CN104213159A - Electroplating liquid and electroplating method - Google Patents
Electroplating liquid and electroplating method Download PDFInfo
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- CN104213159A CN104213159A CN201410476939.5A CN201410476939A CN104213159A CN 104213159 A CN104213159 A CN 104213159A CN 201410476939 A CN201410476939 A CN 201410476939A CN 104213159 A CN104213159 A CN 104213159A
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- electroplating
- electroplate liquid
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Abstract
The invention discloses electroplating liquid. The electroplating liquid comprises 100-120 g/L of stannous mono-sulphate, 30-60 g/L of zinc sulfate, 30-50 g/L of copper pyrophosphate, 10-20 g/L of potassium citrate, 10-20 g/L of ampholytic surfactant and 0.5-10 g/L of alkalified tetraisopropamide; and the pH of the electroplating liquid is 4-8. The electroplating liquid is adopted, and fits electroplating conditions, so that an obtained plated layer is high in brightness and strong in corrosion resistance; the white rust generation time and the red rust generation time of the plated layer are both largely prolonged; the white rust generation time can reach above 70 hours; the red rust generation time can reach above 450 hours; and the corrosion resistance is prominently improved, so that the use requirements in severe rugged environment can be satisfied.
Description
Technical field
The present invention relates to a kind of electroplate liquid and electro-plating 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 plating solution, and after adopting this electroplate liquid to electroplate, the tin-zinc alloy coating erosion resistance that obtains is strong, can decreasing pollution, is the desirable coating for cadmium.
In order to achieve the above object, present invention employs following technical scheme:
A kind of electroplate liquid, it comprises:
The pH of described electroplate liquid is 4 ~ 8.
The content of described stannous sulfate is such as 101g/L, 102g/L, 103g/L, 104g/L, 105g/L, 106g/L, 107g/L, 108g/L, 109g/L, 110g/L, 111g/L, 112g/L, 113g/L, 114g/L, 115g/L, 116g/L, 117g/L, 118g/L or 119g/L.
The content of described zinc sulfate is such as 32g/L, 34g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L, 48g/L, 50g/L, 52g/L, 54g/L, 56g/L or 58g/L.
The content of described cupric pyrophosphate is such as 32g/L, 34g/L, 36g/L, 38g/L, 40g/L, 42g/L, 44g/L, 46g/L or 48g/L.
The content of described Tripotassium Citrate is such as 10.5g/L, 11g/L, 11.5g/L, 12g/L, 12.5g/L, 13g/L, 13.5g/L, 14g/L, 14.5g/L, 15g/L, 15.5g/L, 16g/L, 16.5g/L, 17g/L, 17.5g/L, 18g/L, 18.5g/L, 19g/L or 19.5g/L.
The content of described amphoterics is such as 10.5g/L, 11g/L, 11.5g/L, 12g/L, 12.5g/L, 13g/L, 13.5g/L, 14g/L, 14.5g/L, 15g/L, 15.5g/L, 16g/L, 16.5g/L, 17g/L, 17.5g/L, 18g/L, 18.5g/L, 19g/L or 19.5g/L.
The content of described alkalization four Isopropylamine is such as 1g/L, 1.5g/L, 2g/L, 2.5g/L, 3g/L, 3.5g/L, 4g/L, 4.5g/L, 5g/L, 5.5g/L, 6g/L, 6.5g/L, 7g/L, 7.5g/L, 8g/L, 8.5g/L, 9g/L or 9.5g/L.
The pH of described electroplate liquid is such as 4.2,4.4,4.6,4.8,5,5.2,5.4,5.6,5.8,6,6.2,6.4,6.6,6.8,7,7.2,7.4,7.6 or 7.8.
Preferably, described electroplate liquid, it comprises:
Preferably, described electroplate liquid, it comprises:
The above-mentioned electroplate liquid of a kind of use carries out electric plating method, and described method is carried out under the following conditions:
Temperature of electroplating solution: 15 ~ 35 DEG C;
Cathode current density: 8 ~ 20A/dm
2
Electroplating time: 10 ~ 20min.
Described temperature of electroplating solution is 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, 25 DEG C, 26 DEG C, 27 DEG C, 28 DEG C, 29 DEG C, 30 DEG C, 31 DEG C, 32 DEG C, 33 DEG C or 34 DEG C.
Described cathode current density is such as 9A/dm
2, 10A/dm
2, 11A/dm
2, 12A/dm
2, 13A/dm
2, 14A/dm
2, 15A/dm
2, 16A/dm
2, 17A/dm
2, 18A/dm
2or 19A/dm
2.
Described electroplating time is such as 11min, 12min, 13min, 14min, 15min, 16min, 17min, 18min or 19min.
Preferably, described method is carried out in following condition:
Temperature of electroplating solution: 15 ~ 30 DEG C;
Cathode current density: 10 ~ 20A/dm
2
Electroplating time: 12 ~ 20min.
Preferably, described method is carried out in following condition:
Temperature of electroplating solution: 20 ~ 30 DEG C;
Cathode current density: 12 ~ 20A/dm
2
Electroplating time: 14 ~ 20min.
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.
In electro-plating method of the present invention, after plated body carries out pre-treatment by ordinary method, then carry out electroplating work procedure.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.
Compared with the prior art, the present invention is by adopting above-mentioned electroplate liquid, and coordination galvanization condition, the brightness of the coating obtained is high, and rotproofness is strong, and going out the white rust time and going out the red rust time of coating all significantly extends, going out the white rust time can reach more than 70 hours, going out the red rust time can reach more than 450 hours, and it is corrosion-resistant significantly improves, and can meet the service requirements of severe rugged environment.
Embodiment
Technical scheme of the present invention is further illustrated below by embodiment.
Embodiment 1
A kind of electroplate liquid, it comprises:
The pH of described electroplate liquid is 4.
The above-mentioned electroplate liquid of a kind of use carries out electric plating method, and described method is carried out under the following conditions:
Temperature of electroplating solution: 15 DEG C;
Cathode current density: 8A/dm
2
Electroplating time: 10min.
Embodiment 2
A kind of electroplate liquid, it comprises:
The pH of described electroplate liquid is 4 ~ 8.
The above-mentioned electroplate liquid of a kind of use carries out electric plating method, and described method is carried out under the following conditions:
Temperature of electroplating solution: 35 DEG C;
Cathode current density: 20A/dm
2
Electroplating time: 20min.
Embodiment 3
A kind of electroplate liquid, it comprises:
The pH of described electroplate liquid is 5.
The above-mentioned electroplate liquid of a kind of use carries out electric plating method, and described method is carried out under the following conditions:
Temperature of electroplating solution: 25 DEG C;
Cathode current density: 12A/dm
2
Electroplating time: 12min.
Embodiment 4
A kind of electroplate liquid, it comprises:
The pH of described electroplate liquid is 6.
The above-mentioned electroplate liquid of a kind of use carries out electric plating method, and described method is carried out under the following conditions:
Temperature of electroplating solution: 20 DEG C;
Cathode current density: 14A/dm
2
Electroplating time: 14min.
Coating after electroplating plated body adopting the method for embodiment 1 ~ 4 and comparative example 1 ~ 3 carries out performance test, and result is as shown in the table:
| Embodiment | Thickness of coating μm | Go out white rust time h | Go out red rust time h |
| Embodiment 1 | 5 | 70 | 450 |
| Embodiment 2 | 5 | 80 | 450 |
| Embodiment 3 | 5 | 70 | 500 |
| Embodiment 4 | 5 | 70 | 520 |
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 (6)
1. an electroplate liquid, is characterized in that, it comprises:
The pH of described electroplate liquid is 4 ~ 8.
2. electroplate liquid as claimed in claim 1, it is characterized in that, described electroplate liquid, it comprises:
3. electroplate liquid as claimed in claim 1 or 2, it is characterized in that, described electroplate liquid, it comprises:
4. use one of claim 1-3 described electroplate liquid to carry out an electric plating method, it is characterized in that, described method is carried out under the following conditions:
Temperature of electroplating solution: 15 ~ 35 DEG C;
Cathode current density: 8 ~ 20A/dm
2
Electroplating time: 10 ~ 20min.
5. method as claimed in claim 4, it is characterized in that, described method is carried out in following condition:
Temperature of electroplating solution: 15 ~ 30 DEG C;
Cathode current density: 10 ~ 20A/dm
2
Electroplating time: 12 ~ 20min.
6. the method as described in claim 4 or 5, is characterized in that, described method is carried out in following condition:
Temperature of electroplating solution: 20 ~ 30 DEG C;
Cathode current density: 12 ~ 20A/dm
2
Electroplating time: 14 ~ 20min.
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|---|---|---|---|
| CN201410476939.5A CN104213159A (en) | 2014-09-17 | 2014-09-17 | Electroplating liquid and electroplating method |
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|---|---|---|---|
| CN201410476939.5A CN104213159A (en) | 2014-09-17 | 2014-09-17 | Electroplating liquid and electroplating method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105220190A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of samarium-zinc-iron alloys electroplate liquid and electro-plating method thereof |
| CN109957794A (en) * | 2019-04-26 | 2019-07-02 | 山东金宝电子股份有限公司 | A kind of chemical deactivation process of copper foil surface |
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| JP2004359996A (en) * | 2003-06-03 | 2004-12-24 | Ishihara Chem Co Ltd | Neutral bath for bright tin-zinc alloy plating |
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| CN102690975A (en) * | 2012-06-11 | 2012-09-26 | 东莞市闻誉实业有限公司 | Ternary tin-zinc alloy and electroplating method thereof |
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2014
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| KR20020003475A (en) * | 2000-07-05 | 2002-01-12 | 이구택 | Additive of sn-zn alloy deposit solution of high current density deposit and good surface appearance and the sn-zn deposit steel plate by depositing the additive |
| JP2004359996A (en) * | 2003-06-03 | 2004-12-24 | Ishihara Chem Co Ltd | Neutral bath for bright tin-zinc alloy plating |
| JP2005120425A (en) * | 2003-10-16 | 2005-05-12 | Ishihara Chem Co Ltd | Tin and tin alloy plating bath |
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| CN102690975A (en) * | 2012-06-11 | 2012-09-26 | 东莞市闻誉实业有限公司 | Ternary tin-zinc alloy and electroplating method thereof |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105220190A (en) * | 2015-10-30 | 2016-01-06 | 无锡市嘉邦电力管道厂 | A kind of samarium-zinc-iron alloys electroplate liquid and electro-plating method thereof |
| CN109957794A (en) * | 2019-04-26 | 2019-07-02 | 山东金宝电子股份有限公司 | A kind of chemical deactivation process of copper foil surface |
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Application publication date: 20141217 |
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