CN102634827A - Tin-zinc alloy electroplating method - Google Patents
Tin-zinc alloy electroplating method Download PDFInfo
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- CN102634827A CN102634827A CN2012101396558A CN201210139655A CN102634827A CN 102634827 A CN102634827 A CN 102634827A CN 2012101396558 A CN2012101396558 A CN 2012101396558A CN 201210139655 A CN201210139655 A CN 201210139655A CN 102634827 A CN102634827 A CN 102634827A
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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 to utilize electrolysis principle on some metallic surface, to plate the process of other metal or alloy of skim; Be to utilize electrolytic action that thereby the technology of the surface attachment layer of metal film of metal or other material product is played to prevent corrosion, improve wear resistance, electroconductibility, reflective and promote effects such as attractive in appearance.
Utilize electrolytic action on machinework, to deposit to adhere to good but the technology of performance and body material different metallic coating.Electrolytic coating is more even than hot dipping layer, and is generally all thinner, do not wait to tens microns from several microns.Through electroplating, can on machinework, obtain to decorate protectiveness and various functional upper layer, can also repair the workpiece of wearing and tearing and processing error.
Sexavalent chrome coating has light, hard, anti-discolouring, characteristics such as heat-resisting, wear-resisting, under atmospheric condition, can keep original gloss muchly; In acid, all have very high chemicalstability in the alkali, be a kind of ideal coating, ornamental and functional aspect all obtained the effect of being satisfied with.The galvanized shortcoming of sexavalent chrome also is clearly: chromed cathode efficiency is extremely low, only has 8%～16%, a large amount of hydrogen separate out the formation acid mist, environment and workers'health are caused damage; Sexavalent chrome can not natural degradation, and it is accumulated in biological and human body, causes secular harm.In all electroplating technologies, galvanized dispersive ability of sexavalent chrome and covering power are the poorest, must adopt the pictograph anode for the part of shape more complicated, could guarantee the homogeneity of coating.The enhancing of Along with people's environmental consciousness, the reform of sexavalent chrome electroplating technology is imperative.Electroplate for the sexavalent chrome that replaces heavily contaminated, people have carried out many researchs, mainly are trivalent chromium platings.Low toxicity, the low pollution are the great advantage of trivalent chromium plating, and its toxicity has only about 1% of hexavalent chromium compound; The Chrome-free mist is overflowed, and the chromium plating workman can not produce relevant occupational illness; Cr
3+Wastewater treatment compare Cr
6+Simply, omitted Cr
6+Reduction step, as long as wastewater pH is transferred to about 8, Cr3+ just can become oxyhydroxide and precipitate and separate; Cr
3+The waste water treatment and integral expense have only Cr
6+About 20% of plating bath.
Cadmium coater is considered to best solidity to corrosion coating.But cadmium plating technology is because 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 electroplating, and tin one zinc coating then is the good high anti-corrosion base binary alloy plating of a kind of character.
Tin-zinc alloy electrodeposits is silvery white, light, soft texture, can polish, and be colourless or faint yellow after Passivation Treatment.It has the advantage of tin and two kinds of metals of zinc concurrently, and its current potential has the performance of good anti-chlorine ion corrosion between tin and zinc, and the cadmium coater of alternative seawater corrosion resistance reduces cost, pollution abatement.In addition, it also has good welding property, and is indeformable under 700 ℃ of high temperature, does not peel.Therefore, can be widely used in fields such as aviation, navigation, machinery, electronics.
The plating system of the tin-zinc alloy of living at present, has multiple: prussiate system, fluoroboric acid system, pyrophosphate salt system, glucono-salt system and citrate system.Domestic main application be prussiate, pyrophosphate salt system.The prussiate system is seriously polluted, and plating bath is unstable, causes quality of coating relatively poor.This mainly is because Bivalent Tin is prone to be oxidized to tetravalent tin in the aqueous solution, causes that coating is muddy, therefore, must add suitable stablizer and additive, improves the overpotential of metals ion at cathodic discharge, to obtain the coating of excellent performance.
Summary of the invention
One of the object of the invention is to provide a kind of tin-zinc alloy electroplating method; Through selecting plating bath temperature and cathode current density etc.; And use specific tin-zinc alloy plating bath, thus obtaining a kind of tin-zinc alloy electroplating method, the tin-zinc alloy coating erosion resistance that said method obtains after electroplating is strong; Can reduce pollution, be desirable coating for cadmium.
In order to achieve the above object, the present invention has adopted following technical scheme:
Said tin-zinc alloy electroplating method is characterized in that, said method is carried out under following condition:
The plating bath temperature: 15～25 ℃,
The stirring velocity of plating bath: 50 ~ 200m/min, and
Cathode current density: 5～100A/dm
2
As preferred version, said method is carried out in following condition:
The plating bath temperature: 15～25 ℃,
The stirring velocity of plating bath: 70 ~ 180m/min, and
Cathode current density: 20～80A/dm
2
As further preferred version, said method is carried out in following condition:
The plating bath temperature: 18～23 ℃,
The stirring velocity of plating bath: 100 ~ 150m/min, and
Cathode current density: 30～70A/dm
2
Plating bath temperature in the electro-plating method according to the invention is 15～25 ℃, for example 16 ℃, 17 ℃, 18 ℃, 19 ℃, 20 ℃, 21 ℃, 22 ℃, 23 ℃, 24 ℃, is preferably 18～23 ℃.The stirring velocity of plating bath is 5～200m/min; For example 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, further be preferably 100～150m/min.Cathode current density is 5～100A/dm
2, 10A/dm for example
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, further preferred 30～70A/dm
2
The stirring of plating bath specifically can be suitable for by pump carries out the electroplanting device of liquid round-robin jet flow, the electroplanting device of steel plate etc.Electroplanting device is so long as the device of the material of heat-resisting, chemical proofing, then arbitrarily all can, can use metals such as stainless steel, titanium; Vinylchlorid, ZX 21 (registered trademark), ABS resin etc.In addition, in order to improve the homogeneity that coating film thickness and alloy plating are formed, be preferably the device that can obtain to plated body overall uniform plating bath stirring velocity.
For the tin-zinc alloy electroplating that uses in the electro-plating method of the present invention is bathed; Can also use and well known to a person skilled in the art plating bath arbitrarily; Be preferably and contain Hydrocerol A or/and the plating bath of Citrate trianion; Further preferably contain Hydrocerol A or/and the plating bath of Hydrocerol A organic ammonium salt more has and preferably contains Hydrocerol A or/and the plating bath of dibasic ammonium citrate.
As the concrete example of Citrate trianion, an alkali metal salt (sodium, potassium, lithium salts), alkali earth metal salt (magnesium, calcium, barium salt etc.), stannous salt, zinc salt, ammonium salt and the organic amine salt (single methylamine, n n dimetylaniline, Trimethylamine 99, ethamine, Isopropylamine, quadrol, Diethylenetriamine etc.) of Hydrocerol A for example arranged.Hydrocerol A and salt thereof can use separately, also can mix use, and the concentration of citrate ion is 100 ~ 160g/L in the plating bath, preferred 110 ~ 150g/L, further preferred 120 ~ 150g/L.In addition, when using Citrate trianion as stannous salt and/or zinc salt, the gegenion Hydrocerol A of metals ion also constitutes the part of above-mentioned concentration.
The pH of tin-zinc alloy plating bath is 4～8, for example 4.2,4.4,4.6,4.8,5.0,5.2,5.4,7.8,7.6,7.4,7.2,7.0, and preferred 4.5 ~ 7.0, further preferred 5.6 ~ 6.0.The method that the knowledge that those skilled in the art can grasp according to oneself selects to regulate pH voluntarily.
In addition, for the employed tin-zinc alloy electroplating of electro-plating method of the present invention is bathed, can also use the plating bath that contains amphoterics.As amphoterics, can enumerate imidazoline type, betaine type, alanine type, glycine type and acid amide type etc.These amphotericses can use separately, also can mix more than 2 kinds and use.The concentration of said amphoterics is 0.005 ~ 20g/L, for example 0.01g/L, 0.02g/L, 0.05g/L, 0.10g/L, 0.20g/L, 19g/L, 18g/L, 17g/L, 16g/L, preferred 0.01 ~ 15g/L, further preferred 0.01 ~ 10g/L.
Said tin-zinc alloy plating bath also contains additive, and said additive comprises formaldehyde and/or ammonium compounds, preferred formaldehyde and/or quaternary ammonium compound, the further particular methanol and/or four different third ammoniums that alkalize.As quaternary ammonium compound, for example can also enumerate the reaction product of tertiary amine compound and haloalkane.As concrete tertiary amine compound, for example can enumerate imidazoles, 1-Methylimidazole, 1-ethyl imidazol(e), glyoxal ethyline, 1-ethyl-glyoxal ethyline, 1-hydroxy methylimidazole, 1-vinyl imidazole and 1,5-methylimidazole as glyoxaline compound; As fatty amine, can enumerate monoethanolamine, diethylolamine, trolamine, n n dimetylaniline, quadrol, Diethylenetriamine, the two propylamine of imino-, three second tetramines, tetraethylene-pentamine, N, N-pair-(3-aminopropyl) quadrol etc.It has stronger reductive action, stops the oxidation of tin consumingly, helps the absorption of organism on electrode surface simultaneously, further improves stannous deposition potential, improves cathodic polarization, and coating is had tangible refinement and light effect.The concentration of said additive is 0.001 ~ 29g/L, preferred 0.001 ~ 25g/L, further preferred 0.005 ~ 20g/L.In addition, as the inhibitor of tin, can also use phenylor compounds such as pyrocatechol, pyrogallol, Resorcinol, sulphosalicylic acid, dihydroxy benzenes sulfonic acid potassium and salt thereof, L-xitix, Sorbitol Powder etc.
With regard to the tin ion concentration in the employed plating bath of electro-plating method of the present invention, divalent tin ion is 10～50g/L, preferred 15 ~ 45g/L, further preferred 20 ~ 40g/L.Zinc ion concentration is 10 ~ 80g/L, preferred 15 ~ 70g/L, further preferred 25 ~ 60g/L, more preferably 50g/L.As these metal ion sources, for example can enumerate oxyhydroxide, oxide compound, vitriol, hydrochloride, sulfamate, pyrophosphate salt, hydroxycarboxylate, sulphonate and the amino acid salts of each metal.Be preferably oxide compound, vitriol, hydrochloride, the oxyhydroxide of each metal.
Energising property when electroplating in order to make is good, can also in the employed plating bath of electro-plating method of the present invention, contain an alkali metal salt (sodium, potassium, lithium salts), alkali earth metal salt (magnesium, calcium, barium salt), ammonium salt, the organic amine salt (single methylamine, n n dimetylaniline, Trimethylamine 99, ethamine, Isopropylamine, quadrol, Diethylenetriamine etc.) of sulfuric acid, hydrochloric acid, thionamic acid, tetra-sodium, sulfonic acid, oxyhydroxide, carbonated.Particularly, can enumerate ammonium sulfate, ammonium chloride, trisodium phosphate, thionamic acid mono-methyl, sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood etc., special preferably sulfuric acid ammonium, ammonium chloride, Pottasium Hydroxide, salt of wormwood.The content of these salt is 10～300g/L, is preferably 50～200g/L.
Plated body in the electro-plating method of the present invention is with Fe, Ni, Cu or with the metallic substance of these alloys that are the basis, electroplates these metallic substance as negative electrode.To in extremely, can use tin-zinc alloy or on the Ti material, implement the insoluble electrode, carbon electrode etc. of Pt plating.When using insoluble anode, directly be dissolved in the method in the plating bath or with high concentration of dissolved the aqueous solution of the metal-salt of tin and zinc arranged, can keep the metal concentration of employed plating bath through additional through metal-salt with aforesaid tin and zinc.The high concentration solution of this metal can also be contained aforementioned Hydrocerol A or its salt and hydroxide alkalescence compound.
Compared with prior art, the present invention has following beneficial effect:
(1) through the tin ion in the employed plating bath of change and the ratio of zine ion, can implement the wideer tin-zinc alloy electroplating of compositing range.For example, in electronic unit, can implement to contain the tin-zinc alloy electroplating of zinc rate 1～20%, when special reinforcement resistance to salt water and erosion resistance, can implement to contain the tin-zinc alloy electroplating of zinc rate 15～45%.And then for the high overlay film of the erosion resistance that obtains considering atmospheric exposure property the time, can implement to contain the tin-zinc alloy electroplating of zinc rate 30～95%;
(2) in the electro-plating method of the present invention, plated body carries out through ordinary method carrying out electroplating work procedure again after the pre-treatment.In the pretreatment process, flood at least a kind of operation in degreasing, pickling, electrolytic scrubbing and the activation.After the plating, with water washing, dry get final product, can also implement to use the chromate treating of ordinary method and chemical surface control perhaps to use inorganics and organic coating processing the overlay film of gained;
(3) through selecting plating bath temperature and cathode current density etc.; And use specific tin-zinc alloy plating bath, thus obtaining a kind of tin-zinc alloy electroplating method, the tin-zinc alloy coating erosion resistance that said method obtains after electroplating is strong; Can reduce pollution, be desirable coating for cadmium.
Embodiment
For the present invention is described better, be convenient to understand technical scheme of the present invention, typical case of the present invention but non-restrictive example is following:
Embodiment 1
Steel plate is carried out using following plating bath after the pre-treatment, is that 15 ℃, the stirring velocity of plating bath are that 10m/min, cathode current density are 50A/dm in the plating bath temperature
2Condition under implement electroplating processes.
Embodiment 2
Steel plate is carried out using following plating bath after the pre-treatment, is that 20 ℃, the stirring velocity of plating bath are that 10m/min, cathode current density are 100A/dm in the plating bath temperature
2Condition under implement electroplating processes.
Embodiment 3
Steel plate is carried out using following plating bath after the pre-treatment, is that 25 ℃, the stirring velocity of plating bath are that 50m/min, cathode current density are 5A/dm in the plating bath temperature
2Condition under implement electroplating processes.
Comparative example 1
Steel plate being carried out after the pre-treatment, use the plating bath of embodiment 1, is that 10 ℃, the stirring velocity of plating bath are to implement electroplating processes under the condition of 50m/min in the plating bath temperature.
Comparative example 2
Steel plate being carried out after the pre-treatment, use the plating bath of embodiment 2, is that 20 ℃, the stirring velocity of plating bath are to implement electroplating processes under the condition of 2m/min in the plating bath temperature.
Comparative example 3
Steel plate being carried out after the pre-treatment, use the plating bath of embodiment 3, is that 18 ℃, the stirring velocity of plating bath are to implement electroplating processes under the condition of 3m/min in the plating bath temperature.
Tin-zinc alloy coating has superior corrosion resistance; When coating surface is not handled through chromating, can be through the neutral salt spray test of 720h, handle through chromating on the surface; Can be through the neutral salt spray test of 2000h, its corrosion resistance nature is very good.
The corrosion resistance nature test that is respectively embodiment 1-3 and Comparative Examples 1-3 processing back coating as shown in table 1.
Table 1. embodiment 1-3 and comparative example 1-3 handle back coating corrosion resistance nature
| Embodiment | Chromating | Thickness of coating μ m | 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 Examples 1 | Passivation | 5 | 12 | 200 |
| Comparative Examples 2 | Passivation | 5 | 15 | 220 |
| Comparative Examples 3 | Passivation | 5 | 20 | 250 |
Can find through table 1, compare embodiment 1-3 with comparative example and handle going out the white rust time and going out all prolongations significantly of red rust time, its corrosion-resistant obvious raising of back coating.
Should be noted that and understand, under the situation that does not break away from the desired the spirit and scope of the present invention of accompanying Claim, can make various modifications and improvement the present invention of above-mentioned detailed description.Therefore, the scope of the technical scheme of requirement protection does not receive the restriction of given any specific exemplary teachings.
Applicant's statement, the present invention explains detailed method of the present invention through the foregoing description, but the present invention is not limited to above-mentioned detailed method, does not mean that promptly the present invention must rely on above-mentioned detailed method and could implement.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and ancillary component, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. a tin-zinc alloy electroplating method is characterized in that, said method is carried out under following condition:
Tin-zinc alloy plating bath temperature: 15～25 ℃,
The stirring velocity of plating bath: 50 ~ 200m/min, and
Cathode current density: 5～100A/dm
2
2. the method for claim 1 is characterized in that, said method is carried out in following condition:
Tin-zinc alloy plating bath temperature: 15～25 ℃,
The stirring velocity of plating bath: 70 ~ 180m/min, and
Cathode current density: 20～80A/dm
2
3. according to claim 1 or claim 2 method is characterized in that said method is carried out in following condition:
Tin-zinc alloy plating bath temperature: 18～23 ℃,
The stirring velocity of plating bath: 100 ~ 150m/min, and
Cathode current density: 30～70A/dm
2
4. like the described tin-zinc alloy electroplating method of one of claim 1-3, it is characterized in that said tin-zinc alloy plating bath contains Hydrocerol A or/and Citrate trianion, optimization citric acid is or/and the Hydrocerol A organic ammonium salt, and further optimization citric acid is or/and dibasic ammonium citrate.
5. like the described tin-zinc alloy electroplating method of one of claim 1-4, it is characterized in that the concentration of citrate ion is 100 ~ 160g/L in the said tin-zinc alloy plating bath, preferred 110 ~ 150g/L, further preferred 120 ~ 150g/L.
6. according to the described tin-zinc alloy electroplating method of one of claim 1-5, it is characterized in that the pH of tin-zinc alloy plating bath is 4～8, preferred 4.5 ~ 7.0, further preferred 5.6 ~ 6.0.
7. according to the described tin-zinc alloy electroplating method of one of claim 1-6, it is characterized in that the tin-zinc alloy plating bath contains amphoterics;
Preferably, the concentration of said amphoterics is 0.005 ~ 20g/L, preferred 0.01 ~ 15g/L, further preferred 0.01 ~ 10g/L.
8. like the described tin-zinc alloy electroplating method of one of claim 1-7; It is characterized in that the tin-zinc alloy plating bath also contains additive, said additive comprises formaldehyde and/or ammonium compounds; Preferred formaldehyde and/or quaternary ammonium compound, the further particular methanol and/or four different third ammoniums that alkalize;
Preferably, the concentration of said additive is 0.001 ~ 29g/L, preferred 0.001 ~ 25g/L, further preferred 0.005 ~ 20g/L.
9. like each described tin-zinc alloy electroplating method of claim 1-8, it is characterized in that the divalent tin ion concentration in the tin-zinc alloy plating bath is 10～50g/L, preferred 15 ~ 45g/L, further preferred 20 ~ 40g/L.
10. like each described tin-zinc alloy electroplating method of claim 1-9, it is characterized in that the zinc ion concentration in the tin-zinc alloy plating bath is 10 ~ 80g/L, preferred 15 ~ 70g/L, further preferred 25 ~ 60g/L, more preferably 50g/L.
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103757672A (en) * | 2014-01-20 | 2014-04-30 | 广州市海科顺表面处理有限公司 | Zinc-tin alloy electroplating method |
| CN104178785A (en) * | 2014-09-17 | 2014-12-03 | 朱忠良 | Electroplating solution and electroplating method |
| CN104213159A (en) * | 2014-09-17 | 2014-12-17 | 朱忠良 | Electroplating liquid and electroplating method |
| CN104499020A (en) * | 2014-12-22 | 2015-04-08 | 常熟市伟达电镀有限责任公司 | Jewelry electroplating process |
| CN105063694A (en) * | 2015-08-21 | 2015-11-18 | 无锡桥阳机械制造有限公司 | Metal part electroplating method |
| CN105200473A (en) * | 2015-10-30 | 2015-12-30 | 无锡市嘉邦电力管道厂 | Electroplating method of metal piece |
| CN105350056A (en) * | 2015-11-24 | 2016-02-24 | 安徽天思朴超精密模具股份有限公司 | Anti-abrasion electroplating liquid material combination and manufacturing method and application of anti-abrasion electroplating liquid |
| CN105750354A (en) * | 2016-03-31 | 2016-07-13 | 常州易藤电气有限公司 | Method for manufacturing copper-magnesium alloy stranded wire for cold tinned railway |
| CN106119938A (en) * | 2016-08-31 | 2016-11-16 | 厦门同恒金属有限公司 | A kind of barrel plating tank red brass electroplanting device and technique |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103757672A (en) * | 2014-01-20 | 2014-04-30 | 广州市海科顺表面处理有限公司 | Zinc-tin alloy electroplating method |
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| CN104178785A (en) * | 2014-09-17 | 2014-12-03 | 朱忠良 | Electroplating solution and electroplating method |
| CN104213159A (en) * | 2014-09-17 | 2014-12-17 | 朱忠良 | Electroplating liquid and electroplating method |
| CN104499020A (en) * | 2014-12-22 | 2015-04-08 | 常熟市伟达电镀有限责任公司 | Jewelry electroplating process |
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| CN105350056A (en) * | 2015-11-24 | 2016-02-24 | 安徽天思朴超精密模具股份有限公司 | Anti-abrasion electroplating liquid material combination and manufacturing method and application of anti-abrasion electroplating liquid |
| CN105750354A (en) * | 2016-03-31 | 2016-07-13 | 常州易藤电气有限公司 | Method for manufacturing copper-magnesium alloy stranded wire for cold tinned railway |
| CN106119938A (en) * | 2016-08-31 | 2016-11-16 | 厦门同恒金属有限公司 | A kind of barrel plating tank red brass electroplanting device and technique |
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