CN105420770A - Color-change-preventing cyanide-free silver plating electroplating liquid and electroplating method thereof - Google Patents

Color-change-preventing cyanide-free silver plating electroplating liquid and electroplating method thereof Download PDF

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Publication number
CN105420770A
CN105420770A CN201510853444.4A CN201510853444A CN105420770A CN 105420770 A CN105420770 A CN 105420770A CN 201510853444 A CN201510853444 A CN 201510853444A CN 105420770 A CN105420770 A CN 105420770A
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China
Prior art keywords
plating
electroplating
electroplate liquid
sodium
solution
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CN201510853444.4A
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Inventor
冯正元
冯育华
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Suzhou Venus Craft Plating Decoration Co Ltd
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Suzhou Venus Craft Plating Decoration Co Ltd
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Priority to CN201510853444.4A priority Critical patent/CN105420770A/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00Electroplating: Baths therefor
    • C25D3/02Electroplating: Baths therefor from solutions
    • C25D3/46Electroplating: Baths therefor from solutions of silver
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25DPROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00Electroplating characterised by the process; Pretreatment or after-treatment of workpieces

Abstract

The invention discloses color-change-preventing cyanide-free silver plating electroplating liquid and an electroplating method thereof. The electroplating liquid comprises, by mass volume concentration, 38-50 g/L of silver nitrate, 110-120 g/L of 2-sulpho-5,5-dimethyl hydantoin, 10-30 g/L of succinimide, 40-100 g/L of sodium pyrophosphate, 30-70 g/L of pyrophosphoric acid, 35-55 g/L of methionine, 0.5-2 g/L of polyethylene glycol, 4-10 g/L of benzotriazole, 1-8 g/L of nonylphenol polyoxyethylene laurel ether and 20-150 g/L of sodium sulfite. The pyrophosphoric acid is used for adjusting the pH to range from 3 to 5, and the temperature of the electroplating liquid ranges from 20 DEG to 55 DEG C. According to the color-change-preventing cyanide-free silver plating electroplating liquid and the electroplating method thereof, the combining force between a silver plating layer obtained through the electroplating method and a plating part base material is good, the leveling capability is good, the covering capability is excellent, the color is bright and not likely to become dark, an intermediate layer does not need to be pre-plated on the surface of the base material, the electroplating liquid can be used in a wide current range, and repeatability is good.

Description

A kind of Anti-tarnishing cyanogen-free silver-plating solution and electro-plating method thereof
Technical field
The invention belongs to alloy plating liquid field, be specifically related to a kind of Anti-tarnishing plate silver plating solution and electro-plating method thereof.
Background technology
Argent, with its excellent performance and lower cost, becomes one of precious metal be most widely used, especially its distinctive silvery white metalluster, is often applied to family high-grade apparatus, artwork and jewellery etc. as ornament layer.Sulfurous gas in air or hydrogen sulfide easily with silvering generation deferred reaction, cause silver coating from coloring dimmed, usually through plating posttreatment, will mainly soak bright, chemical and electrochemical passivation, painting tectum etc.
Cyaniding plant of silver technique because of its bath stability good, current silver plating solution is most based on hydride systems, and serious harm human body and ecotope, just progressively replaced by non-cyanide silver coating.The non-cyanide silver electroplating solution ion and silver ions not containing cyanogen carries out complexing, obtains coating by electrochemical reaction deposition.But the poor stability of current used non-cyanide silver coating system ubiquity plating solution, the stress of silvered film are large, with the problem such as the associativity current density range that is poor, that allow of substrate is narrow, thus non-cyanide silver coating is not widely used in electrosilvering industry.
In order to obtain good bonding force, in cyanide-free silver plating process, adopt first plates one deck nickel at substrate surface more, then electroless plating one deck silver, last electrosilvering, the binding force of cladding material obtained through this method and compactness good.This processing step is complicated, and energy consumption is larger.Developing a kind of can the cyanide-free silver plating process of industrial applications be the target of people's unremitting pursue.
Summary of the invention
Goal of the invention: for overcoming defect of the prior art, the invention provides a kind of Anti-tarnishing plate silver plating solution and electro-plating method thereof, and to solve, existing non-cyanide silver electroplating system bath stability is poor, current density range is narrow and the allochroic technical problem of coating.
Technical scheme: the invention provides a kind of without cyanogen Anti-tarnishing cyanogen-free silver-plating solution, comprise the component of following mass body volume concentrations: Silver Nitrate 38 ~ 50g/L, 2-sulfo--5,5-T10 110 ~ 120g/L, succimide 10 ~ 30g/L, trisodium phosphate 40 ~ 100g/L, tetra-sodium 30 ~ 70g/L, methionine(Met) 35 ~ 55g/L, polyoxyethylene glycol 0.5 ~ 2g/L, benzotriazole 4-10g/L, Nonyl pheno bay ether 1-8g/L and S-WAT 20 ~ 150g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 3 ~ 5, and temperature of electroplating solution is 20 ~ 55 DEG C.
Wherein, as preferably, Anti-tarnishing cyanogen-free silver-plating solution, comprise the component of following mass body volume concentrations: Silver Nitrate 40 ~ 50g/L, 2-sulfo--5,5-T10 110 ~ 120g/L, succimide 25 ~ 30g/L, trisodium phosphate 50 ~ 100g/L, tetra-sodium 30 ~ 60g/L, methionine(Met) 45 ~ 52g/L, polyoxyethylene glycol 0.5 ~ 2g/L, benzotriazole 6-10g/L, Nonyl pheno bay ether 3-8g/L and S-WAT 50 ~ 150g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 4 ~ 5, and temperature of electroplating solution is 20 ~ 55 DEG C.
Particularly, Anti-tarnishing cyanogen-free silver-plating solution, comprise the component of following mass body volume concentrations: Silver Nitrate 43g/L, 2-sulfo--5,5-T10 118g/L, succimide 30g/L, trisodium phosphate 70g/L, tetra-sodium 55g/L, methionine(Met) 52g/L, polyoxyethylene glycol 1g/L, benzotriazole 8g/L, Nonyl pheno bay ether 8g/L and S-WAT 130g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 5, and temperature of electroplating solution is 20 ~ 55 DEG C.
According to above-mentioned plating solution formula, the present invention also provides a kind of electro-plating method, comprises the following steps:
(1) plating piece substrate surface pre-treatment, i.e. Solvent degreasing, alkali solution oil removing, washing post-drying or dry; Wherein alkali solution comprises NaOH8-12g/L, Na 2cO 345g/L, Na 3pO 440 ~ 50g/L, Na 2siO 38g/L.
(2) electrosilvering: place the electroplate liquid described in any one of claims 1 to 3 in plating tank, silver plate or platinized platinum are anode, and plating piece is working electrode, and the distance between anode and working electrode is 8 ~ 20cm.Current density is 0.2 ~ 2A/dm 2, solution pump circulation stirring, electroplate 10 ~ 30min at 35 ~ 70 DEG C and obtain silvering, 25min electroplating time is best;
(3) plating piece being silvering by the surface that step (2) obtains is placed in deionized water and cleans, packaging after dry.
Beneficial effect: compared with prior art, the present invention has the following advantages: this Anti-tarnishing cyanogen-free silver-plating solution environmental protection is easy to get, and adopts multiple coordination agent to carry out coordination, electroplate liquid good stability.Between the silvered film adopting electro-plating method of the present invention to obtain and plating piece base material, bonding force is good, and leveling ability is good, and covering power is excellent, color light, not easily dimmed, and without the need in substrate surface preplating middle layer, electroplate liquid can use in wider range of current, reproducible.
Embodiment
Below technical solution of the present invention is described in detail, but protection scope of the present invention is not limited to described embodiment.
Embodiment 1
First, conveniently pre-treating process pre-treatment plating piece base material, plating piece base material is copper or copper alloy, and pre-treatment comprises Solvent degreasing, alkali solution oil removing, washing post-drying or dries; Wherein alkali solution comprises NaOH10g/L, Na 2cO 345g/L, Na 3pO 440g/L, Na 2siO 38g/L.Pretreated plating piece is put into electroplate liquid as working electrode, the composition of electroplate liquid comprises: Silver Nitrate 38g/L, 2-sulfo--5,5-T10 110g/L, succimide 15g/L, trisodium phosphate 40g/L, tetra-sodium 30g/L, methionine(Met) 35g/L, polyoxyethylene glycol 0.5g/L, benzotriazole 4g/L, Nonyl pheno bay ether 2g/L and S-WAT 50g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 4.7, and temperature of electroplating solution is 30 DEG C.Platinized platinum is anode, and the distance between anode and working electrode is 20cm, and current density is set to 0.5A/dm 2, plating 30min, after electroplate, deionization washing, air-dryly to pack respectively afterwards.Silvered film color that the present embodiment obtains silvery white light, fine and closely woven smooth, cover complete, have strong anti-tarnishing ability, through repeatedly bending, coating do not occur peeling off skin effect phenomenon, and description taken in conjunction power is good.
Embodiment 2
Other operational conditions are with embodiment 1, difference is: electroplate liquid comprises the component of following mass body volume concentrations: Silver Nitrate 50g/L, 2-sulfo--5, 5-T10 120g/L, succimide 30g/L, trisodium phosphate 100g/L, tetra-sodium 60g/L, methionine(Met) 52g/L, polyoxyethylene glycol 2g/L, benzotriazole 10g/L, Nonyl pheno bay ether 8g/L and S-WAT 150g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 5, temperature of electroplating solution is 30 DEG C, anode is silver plate, distance between anode and working electrode is 15cm, current density is set to 2A/dm 2, plating 30min, after electroplate, deionization washing, air-dryly to pack respectively afterwards.Silvered film color that the present embodiment obtains silvery white light, fine and closely woven smooth, have strong anti-tarnishing ability, through repeatedly bending, coating do not occur peeling off skin effect phenomenon, and description taken in conjunction power is good.
Embodiment 3
Other elementary operation conditions are with embodiment 1, difference is: electroplate liquid comprises the component of following mass body volume concentrations: Silver Nitrate 43g/L, 2-sulfo--5, 5-T10 118g/L, succimide 30g/L, trisodium phosphate 70g/L, tetra-sodium 55g/L, methionine(Met) 52g/L, polyoxyethylene glycol 1g/L, benzotriazole 8g/L, Nonyl pheno bay ether 8g/L and S-WAT 130g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 5, temperature of electroplating solution is 25 DEG C, anode is silver plate, distance between anode and working electrode is 8cm, plating 25min, current density is set to 1A/dm 2, after having electroplated, deionization is washed, and air-dryly to pack respectively afterwards.Silvered film color that the present embodiment obtains silvery white light, fine and closely woven smooth, have strong anti-tarnishing ability, through repeatedly bending, coating do not occur peeling off skin effect phenomenon, and description taken in conjunction power is good.
Above embodiment just plays illustrated example effect to technical conceive of the present invention; can not limit the scope of the invention with this; those skilled in the art are not departing from the spirit and scope of technical solution of the present invention; modify and be equal to replacement, all should drop within protection scope of the present invention.

Claims (7)

1. an Anti-tarnishing cyanogen-free silver-plating solution, it is characterized in that, described electroplate liquid comprises the component of following mass body volume concentrations: Silver Nitrate 38 ~ 50g/L, 2-sulfo--5,5-T10 110 ~ 120g/L, succimide 10 ~ 30g/L, trisodium phosphate 40 ~ 100g/L, tetra-sodium 30 ~ 70g/L, methionine(Met) 35 ~ 55g/L, polyoxyethylene glycol 0.5 ~ 2g/L, benzotriazole 4-10g/L, Nonyl pheno bay ether 1-8g/L and S-WAT 20 ~ 150g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 3 ~ 5, and temperature of electroplating solution is 20 ~ 55 DEG C.
2. Anti-tarnishing cyanogen-free silver-plating solution according to claim 1, it is characterized in that, described electroplate liquid comprises the component of following mass body volume concentrations: Silver Nitrate 40 ~ 50g/L, 2-sulfo--5, 5-T10 110 ~ 120g/L, succimide 25 ~ 30g/L, trisodium phosphate 50 ~ 100g/L, tetra-sodium 30 ~ 60g/L, methionine(Met) 45 ~ 52g/L, polyoxyethylene glycol 0.5 ~ 2g/L, benzotriazole 6-10g/L, Nonyl pheno bay ether 3-8g/L and S-WAT 50 ~ 150g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 4 ~ 5, temperature of electroplating solution is 20 ~ 55 DEG C.
3. Anti-tarnishing cyanogen-free silver-plating solution according to claim 1, it is characterized in that, described electroplate liquid comprises the component of following mass body volume concentrations: Silver Nitrate 43g/L, 2-sulfo--5,5-T10 118g/L, succimide 30g/L, trisodium phosphate 70g/L, tetra-sodium 55g/L, methionine(Met) 52g/L, polyoxyethylene glycol 1g/L, benzotriazole 8g/L, Nonyl pheno bay ether 8g/L and S-WAT 130g/L, the pH of electroplate liquid adopts tetra-sodium to be adjusted to 5, and temperature of electroplating solution is 20 ~ 55 DEG C.
4. an electro-plating method for the electroplate liquid according to any one of claims 1 to 3, is characterized in that, comprises the following steps:
(1) plating piece substrate surface pre-treatment, i.e. Solvent degreasing, alkali solution oil removing, washing post-drying or dry;
(2) electrosilvering: place the electroplate liquid described in any one of claims 1 to 3 in plating tank, silver plate or platinized platinum are anode, and plating piece is working electrode, and current density is 0.2 ~ 2A/dm 2, solution pump circulation stirring, electroplates 10 ~ 30min and obtains silvering at 35 ~ 70 DEG C;
(3) plating piece being silvering by the surface that step (2) obtains is placed in deionized water and cleans, packaging after dry.
5. electro-plating method according to claim 4, is characterized in that, the alkali solution described in step (1) comprises the component of following mass body volume concentrations: NaOH8-12g/L, Na 2cO 345g/L, Na 3pO 440 ~ 50g/L, Na 2siO 38g/L.
6. electro-plating method according to claim 4, is characterized in that, the anode described in step (2) and the distance between working electrode are 8 ~ 20cm.
7. electro-plating method according to claim 4, is characterized in that, the preferred 25min of electroplating time in step (2).
CN201510853444.4A 2015-11-30 2015-11-30 Color-change-preventing cyanide-free silver plating electroplating liquid and electroplating method thereof Pending CN105420770A (en)

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CN106245074A (en) * 2016-08-30 2016-12-21 湖北吉和昌化工科技有限公司 The electroplate liquid of a kind of Anti-tarnishing electrosilvering and electroplating technology thereof
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CN109504989A (en) * 2018-12-11 2019-03-22 湖北工程学院 A kind of bright brush plating silver plating liquid and its preparation process, application method
CN109853014A (en) * 2019-01-29 2019-06-07 广州鸿葳科技股份有限公司 A kind of silver oxidation resistance agent of resistance to potassium sulfide and preparation method thereof
CN111118559A (en) * 2019-12-20 2020-05-08 常州极太汽车配件有限公司 Composition for surface treatment of copper flexible connection

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106245074A (en) * 2016-08-30 2016-12-21 湖北吉和昌化工科技有限公司 The electroplate liquid of a kind of Anti-tarnishing electrosilvering and electroplating technology thereof
CN107313084A (en) * 2017-08-10 2017-11-03 佛山市南博旺环保科技有限公司 A kind of alkaline non-cyanide plate silver plating solution and silver-coating method
CN109504989A (en) * 2018-12-11 2019-03-22 湖北工程学院 A kind of bright brush plating silver plating liquid and its preparation process, application method
CN109853014A (en) * 2019-01-29 2019-06-07 广州鸿葳科技股份有限公司 A kind of silver oxidation resistance agent of resistance to potassium sulfide and preparation method thereof
CN111118559A (en) * 2019-12-20 2020-05-08 常州极太汽车配件有限公司 Composition for surface treatment of copper flexible connection

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Application publication date: 20160323