technology is produced.The working temperature of electroplating copper-nickel alloy tin is 30 ℃, and the working hour is 15min, and current density is 1A/dm
2
(11) electroplate rose gold
Magnesium alloy die casting behind the above-mentioned plating copper-nickel alloy tin is electroplated rose gold, electroplate liquid formulation is: gold sodium sulfide 5g/L, sodium sulphite anhydrous 99.3 130g/L, dipotassium hydrogen phosphate 40g/L, Tripotassium Citrate 90g/L, Repone K 110g/L, brightening agent 1g/L, stablizer 0.2g/L, adopt the graphite cake anode, experimental temperature is 60 ℃, the pH value is 9.0, and current density is 0.3A/dm
2, the time is 40s.
Embodiment 3
Step (1)-(6) are identical with embodiment 1.
(7) pre-copper facing:
The above-mentioned magnesium alloy die casting that soaks behind the zinc is carried out pre-copper facing, and pre-copper-plated plating bath is: cupric pyrophosphate 20 grams per liters, potassium pyrophosphate 300 grams per liters, ethylenediamine tetraacetic acid (EDTA) 2 grams per liters, Tripotassium Citrate 5 grams per liters, thionamic acid potassium 0.3 grams per liter and potassium dithiocarbonate 0.1 grams per liter.With the pH value of phosphoric acid adjustment plating bath, making pH is 7.0, and electroplating time is 5min, and current density is 1A/dm
2
(8) acid bright copper:
Magnesium alloy die casting after the above-mentioned pre-copper facing is carried out bright copper plating, and this process using is the UB-X series acid bright copper plating electroplating technology of star Chemical Manufacture forever.The working temperature of acid bright copper plating is 30 ℃, and the working hour is 30min, and current density is 4A/dm
2
(9) the heavy tin of chemistry
Magnesium alloy die casting behind the above-mentioned acid bright copper plating is carried out the heavy tin of chemistry, SnCl
22H
2O 40g/L, NaH
2PO
2H
2O 30g/L, CS (NH
2)
270g/L, HCl (37%) 100mL/L, dodecyl chloropyridine 0.5-4g/L.The working temperature of the heavy tin of chemistry is 60 ℃, and the working hour is 3min.
(10) electroplate copper-nickel alloy tin:
Magnesium alloy die casting behind the heavy tin of above-mentioned chemistry is electroplated copper-nickel alloy tin, and this process using reaches the CS-138 plating copper-nickel alloy process of tin that will science and technology is produced.The working temperature of electroplating copper-nickel alloy tin is 30 ℃, and the working hour is 15min, and current density is 1A/dm
2
(11) the rifle look is electroplated
Magnesium alloy die casting behind the above-mentioned plating copper-nickel alloy tin is carried out the rifle look electroplate, the no nickel rifle look electroplating technology of the SCA-422 model of the international Chemical Manufacture of this process using.Working temperature is 50 ℃, and the working hour is 10min, and current density is 0.7A/dm
2
Comparative Examples 1
Step (1)-(6) are identical with embodiment 1.
(7) pre-copper facing:
The above-mentioned magnesium alloy die casting that soaks behind the zinc is carried out pre-copper facing, and pre-copper-plated plating bath is: cupric pyrophosphate 20 grams per liters, potassium pyrophosphate 300 grams per liters, ethylenediamine tetraacetic acid (EDTA) 2 grams per liters, Tripotassium Citrate 5 grams per liters, thionamic acid potassium 0.3 grams per liter and potassium dithiocarbonate 0.1 grams per liter.With the pH value of phosphoric acid adjustment plating bath, making pH is 7.0, and electroplating time is 5min, and current density is 1A/dm
2
(8) acid bright copper plating:
Magnesium alloy die casting after the above-mentioned pre-copper facing is carried out bright copper plating, and this process using is the UB-X series acid bright copper plating electroplating technology of star Chemical Manufacture forever.The working temperature of acid bright copper plating is 30 ℃, and the working hour is 30min, and current density is 4A/dm
2
(9) electroplate copper-nickel alloy tin
Magnesium alloy die casting behind the heavy tin of above-mentioned chemistry is electroplated copper-nickel alloy tin, and this process using reaches the CS-138 plating copper-nickel alloy process of tin that will science and technology is produced.The working temperature of electroplating copper-nickel alloy tin is 30 ℃, and the working hour is 15min, and current density is 1A/dm
2
(10) electroplate the white chromium of trivalent
Magnesium alloy die casting behind the above-mentioned plating copper-nickel alloy tin is electroplated the white chromium of trivalent, this process using white chromium plating bath of scientific and technological TVC series trivalent that starts.The working temperature of electroplating the white chromium of trivalent is 30 ℃, and pH is 3.0, and the working hour is 2min, and current density is 20A/dm
2
Comparative Examples 2
Step (1)-(6) are identical with embodiment 1.
(7) pre-copper facing:
The above-mentioned magnesium alloy die casting that soaks behind the zinc is carried out pre-copper facing, and pre-copper-plated plating bath is: cupric pyrophosphate 20 grams per liters, potassium pyrophosphate 300 grams per liters, ethylenediamine tetraacetic acid (EDTA) 2 grams per liters, Tripotassium Citrate 5 grams per liters, thionamic acid potassium 0.3 grams per liter and potassium dithiocarbonate 0.1 grams per liter.With the pH value of phosphoric acid adjustment plating bath, making pH is 7.0, and electroplating time is 5min, and current density is 1A/dm
2
(8) acid bright copper plating:
Magnesium alloy die casting after the above-mentioned pre-copper facing is carried out bright copper plating, and this process using is the UB-X series acid bright copper plating electroplating technology of star Chemical Manufacture forever.The working temperature of acid bright copper plating is 30 ℃, and the working hour is 30min, and current density is 4A/dm
2
(9) electroplate copper-nickel alloy tin
Magnesium alloy die casting behind the heavy tin of above-mentioned chemistry is electroplated copper-nickel alloy tin, and this process using reaches the CS-138 plating copper-nickel alloy process of tin that will science and technology is produced.The working temperature of electroplating copper-nickel alloy tin is 30 ℃, and the working hour is 10min, and current density is 1A/dm
2
(10) electroplate the white chromium of trivalent
Magnesium alloy die casting behind the above-mentioned plating copper-nickel alloy tin is electroplated the white chromium of trivalent, this process using white chromium plating bath of scientific and technological TVC series trivalent that starts.The working temperature of electroplating the white chromium of trivalent is 30 ℃, and pH is 3.0, and the working hour is 2min, and current density is 20A/dm
2
Comparative Examples 3
Step (1)-(6) are identical with embodiment 1.
(7) pre-copper facing:
The above-mentioned magnesium alloy die casting that soaks behind the zinc is carried out pre-copper facing, adopt the Mai Demei CuMacStrike XD7453 of company model non-cyanide alkali electroplating technology.The pH value is 10.00, and electroplating time is 5min, and current density is 2A/dm
2
(8) acid bright copper plating:
Magnesium alloy die casting after the above-mentioned pre-copper facing is carried out bright copper plating, and this process using is the UB-X series acid bright copper plating electroplating technology of star Chemical Manufacture forever.The working temperature of acid bright copper plating is 30 ℃, and the working hour is 30min, and current density is 4A/dm
2
(9) the heavy tin of chemistry
Magnesium alloy die casting behind the above-mentioned acid bright copper plating is carried out the heavy tin of chemistry, technology that the intelligent CWF-807 series of insulting science and technology production of this process using " is dyed silver-colored water ".The working temperature of the heavy tin of chemistry is 50 ℃, and the working hour is 5min.
(10) electroplate copper-nickel alloy tin
Magnesium alloy die casting behind the heavy tin of above-mentioned chemistry is electroplated copper-nickel alloy tin, and this process using reaches the CS-138 plating copper-nickel alloy process of tin that will science and technology is produced.The working temperature of electroplating copper-nickel alloy tin is 30 ℃, and the working hour is 15min, and current density is 1A/dm
2
(11) electroplate the white chromium of trivalent
Magnesium alloy die casting behind the above-mentioned plating copper-nickel alloy tin is electroplated the white chromium of trivalent, this process using white chromium plating bath of scientific and technological TVC series trivalent that starts.The working temperature of electroplating the white chromium of trivalent is 30 ℃, and pH is 3.0, and the working hour is 2min, and current density is 20A/dm
2
Testing method:
(1) sticking power test
The standard of test: ISO 2409.
Testing method: use the knife back of surgical knife or specified intersection cutter on coating, to draw 12 road cuts, article two, scratch mutually at an angle of 90, so that form grid from the teeth outwards, cut be spaced apart 1mm (if surface too only standardized the fork of I, i.e. 2 road cuts).Guarantee to be cut to body material.Otherwise cut again the position of Ying Zaixin.Direction along cut is brushed 5 times with brush.3M adhesive tape (600 or similar model) is bonded on the surface, with finger tip that wiping belt is tight, guarantee to contact with the good of coating, in 5 minutes, tear adhesive tape well-regulated open off adhesive tape at 0.5-1 in second with 60 ° angle from the free end of adhesive tape.Test result sees Table 2.
Accept standard: 0 grade and 1 grade of reception.Cut for an intersection does not allow angle of cut perk or becomes big.
0 grade: the edge of otch is level and smooth fully, and the square of grid does not all peel off.
1 grade: peel off and be subjected to this part that influences can not be obviously greater than 5%.
2 grades: peel off and be subjected to this part that influences, and be no more than 15% obviously greater than 5%.
3 grades: peel off and be subjected to this part that influences, and be no more than 35% greater than 15%.
4 grades: peel off and be subjected to this part that influences, and be no more than 65% greater than 35%.
5 grades: can not be classified as the 4th grade the peeling off of other degree.
(2) temperature shock test
Keep 2H at-40 ℃ respectively, be warmed up to 85 ℃ and keep 2H then within 3 minutes, and then cooled to-40 ℃ and keep 2H within 3 minutes, circulate 5 cycles, test and at room temperature recovered 2 hours after finishing, mechanical property is normal.
Accept standard: mechanical part not breakage is not out of shape.Test result sees Table 3.
(3) wallet test (wear resisting property of assessment product surface)
Testing method:
A. coat the state adjustment grease of skim at sample;
B. be 65 ℃ in temperature, relative humidity is in 95% the envrionment conditions, and three samples were wherein placed 3 hours, places 24 hours for other three;
C. be with emgloves, clean each sample with paper handkerchief, the state of removing is adjusted grease;
D. hang sample under the room temperature condition, do the upset test then.
Wherein the test of the upset in steps d concrete steps are as follows:
1. the sample after handling through step a-c is put into handbag, zip up is also fixed with clasp;
2. 6 handbags are put into roller, rollover test 45 minutes.
Appraisal procedure:
With IPA (Virahol) cleaning sample, remove fragment and friction trace.The defective of each sample or assembly decorative cover (as: matrix distortion, galled spots, fragment, break and tiny crack etc.) is assessed.The performance of each sample or assembly should be by following deciding grade and level:
5 grades of damages that (can accept)-decorative cover is very small;
4 grades of damages that (can accept)-decorative cover is small;
The damage of 3 grades of (accepting the limit)-decorative cover moderates;
2 grades of (unacceptable)-decorative cover obvious impairment;
1 grade of damage that (unacceptable)-decorative cover is serious.
Test result sees Table 4.
(4) SaltSprayTest
Spraying (NaCl accounts for 5% of quality, pH 6.5-7.2) is 2 hours under 35 ℃ of conditions, and then at 40 ℃, 80% humidity was placed 168 hours.
Accept standard: working properly after placing 2 hours, there are not oxidation of any visible burn into and distortion.
Test result part table 5.
Table 1
Table 2
| Experiment | The sticking power test result |
| Embodiment 1 | 0 grade |
| Embodiment 2 | 0 grade |
| Embodiment 3 | 0 grade |
| Comparative Examples 1 | 1 grade |
| Comparative Examples 2 | 0 grade |
| Comparative Examples 3 | 2 grades |
Table 3
| Experiment | The temperature shock test result |
| Embodiment 1 | Coating does not have peeling, foaming and rimose phenomenon |
| Embodiment 2 | Coating does not have peeling, foaming and rimose phenomenon |
| Embodiment 3 | Coating does not have peeling, foaming and rimose phenomenon |
| Comparative Examples 1 | Coating has tangible cracking phenomena |
| Comparative Examples 2 | Coating does not have peeling, foaming and rimose phenomenon |
| Comparative Examples 3 | Coating has tangible foaming phenomenon |
Table 4
| Experiment | Vibrate wear-resisting test result |
| Embodiment 1 | 5 grades |
| Embodiment 2 | 5 grades |
| Embodiment 3 | 5 grades |
| Comparative Examples 1 | 4 grades |
| Comparative Examples 2 | 3 grades |
| Comparative Examples 3 | 3 grades |
Table 5
| Experiment | The SaltSprayTest result |
| Embodiment 1 | There are not oxidation of any visible burn into and distortion |
| Embodiment 2 | There are not oxidation of any visible burn into and distortion |
| Embodiment 3 | There are not oxidation of any visible burn into and distortion |
| Comparative Examples 1 | There are not oxidation of any visible burn into and distortion |
| Comparative Examples 2 | Product surface has slight hot spot |
| Comparative Examples 3 | The product surface heavy corrosion |
As can be seen, the product appearance light of embodiment 1-3 is smooth from table 1-5, and flawless produces; Place outward appearance no change after 2 days; Toast 30min under 120 ℃ of environment, also the flawless phenomenon takes place, and product does not have peeling foaming phenomenon.The sticking power test of the product of embodiment 1-3 all is 0 grade, reaches the requirement of sticking power.The coating behind temperature shock test of the product of embodiment 1-3 does not have peeling, foaming and rimose phenomenon.The wear-resisting test result of the vibration of the product of embodiment 1-3 all is 5 grades, meets the requirements.The product of embodiment 1-3 is being incured loss through delay test back no any visible burn into oxidation and distortion.In sum, no matter the product of embodiment 1-3 reaches requirement at outward appearance, sticking power, temperature shock, the wear-resisting test of vibration and salt-fog test everyway.
As can be seen, though the sticking power of the product of Comparative Examples 1, the wear-resisting test of vibration and salt-fog test can both reach requirement, his outward appearance has slight peeling situation after baking from table 1-5, and coating has tangible cracking phenomena behind the temperature shock test.
As can be seen, though the outward appearance of the product of Comparative Examples 2, sticking power and temperature shock test can both reach requirement, the wear-resisting test grade of his vibration is 3, does not reach requirement from table 1-5; Product surface has slight hot spot after the salt-fog test.
As can be seen, there is the hot spot of a large amount of pits, impurity class in the product appearance of Comparative Examples 3, places 2 days surperficial flawless phenomenons from table 1-5, and there is a large amount of foaming situations baking 30min rear surface under 120 ℃ of environment.2 grades of his sticking power do not reach requirement.The temperature shock test back coating of the product of Comparative Examples 3 has tangible foaming phenomenon.The product of Comparative Examples 3 is at salt-fog test rear surface heavy corrosion.
In sum, good chemistry and mechanical property are arranged, can satisfy service requirements with the galvanized product of electro-plating method of the present invention.
Claims (10)
1. electro-plating method, this method comprises the following steps:
Pre-copper facing: carry out pre-copper facing at substrate surface;
Acid bright copper plating: the substrate surface after pre-copper facing carries out acid bright copper plating;
Electroplate copper-nickel alloy tin: the substrate surface behind acid bright copper plating is electroplated copper-nickel alloy tin again;
It is characterized in that also comprise the heavy tin of chemistry between described acid bright copper plating and described plating copper-nickel alloy tin, described electroless plating tin is deposit tin on the substrate surface behind the acid bright copper plating.
2. electro-plating method according to claim 1, the plating bath of the heavy tin of described chemistry is
SnCl
2·2H
2O 20-40g/L，
NaH
2PO
2·H
2O 15-30g/L，
CS(NH
2)
2 250-70g/L，
HCl(37％) 60-100mL/L，
Dodecyl chloropyridine 0.5-4g/L.
3. electro-plating method according to claim 1, the working temperature of the heavy tin of described chemistry is 40-60 ℃, the working hour is 3-10min.
4. electro-plating method according to claim 1, described pre-copper-plated plating bath is the aqueous solution that contains cupric salt and complexing agent, described electroplate liquid also contains auxiliary agent, described auxiliary agent is at least two kinds in an alkali metal salt of an alkali metal salt, allyl group sulphonamide, vinyl sulfonic acid of an alkali metal salt, the allyl sulphonic acid of an alkali metal salt, the dithiocarbonic acid of thionamic acid and the asccharin, and the pH value of described electroplate liquid is 6.5-7.5.
5. electro-plating method according to claim 4, the content of described auxiliary agent are the 0.06-0.21 grams per liter.
6. electro-plating method according to claim 4, the content of described cupric salt are the 15-25 grams per liter.
7. electro-plating method according to claim 4, the content of described complexing agent are the 2-10 grams per liter.
8. electro-plating method according to claim 4, described cupric salt are one or more in cupric pyrophosphate, cupric ethylene diamine tetraacetate, Cuprocitrol, hydroxy ethylidene-diphosphate copper or the biuret copper.
9. electro-plating method according to claim 4, described complexing agent are one or more in tetra-sodium, tartrate, citric acid, gluconic acid, ethylenediamine tetraacetic acid (EDTA) and hydroxy ethylene diphosphonic acid and their an alkali metal salt and the ammonium salt.
10. electro-plating method according to claim 4, wherein, described pre-copper-plated plating bath also contains an alkali metal salt of tetra-sodium, and the content of an alkali metal salt of described tetra-sodium is the 220-380 grams per liter.
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