CN105002528A - Cyanide-free silver electroplating solution and electroplating method thereof - Google Patents

Cyanide-free silver electroplating solution and electroplating method thereof Download PDF

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Publication number
CN105002528A
CN105002528A CN201510519577.8A CN201510519577A CN105002528A CN 105002528 A CN105002528 A CN 105002528A CN 201510519577 A CN201510519577 A CN 201510519577A CN 105002528 A CN105002528 A CN 105002528A
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CN
China
Prior art keywords
silver
concentration
plating solution
sodium
carboxylic acid
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Pending
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CN201510519577.8A
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Chinese (zh)
Inventor
沈秋
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Wuxi Qingyang Machinery Manufacturing Co Ltd
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Wuxi Qingyang Machinery Manufacturing Co Ltd
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Priority to CN201510519577.8A priority Critical patent/CN105002528A/en
Publication of CN105002528A publication Critical patent/CN105002528A/en
Pending legal-status Critical Current

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Abstract

The invention provides a silver electroplating solution and an electroplating method thereof. 1 L of the silver electroplating solution comprises 60-90 g of silver nitrate, 10-20 g of ammonium acetate, 80 to 120 g of pyridine carboxylic acid, 20 to 40 g of sodium metabisulfite, 60 to 80 g of hydantoin derivative, and 0.5 to 2 g of saccharin soluble hydrate. The silver electroplating solution is free from cyanide ions, waste treatment is reduced, and high safety and environment friendliness are achieved; a clad layer obtained through electroplating is excellent in corrosion resistance, and is excellent in anti-tarish property.

Description

A kind of cyanogen-free silver-plating solution and electro-plating method thereof
Technical field
The present invention relates to electroplating technology field, particularly relate to a kind of cyanogen-free silver-plating solution and electro-plating method thereof.
Background technology
Silvered film is easy to polishing, there are very strong reflective ability and good heat conduction, conduction, welding property, high to the chemical stability of organic bronsted lowry acids and bases bronsted lowry, and its price is cheap relative to other precious metals, has been widely used in the field of electronic industry, ornament, tableware and various artwork.
The advantages such as current efficiency is high, dispersive ability good, covering power is strong owing to having, coating crystallization is careful, at present, mostly still adopt both at home and abroad and have cyanogen silver plating process to electroplate silver layer.But prussiate silver plating liquid has hypertoxicity, serious environment pollution, the health of the harm producer, and also treatment cost of waste liquor is higher, so people wish to replace prussiate electrosilvering technique with other electroplating technology.But the problems such as the non-cyanide silver coating system ubiquity coating performance used at present is lower; therefore from the viewpoint of safety, environment protection etc., a kind of low toxicity, stable silver plating liquid and silver plating process is developed to replace the of far-reaching significance and extremely urgent of prussiate electrosilvering.
Summary of the invention
In view of this, one aspect of the present invention provides a kind of plate silver plating solution, not containing cryanide ion in plate silver plating solution of the present invention, reduces wastewater treatment, safety and environmental protection.
The present invention by the following technical solutions.
A kind of plate silver plating solution, comprises Silver Nitrate 60 ~ 90g/L, ammonium acetate 10 ~ 20g/L, pyridine carboxylic acid 80 ~ 120g/L, Sodium Pyrosulfite 20 ~ 40g/L, hydantoin derivatives 60 ~ 80g/L and o-benzoic sulfimide sodium 0.5 ~ 2g/L.
Preferably, Silver Nitrate 70 ~ 80g/L, ammonium acetate 15 ~ 20g/L, pyridine carboxylic acid 100 ~ 120g/L, Sodium Pyrosulfite 30 ~ 40g/L, hydantoin derivatives 60 ~ 70g/L and o-benzoic sulfimide sodium 0.5 ~ 1g/L is comprised.
Preferably, Silver Nitrate 75g/L, ammonium acetate 15g/L, pyridine carboxylic acid 110g/L, Sodium Pyrosulfite 30g/L, hydantoin derivatives 70g/L and o-benzoic sulfimide sodium 0.6g/L is comprised.
Preferably, plate silver plating solution pH value is 8 ~ 9.
The present invention provides on the other hand a kind of and uses above-mentioned plate silver plating solution electric plating method, and the method electroplate the good and anti-discoloration excellence of the coating corrosion resistance obtained.
The above-mentioned plate silver plating solution electric plating method of a kind of use, comprises the following steps:
(1) electroplate liquid is formulated as follows: the concentration of Silver Nitrate is 60 ~ 90g/L, the concentration of ammonium acetate is 10 ~ 20g/L, the concentration of pyridine carboxylic acid is 80 ~ 120g/L, the concentration of Sodium Pyrosulfite is 20 ~ 40g/L, the concentration of hydantoin derivatives is 60 ~ 80g/L, and the concentration of o-benzoic sulfimide sodium is 0.5 ~ 2g/L;
(2) do anode with silver plate, workpiece does negative electrode, electroplates.
Preferably, in described step (2), the temperature of plating is 30 ~ 45 DEG C.
Preferably, in described step (2), the current density of plating is 20 ~ 30mA/cm 2.
Preferably, in step (2), the distance of negative electrode and positive electrode is 8 ~ 15cm.
Compared with prior art, beneficial effect of the present invention: plate silver plating solution of the present invention comprises Silver Nitrate 60 ~ 90g/L, ammonium acetate 10 ~ 20g/L, pyridine carboxylic acid 80 ~ 120g/L, Sodium Pyrosulfite 20 ~ 40g/L, hydantoin derivatives 60 ~ 80g/L and o-benzoic sulfimide sodium 0.5 ~ 2g/L.Not containing cryanide ion in plate silver plating solution of the present invention, reduce wastewater treatment, safety and environmental protection; The coating corrosion resistance that plating obtains is good and anti-discoloration is excellent.
Embodiment
Further illustrate technical scheme of the present invention respectively below in conjunction with the embodiments.
Raw material involved in following examples is commercially available.
Embodiment 1: the cyanogen-free silver-plating solution of the present embodiment comprises following component:
Use above-mentioned cyanogen-free silver-plating solution electric plating method as follows:
Be formulated as follows electroplate liquid: the concentration of Silver Nitrate is 60g/L, the concentration of ammonium acetate is 10g/L, and the concentration of pyridine carboxylic acid is 80g/L, and the concentration of Sodium Pyrosulfite is 20g/L, the concentration of hydantoin derivatives is 60g/L, and the concentration of o-benzoic sulfimide sodium is 0.5g/L;
Do anode with silver plate, workpiece does negative electrode, and the distance of negative electrode and positive electrode is 8cm, is 30 DEG C at bath temperature, and current density is 20mA/cm 2electroplate under condition.
Embodiment 2: the cyanogen-free silver-plating solution of the present embodiment comprises following component:
Use above-mentioned cyanogen-free silver-plating solution electric plating method as follows:
Be formulated as follows electroplate liquid: the concentration of Silver Nitrate is 70g/L, the concentration of ammonium acetate is 18g/L, and the concentration of pyridine carboxylic acid is 100g/L, and the concentration of Sodium Pyrosulfite is 30g/L, the concentration of hydantoin derivatives is 60g/L, and the concentration of o-benzoic sulfimide sodium is 0.5g/L;
Do anode with silver plate, workpiece does negative electrode, and the distance of negative electrode and positive electrode is 10cm, is 30 DEG C at bath temperature, and current density is 20mA/cm 2electroplate under condition.
Embodiment 3: the cyanogen-free silver-plating solution of the present embodiment comprises following component:
Use above-mentioned cyanogen-free silver-plating solution electric plating method as follows:
Be formulated as follows electroplate liquid: the concentration of Silver Nitrate is 75g/L, the concentration of ammonium acetate is 15g/L, and the concentration of pyridine carboxylic acid is 110g/L, and the concentration of Sodium Pyrosulfite is 30g/L, the concentration of hydantoin derivatives is 70g/L, and the concentration of o-benzoic sulfimide sodium is 0.6g/L;
Do anode with silver plate, workpiece does negative electrode, and the distance of negative electrode and positive electrode is 8cm, is 30 DEG C at bath temperature, and current density is 20mA/cm 2electroplate under condition.
Testing method:
1, K is adopted 2the anti-tarnishing ability of S immersion test inspection coating
Coating is SO in an atmosphere 2, H 2under the effect of the corrosive mediums such as S, can make that Surface Creation is faint yellow, tawny even the silver sulfide film of chocolate.After coating color, not only affect outward appearance, the more important thing is that contact resistance increases, affect electroconductibility, and cause welding difficulty, reduce use value.In order to verify the discoloration-resisting of coating more accurately, carry out K 2s solution soaking is tested, and uses the K of 0.1mol/L at normal temperatures 2s solution coating, the changing conditions of record coating color in immersion, the anti-tarnishing ability of more various coating.
3, the bonding strength of test piece bending test coating is used
After workpiece plating, by workpiece repeatedly 90-degree bent, observe whether have peeling, stripping, break-off.
Above-mentioned test result is as following table
Find that the present invention electroplates the coating obtained and combines good by above-mentioned test result, anti-discoloration is excellent, and especially embodiment 3 best performance, can meet the application that decorative electroplating and functional plating etc. are multi-field; Do not contain cryanide ion in plate silver plating solution of the present invention simultaneously, reduce wastewater treatment, safety and environmental protection.
Additionally by thermal shock method, find the coating bubble-free that plating of the present invention is obtained, also do not peel off, illustrate that the present invention electroplates obtained coating and matrix associativity is good, can effective solution coating stress and fragility is large, bonding force is poor problem.
It should be noted that and understand, when not departing from the spirit and scope of accompanying claim the present invention for required protection, 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 detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process 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 (8)

1. a plate silver plating solution; it is characterized in that, comprise Silver Nitrate 60 ~ 90g/L, ammonium acetate 10 ~ 20g/L, pyridine carboxylic acid 80 ~ 120g/L, Sodium Pyrosulfite 20 ~ 40g/L, hydantoin derivatives 60 ~ 80g/L and o-benzoic sulfimide sodium 0.5 ~ 2g/L.
2. plate silver plating solution according to claim 1; it is characterized in that, comprise Silver Nitrate 70 ~ 80g/L, ammonium acetate 15 ~ 20g/L, pyridine carboxylic acid 100 ~ 120g/L, Sodium Pyrosulfite 30 ~ 40g/L, hydantoin derivatives 60 ~ 70g/L and o-benzoic sulfimide sodium 0.5 ~ 1g/L.
3. plate silver plating solution according to claim 1, is characterized in that, comprises Silver Nitrate 75g/L, ammonium acetate 15g/L, pyridine carboxylic acid 110g/L, Sodium Pyrosulfite 30g/L, hydantoin derivatives 70g/L and o-benzoic sulfimide sodium 0.6g/L.
4. plate silver plating solution according to claim 1, is characterized in that, plate silver plating solution pH value is 8 ~ 9.
5. use the electroplate liquid electric plating method described in claim 1, it is characterized in that, comprise the following steps:
(1) electroplate liquid is formulated as follows: the concentration of Silver Nitrate is 60 ~ 90g/L, the concentration of ammonium acetate is 10 ~ 20g/L, the concentration of pyridine carboxylic acid is 80 ~ 120g/L, the concentration of Sodium Pyrosulfite is 20 ~ 40g/L, the concentration of hydantoin derivatives is 60 ~ 80g/L, and the concentration of o-benzoic sulfimide sodium is 0.5 ~ 2g/L;
(2) do anode with silver plate, workpiece does negative electrode, electroplates.
6. method according to claim 5, is characterized in that, in described step (2), the temperature of plating is 30 ~ 45 DEG C.
7. method according to claim 5, is characterized in that, in described step (2), the current density of plating is 20 ~ 30mA/cm 2.
8. method according to claim 5, is characterized in that, in described step (2), the distance of negative electrode and positive electrode is 8 ~ 15cm.
CN201510519577.8A 2015-08-21 2015-08-21 Cyanide-free silver electroplating solution and electroplating method thereof Pending CN105002528A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105420770A (en) * 2015-11-30 2016-03-23 苏州市金星工艺镀饰有限公司 Color-change-preventing cyanide-free silver plating electroplating liquid and electroplating method thereof
CN107254696A (en) * 2017-06-08 2017-10-17 广东电网有限责任公司电力科学研究院 Silver/graphite alkene composite silver plating liquor and preparation method thereof and electrodeposition technology
CN107313083A (en) * 2017-07-25 2017-11-03 安徽瑞泰汽车零部件有限责任公司 A kind of silver-plated environment-protection electroplating liquid of part

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760768A (en) * 2010-01-20 2010-06-30 河南科技大学 Electroplating solution for cyanide-free silver plating and cyanide-free silver plating method
CN102168290A (en) * 2011-04-08 2011-08-31 哈尔滨工业大学 Cyanide-free silver plating electroplating solution and preparation method and electroplating method thereof
CN102268701A (en) * 2011-08-02 2011-12-07 南京大学 Non-cyanide bright silver electroplating bath and preparation method thereof
CN103046091A (en) * 2013-01-09 2013-04-17 西安交通大学 Plating solution and plating method of cyanide-free plating silver
CN104532310A (en) * 2014-11-14 2015-04-22 无锡信大气象传感网科技有限公司 A cyanide-free silvering electroplating solution and a preparing method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101760768A (en) * 2010-01-20 2010-06-30 河南科技大学 Electroplating solution for cyanide-free silver plating and cyanide-free silver plating method
CN102168290A (en) * 2011-04-08 2011-08-31 哈尔滨工业大学 Cyanide-free silver plating electroplating solution and preparation method and electroplating method thereof
CN102268701A (en) * 2011-08-02 2011-12-07 南京大学 Non-cyanide bright silver electroplating bath and preparation method thereof
CN103046091A (en) * 2013-01-09 2013-04-17 西安交通大学 Plating solution and plating method of cyanide-free plating silver
CN104532310A (en) * 2014-11-14 2015-04-22 无锡信大气象传感网科技有限公司 A cyanide-free silvering electroplating solution and a preparing method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105420770A (en) * 2015-11-30 2016-03-23 苏州市金星工艺镀饰有限公司 Color-change-preventing cyanide-free silver plating electroplating liquid and electroplating method thereof
CN107254696A (en) * 2017-06-08 2017-10-17 广东电网有限责任公司电力科学研究院 Silver/graphite alkene composite silver plating liquor and preparation method thereof and electrodeposition technology
CN107313083A (en) * 2017-07-25 2017-11-03 安徽瑞泰汽车零部件有限责任公司 A kind of silver-plated environment-protection electroplating liquid of part

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