CN102634827B - Tin-zinc alloy electroplating method - Google Patents
Tin-zinc alloy electroplating method Download PDFInfo
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- CN102634827B CN102634827B CN201210139655.8A CN201210139655A CN102634827B CN 102634827 B CN102634827 B CN 102634827B CN 201210139655 A CN201210139655 A CN 201210139655A CN 102634827 B CN102634827 B CN 102634827B
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Abstract
The invention aims to provide a tin-zinc alloy electroplating method. The method is performed under the following conditions: plating bath temperature: 15-25 DEG C; plating solution stirring speed: 50-200m/min; and cathodic current density: 5-100A/dm2. The tin-zinc alloy electroplating method is obtained by selection of a plating bath temperature, a cathode current density and the like and the use of a specific tin-zinc alloy plating bath, and the tin-zinc alloy plating obtained using the method has strong corrosion resistance and reduced pollution, and is an ideal substitute for cadmium plating.
Description
Technical field
The present invention relates to tin-zinc alloy electroplating method.
Background technology
Plating is exactly the process utilizing electrolysis principle to plate other metal or alloy of skim on some metallic surface, be utilize electrolytic action to make the technique of the surface attachment layer of metal film of metal or other material thus play to prevent corrosion, improve the effects such as wear resistance, electroconductibility, reflective and having improved aesthetic appearance.
Utilize electrolytic action on machinework, deposit the good but technology of the metal cover that performance is different with body material of attachment.Electrolytic coating is more even than hot dipping layer, generally all thinner, from several micron to tens microns not etc.By plating, decoration protectiveness and various functional upper layer can be obtained on machinework, the workpiece of wearing and tearing and processing error can also be repaired.
Sexavalent chrome coating has light, hard, anti-discolouring, the feature such as heat-resisting, wear-resisting, under the condition of air, can keep original gloss muchly; In acid, all having very high chemical stability in alkali, is a kind of desirable coating, ornamental and functional in be obtained for satisfied effect.The shortcoming of hexavalent chromium plating is also clearly: the cathode efficiency of chromium plating is extremely low, only has 8% ~ 16%, and the precipitation of a large amount of hydrogen forms acid mist, causes damage to the health of environment and workman; Sexavalent chrome can not natural degradation, and it, at biological and people's body accumulation, causes long-term harm.In all electroplating technologies, dispersive ability and the covering power of hexavalent chromium plating are the poorest, and the part for shape matching complexity must adopt conformal anode, the homogeneity of guarantee coating.Along with the enhancing of people's environmental consciousness, the reform of hexavalent chromium plating technique is imperative.In order to replace the hexavalent chromium plating of heavily contaminated, people have carried out much research, mainly trivalent chromium plating.Low toxicity, low stain are the great advantage of trivalent chromium plating, and its toxicity only has about 1% of hexavalent chromium compound; Chrome-free mist is overflowed, and chromium plating workman can not produce relevant occupational illness; Cr
3+wastewater treatment compare Cr
6+simply, Cr is eliminated
6+reduction step, as long as wastewater pH is transferred to about 8, Cr3+ just can become oxyhydroxide and precipitate and separate; Cr
3+waste water treatment and integral expense only have Cr
6+about 20% of plating solution.
Cadmium coater is considered to best solidity to corrosion coating.But cadmium plating technique is due to poisonous, and exist between serious pollution and inscribe, therefore researching and developing multicomponent alloy electrolytic coating replacement coated coating is one of problem of main research in plating, and tin one zinc coating is then a kind of high anti-corrosion base binary alloy plating of good properties.
Tin-zinc alloy electrodeposits is silvery white, light, soft texture, can polishing, is colourless or faint yellow after Passivation Treatment.It has the advantage of tin and zinc two kinds of metals concurrently, and its current potential, between tin and zinc, has the performance of good anti-chlorine ion corrosion, and the cadmium coater of alternative seawater corrosion resistance, reduces costs, pollution abatement.In addition, it also has good welding property, indeformable under 700 DEG C of high temperature, does not peel.Therefore, the fields such as aviation, navigation, machinery, electronics can be widely used in.
At present, the plating system of the tin-zinc alloy of living has multiple: hydride systems, fluoroboric acid system, pyrophosphate salt system, gluconic acid salt system and citrate system.Domestic main application be prussiate, pyrophosphate salt system.Hydride systems is seriously polluted, and plating solution is unstable, causes quality of coating poor.This is mainly due to Bivalent Tin oxidizable one-tenth tetravalent tin in aqueous, causes coating muddy, therefore, must add suitable stablizer and additive, improves the overpotential of metal ion at cathodic discharge, to obtain the coating of excellent performance.
Summary of the invention
An object of the present invention is to provide a kind of tin-zinc alloy electroplating method, by selecting plating bath and cathode current density etc., and use specific tin-zinc alloy plating bath, thus obtain a kind of tin-zinc alloy electroplating method, the tin-zinc alloy coating erosion resistance obtained after described method plating is strong, can decreasing pollution, be the desirable coating for cadmium.
In order to achieve the above object, present invention employs following technical scheme:
Described tin-zinc alloy electroplating method, is characterized in that, described method is carried out under the following conditions:
Plating bath: 15 ~ 25 DEG C,
The stirring velocity of plating solution: 50 ~ 200m/min, and
Cathode current density: 5 ~ 100A/dm
2.
Preferably, described method is carried out in following condition:
Plating bath: 15 ~ 25 DEG C,
The stirring velocity of plating solution: 70 ~ 180m/min, and
Cathode current density: 20 ~ 80A/dm
2.
As further preferred version, described method is carried out in following condition:
Plating bath: 18 ~ 23 DEG C,
The stirring velocity of plating solution: 100 ~ 150m/min, and
Cathode current density: 30 ~ 70A/dm
2.
Plating bath in electro-plating method of the present invention is 15 ~ 25 DEG C, such as 16 DEG C, 17 DEG C, 18 DEG C, 19 DEG C, 20 DEG C, 21 DEG C, 22 DEG C, 23 DEG C, 24 DEG C, is preferably 18 ~ 23 DEG C.The stirring velocity of plating solution is 5 ~ 200m/min, such as 10m/min, 15m/min, 20m/min, 25m/min, 30m/min, 195m/min, 180m/min, 190m/min, 185m/min, 175m/min, be preferably 70 ~ 180m/min, more preferably 100 ~ 150m/min.Cathode current density is 5 ~ 100A/dm
2, such as 10A/dm
2, 15A/dm
2, 20A/dm
2, 25A/dm
2, 30A/dm
2, 95A/dm
2, 90A/dm
2, 85A/dm
2, 80A/dm
2, 75A/dm
2, preferred 20 ~ 80A/dm
2, preferred 30 ~ 70A/dm further
2.
The stirring of plating solution specifically can be suitable for carries out the electroplanting device of the jet flow of liquid circulation, the electroplanting device etc. of steel plate by pump.As long as electroplanting device is heat-resisting, the device of the material of chemical proofing, then any, the metal such as stainless steel, titanium can be used; Vinylchlorid, teflon (registered trademark), ABS resin etc.In addition, in order to improve the homogeneity of coating film thickness and alloy plating composition, the device to the overall uniform plating solution stirring velocity of plated body can preferably be obtained.
For the tin-zinc alloy electroplating bath used in electro-plating method of the present invention, can also use and well known to a person skilled in the art arbitrary plating bath, be preferably containing citric acid or/and the plating bath of Citrate trianion, preferably contain citric acid further or/and the plating bath of citric acid organic ammonium salt, more have and preferably contain citric acid or/and the plating bath of dibasic ammonium citrate.
As the concrete example of Citrate trianion, such as, there are an alkali metal salt (sodium, potassium, lithium salts) of citric acid, alkali earth metal salt (magnesium, calcium, barium salt etc.), stannous salt, zinc salt, ammonium salt and organic amine salt (MMA, dimethylamine, Trimethylamine 99, ethamine, Isopropylamine, quadrol, Diethylenetriamine etc.).Citric acid and salt thereof can be used alone, also can be used in combination, and in plating bath, the concentration of citrate ion is 100 ~ 160g/L, preferably 110 ~ 150g/L, further preferred 120 ~ 150g/L.In addition, when using Citrate trianion as stannous salt and/or zinc salt, the gegenion citric acid of metal ion also forms a part for above-mentioned concentration.
The pH of tin-zinc alloy plating bath is 4 ~ 8, such as 4.2,4.4,4.6,4.8,5.0,5.2,5.4,7.8,7.6,7.4,7.2,7.0, preferably 4.5 ~ 7.0, further preferably 5.6 ~ 6.0.The knowledge that those skilled in the art can grasp according to oneself selects the method regulating pH voluntarily.
In addition, for the tin-zinc alloy electroplating bath that electro-plating method of the present invention uses, the plating bath containing amphoterics can also be used.As amphoterics, imidazoline type, betaine type, alanine type, glycine type and acid amide type etc. can be enumerated.These amphotericses can be used alone, and also can mix two or more and use.The concentration of described amphoterics is 0.005 ~ 20g/L, such as 0.01g/L, 0.02g/L, 0.05g/L, 0.10g/L, 0.20g/L, 19g/L, 18g/L, 17g/L, 16g/L, preferably 0.01 ~ 15g/L, further preferred 0.01 ~ 10g/L.
Described tin-zinc alloy plating bath is also containing additive, and described additive comprises formaldehyde and/or ammonium compounds, preferred formaldehyde and/or quaternary ammonium compound, further particular methanol and/or alkalization four isopropyl ammoniums.As quaternary ammonium compound, such as, can also enumerate the reaction product of tertiary amine compound and haloalkane.As concrete tertiary amine compound, such as, can enumerate imidazoles, 1-Methylimidazole, 1-ethyl imidazol(e), glyoxal ethyline, 1-Ethyl-2-Methyl imidazoles, 1-hydroxy methylimidazole, 1-vinyl imidazole and 1,5-methylimidazole as glyoxaline compound; As fatty amine, can enumerate monoethanolamine, diethanolamine, trolamine, dimethylamine, quadrol, Diethylenetriamine, iminobispropylamine, three second tetramines, tetraethylene-pentamine, N, N-two-(3-aminopropyl) quadrol etc.It has stronger reductive action, stops the oxidation of tin consumingly, is conducive to organism absorption at the electrode surface simultaneously, improves stannous deposition potential further, improves cathodic polarization, has obvious refinement and light effect to coating.The concentration of described additive is 0.001 ~ 29g/L, preferably 0.001 ~ 25g/L, further preferred 0.005 ~ 20g/L.In addition, as the antioxidant of tin, hydroxyphenyl compound and salt, L-AA, the Sorbitol Powders etc. such as pyrocatechol, pyrogallol, Resorcinol, sulphosalicylic acid, dihydroxy benzenes sulfonic acid potassium can also be used.
With regard to the tin ion concentration in the plating bath that electro-plating method of the present invention uses, divalent tin ion is 10 ~ 50g/L, preferably 15 ~ 45g/L, further preferred 20 ~ 40g/L.Zinc ion concentration is 10 ~ 80g/L, preferably 15 ~ 70g/L, further preferably 25 ~ 60g/L, more preferably 50g/L.As these metal ion sources, such as, can enumerate the oxyhydroxide of each metal, oxide compound, vitriol, hydrochloride, sulfamate, pyrophosphate salt, hydroxycarboxylate, sulfonate and amino acid salts.Be preferably oxide compound, vitriol, hydrochloride, the oxyhydroxide of each metal.
In order to powered when making plating is good, containing sulfuric acid, hydrochloric acid, thionamic acid, tetra-sodium, sulfonic acid, oxyhydroxide, an alkali metal salt (sodium, potassium, lithium salts) of carbonated, alkali earth metal salt (magnesium, calcium, barium salt), ammonium salt, organic amine salt (MMA, dimethylamine, Trimethylamine 99, ethamine, Isopropylamine, quadrol, Diethylenetriamine etc.) in the plating bath that can also use at electro-plating method of the present invention.Specifically, ammonium sulfate, ammonium chloride, trisodium phosphate, thionamic acid mono-methyl, sodium hydroxide, potassium hydroxide, sodium carbonate, salt of wormwood etc. can be enumerated, particularly preferably ammonium sulfate, ammonium chloride, potassium hydroxide, salt of wormwood.The content of these salt is 10 ~ 300g/L, is preferably 50 ~ 200g/L.
Plated body in electro-plating method of the present invention is the metallic substance by Fe, Ni, Cu or the alloy based on these, and these metallic substance are electroplated as negative electrode.To in extremely, tin-zinc alloy can be used or on Ti material, implement the insoluble electrode, carbon electrode etc. of Pt plating.When using insoluble anode, by the metal-salt of aforesaid tin and zinc being directly dissolved in the method in plating solution or the aqueous solution by supplementing the metal-salt being dissolved with tin and zinc with high density, the metal concentration of used plating bath can be maintained.The high concentration solution of this metal can also containing aforementioned citric acid or its salt and hydroxide basic cpd.
Compared with prior art, the present invention has following beneficial effect:
(1) by changing the ratio of tin ion in the plating bath that uses and zine ion, the tin-zinc alloy electroplating that compositing range is wider can be implemented.Such as, the tin-zinc alloy electroplating containing zinc rate 1 ~ 20% can be implemented in electronic unit, when special reinforcement resistance to salt water and erosion resistance, the tin-zinc alloy electroplating containing zinc rate 15 ~ 45% can be implemented.And then when the overlay film that the erosion resistance in order to obtain consideration chemicals is high, the tin-zinc alloy electroplating containing zinc rate 30 ~ 95% can be implemented;
(2), in electro-plating method of the present invention, after plated body carries out pre-treatment by ordinary method, then electroplating work procedure is carried out.In pretreatment process, carry out flooding at least a kind of operation in degreasing, pickling, electrolytic scrubbing and activation.After plating, the overlay film of gained is washed with water, dry, can also implement to use the chromic salt process of ordinary method and chemical surface control or use inorganics and organic coating process;
(3) by selecting plating bath and cathode current density etc., and use specific tin-zinc alloy plating bath, thus obtain a kind of tin-zinc alloy electroplating method, the tin-zinc alloy coating erosion resistance obtained after described method plating is strong, can decreasing pollution, be the desirable coating for cadmium.
Embodiment
For better the present invention being described, be convenient to understand technical scheme of the present invention, typical but non-limiting embodiment of the present invention is as follows:
Embodiment 1
After pre-treatment is carried out to steel plate, use following plating bath, plating bath be 15 DEG C, the stirring velocity of plating solution is 10m/min, cathode current density is 50A/dm
2condition under implement electroplating processes.
Embodiment 2
After pre-treatment is carried out to steel plate, use following plating bath, plating bath be 20 DEG C, the stirring velocity of plating solution is 10m/min, cathode current density is 100A/dm
2condition under implement electroplating processes.
Embodiment 3
After pre-treatment is carried out to steel plate, use following plating bath, plating bath be 25 DEG C, the stirring velocity of plating solution is 50m/min, cathode current density is 5A/dm
2condition under implement electroplating processes.
Comparative example 1
After pre-treatment is carried out to steel plate, use the plating bath of embodiment 1, plating bath be 10 DEG C, the stirring velocity of plating solution implements electroplating processes under being the condition of 50m/min.
Comparative example 2
After pre-treatment is carried out to steel plate, use the plating bath of embodiment 2, plating bath be 20 DEG C, the stirring velocity of plating solution implements electroplating processes under being the condition of 2m/min.
Comparative example 3
After pre-treatment is carried out to steel plate, use the plating bath of embodiment 3, plating bath be 18 DEG C, the stirring velocity of plating solution implements electroplating processes under being the condition of 3m/min.
Tin-zinc alloy coating has superior corrosion resistance, coating surface, can by the neutral salt spray test of 720h not through chromating process, and surface is through chromating process, can by the neutral salt spray test of 2000h, its corrosion resistance nature is very good.
The corrosion resistance nature test being respectively embodiment 1-3 and the rear coating of comparative example 1-3 process as shown in table 1.
Table 1. embodiment 1-3 and the rear coating corrosion resistance nature of comparative example 1-3 process
| Embodiment | Chromating | Thickness of coating μm | Go out white rust time h | Go out red rust time h |
| Embodiment 1 | Passivation | 5 | 70 | 420 |
| Embodiment 2 | Passivation | 5 | 80 | 450 |
| Embodiment 3 | Passivation | 5 | 60 | 500 |
| Comparative example 1 | Passivation | 5 | 12 | 200 |
| Comparative example 2 | Passivation | 5 | 15 | 220 |
| Comparative example 3 | Passivation | 5 | 20 | 250 |
Can be found by table 1, the going out the white rust time and go out the red rust time and all significantly extend of coating after embodiment 1-3 process compared with comparative example, it is corrosion-resistant significantly improves.
It should be noted that and understand, when not departing from the spirit and scope of the present invention required by accompanying claim, 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.
Applicant states, the present invention illustrates method detailed of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned method detailed, does not namely mean that the present invention must rely on above-mentioned method detailed and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (1)
1. a tin-zinc alloy electroplating method, is characterized in that, described method is:
After pre-treatment is carried out to steel plate, use following plating bath, plating bath be 20 DEG C, the stirring velocity of plating solution is 10m/min, cathode current density is 100A/dm
2condition under implement electroplating processes:
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| CN1039629A (en) * | 1989-06-30 | 1990-02-14 | 天津通信广播公司 | A kind of bright tin plating-Zinc alloy electroplating solution |
| EP0663460B1 (en) * | 1992-09-25 | 2000-03-22 | Dipsol Chemicals Co., Ltd. | Tin-zinc alloy electroplating bath and method for electroplating using the same |
| CN1321205A (en) * | 1998-11-12 | 2001-11-07 | 马克斯·施洛特尔股份有限两合公司 | Aqueous solution for electrodepositing tin-zinc alloys |
| CN101001982A (en) * | 2004-08-10 | 2007-07-18 | 迪普索尔化学株式会社 | Tin-zinc alloy electroplating method |
-
2012
- 2012-05-07 CN CN201210139655.8A patent/CN102634827B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039629A (en) * | 1989-06-30 | 1990-02-14 | 天津通信广播公司 | A kind of bright tin plating-Zinc alloy electroplating solution |
| EP0663460B1 (en) * | 1992-09-25 | 2000-03-22 | Dipsol Chemicals Co., Ltd. | Tin-zinc alloy electroplating bath and method for electroplating using the same |
| CN1321205A (en) * | 1998-11-12 | 2001-11-07 | 马克斯·施洛特尔股份有限两合公司 | Aqueous solution for electrodepositing tin-zinc alloys |
| CN101001982A (en) * | 2004-08-10 | 2007-07-18 | 迪普索尔化学株式会社 | Tin-zinc alloy electroplating method |
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