CN102383154A - Cyanide-free gold-plating electroplating solution - Google Patents
Cyanide-free gold-plating electroplating solution Download PDFInfo
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- CN102383154A CN102383154A CN2011103697339A CN201110369733A CN102383154A CN 102383154 A CN102383154 A CN 102383154A CN 2011103697339 A CN2011103697339 A CN 2011103697339A CN 201110369733 A CN201110369733 A CN 201110369733A CN 102383154 A CN102383154 A CN 102383154A
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Abstract
The invention provides a cyanide-free gold-plating electroplating solution which mainly comprises the components of gold inorganic acid, main complexing agent of alkane compound and auxiliary complexing agent of nonnutritive sweetener. The electroplating solution has the advantages that the cost of required raw materials is low, the preparation method is simple and feasible, the plating solution is non-toxic or low toxic, the stability is good, the plating solution is neutral and has buffer capacity, no great change occurs on the pH value of the plating solution placed for a long time, the replacement rate with the metal base such as nickel and copper is low, the pre-gold-plating is not needed, the application range of current density is wide, the binding force of the plating layer after electro-deposition is good, the plating layer is bright and can meet the application in multiple fields of ordinary decorative electroplating and functional electroplating, not contain cyanide is contained in the waste water of the plating solution, the treatment is relatively simple, and damages to the human body and the environment are small.
Description
Technical field
The present invention relates to a kind of cyanogen-less gold plating solution.
Background technology
The simple substance of gold is commonly referred to as " gold ", is rare, the special and valuable metal of a kind of ten minutes.Gold utensil has flavous appearance, and ductility is good, is easy to polishing; The chemical property torpescence is not easy and other element generation chemical reactions, can only be dissolved in the stronger material of corrodibility such as chloroazotic acid and can not be dissolved in other type acid; It is strong to have solidity to corrosion, and good discoloration-resisting.Thereby the extensive use of gold mainly contains, and as international reserve, is used for the decoration of jewelry, jewellery etc., is applied among industry and the modern high technology industry.
Craft of gilding mainly adopts cyaniding gold-plated both at home and abroad.In the cyaniding craft of gilding, the water of prussiate ability dissolve gold generates water-soluble KAu (CN)
2, generation potassium cyanide solution both well dissolved gold, chemicalstability is also fine, gained gold plating liquid dispersive ability and degree of depth ability are good, galvanic deposit gained coating light property is good.But, the prussiate severe toxicity, harm humans health and environment protection greatly all must take safety measures in production and use, such as possessing good ventilation installation and wastewater treatment condition etc. in strictness.Along with the development of electroplating technology, the development of new electroplating technology, and people are for the concern of world environments protection, so countries in the world launch respectively relevant policy, progressively eliminate the cyaniding depositing process.Also issued a series of policy in China; For example in order to promote the development of electroplating industry; Improve the production status of electroplating industry; Former State Economic and Trade Commission issues the 32nd command on June 2nd, 2002, has announced the catalogue of technology and product " eliminate outmoded production capacity, " (the 3rd batch), and time limit is eliminated to require will " have cyanogen to electroplate " in 2003.On February 27th, 2003; Former State Economic and Trade Commission and State Environmental Protection Administration have announced " state key industry clearer production technology guiding catalogue " (second batch), propose the nontoxic gas protection wire two-wire electroless copper technology of applying, low chromic acid hard chrome plating technology, Repone K galvanizing technique, zinc coating low chromium passivating technology and zinc-nickel alloy technology.On February 1st, 2007, State Environmental Protection Administration came into effect " electroplating industry cleaner production standard ".
Along with the progress of electroplating technology, people protect the reinforcement of Environmental awareness, and the galvanizer authors put among the research work of cyanideless electro-plating one after another.The Citrate trianion that has proposed is gold-plated, had a lot of manufacturers using now, but employed golden salt is to use potassium auric cyanide, is still prussiate, does not truly realize no cyaniding.In order to realize not having cyaniding, galvanizer author has proposed successively that sulfurous acid is gold-plated, thiosulfuric acid is gold-plated, and quadrol is gold-plated, sulfydryl sulfonic acid is gold-plated, the L-halfcystine is gold-plated, NSC 9226 is gold-plated etc., and has applied for corresponding patent.For example Japanese Patent JP11193474, JP2000204496, JP2000355792 etc.
Cyanide-free plating bath is used more with the sulphite gold plating liquid, but these cyanogen-less gold liquid compare with the cyaniding gold plating liquid some shortcomings still arranged, such as the bath stability problem.No matter be at acid, neutral or alkaline cyanogen-less gold liquid; Sulfite ion easily and the dissolved oxygen generation redox reaction in the plating bath; Inferior sulfate radical becomes sulfate radical, causes plating bath to be formed and changes, and this gives actual deposit and use brings many inconvenience.Secondly Gold plated Layer wears no resistance, and before just gold-plated, often needs the preplating gold, changes normal gold-plated process again over to after promptly before just gold-plated, in a specific gold plating liquid, carrying out the preplating gold.The cost of plating bath is higher in addition, and a lot of cyanogen-less gold liquid preparations are very complicated, and the loss gold is many in process for preparation, causes the bigger wasting of resources.Therefore, the popularization of cyanogen-less gold technology and use receive great restriction.In view of the situation, seek a kind of low toxicity or cyanogen-less gold liquid nontoxic, good stability, simple to operate and that cost is low, become a main striving direction of the research and development and the application of researcher.
Summary of the invention
In order to address the above problem, the invention provides a kind of cyanogen-less gold plating solution, the toxicity of this plating bath own is very little or nontoxic, and the bath composition cost is low, has stability preferably.
A kind of cyanogen-less gold plating solution provided by the invention, its prescription comprises following component: the mineral acid of gold, main complexing agent, auxiliary complex-former; Said main complexing agent is an alkane compound, and auxiliary complex-former is a non-nutritive sweetener.
The mass concentration of said component is: mineral acid 1～30 g/L of gold, main complexing agent 5～90 g/L, auxiliary complex-former 1～100 g/L.
The mineral acid of said gold is a hydrochloro-auric acid.
Described alkane compound is Tutofusin tris or its hydrochloride, and described non-nutritive sweetener is asccharin or its esters.
Add electroplating additive in the prescription of said cyanogen-less gold plating solution.Said electroplating additive is polymine, piperazine or Vinylpyrrolidone polymer.
The operational condition of described cyanogen-less gold plating solution is: pH is 7～9, and current density is 0.05 A/dm
2～0.5 A/dm
2, temperature is 20～60 ℃.
A kind of cyanogen-less gold plating solution provided by the invention does not contain the inferior sulfate radical plasma, and the chemicalstability of each component is better, and plating bath itself has certain surge capability, and bath pH value can not have greatly changed with the increase of storage period.Plating bath does not contain the objectionable impurities of prussiate or other strong toxicity of strong toxicity; Therefore depositing of plating bath need not special protection, and plating bath originally as neutral or near neutral solution, can not produce effects such as deep-etching to plating piece in the process of galvanic deposit; Plating piece is handled simple relatively; And need not the preplating gold and practiced thrift cost, cyanide-free can not cause huge harm to environment and human body yet simultaneously, and sewage waste liquor is handled simple relatively.Cyanogen-less gold plating solution provided by the invention is formed simple, and desired raw material is cheap, advantages of simple and practicable preparation method; Metal base replacement rates such as plating bath and nickel, copper are low; Chemicalstability is good, and in electroplating process, need not logical nitrogen deoxygenation, and the current density scope of application compares broad; The crystal grain of gained Gold plated Layer is careful, light and bonding force are good, can satisfy multi-field application such as daily decorative electroplating and functional plating.
Embodiment
The invention provides a kind of cyanogen-less gold plating solution.
The prescription of said cyanogen-less gold plating solution comprises following component: the mineral acid of gold, main complexing agent, auxiliary complex-former; Said main complexing agent is an alkane compound, and auxiliary complex-former is a non-nutritive sweetener.
The mineral acid of the gold that gold plating liquid uses is hydrochloro-auric acid.
Main complexing agent alkane compound is Tutofusin tris or its hydrochloride, and the auxiliary complex-former non-nutritive sweetener is asccharin or its esters.
The operational condition of a kind of cyanogen-less gold plating solution that uses among the present invention is: the pH scope is 7～9, and current density range is 0.05 A/dm
2～0.5 A/dm
2, TR is 20～60 ℃.
The plating step of using a kind of cyanogen-less gold plating solution of the present invention is: earlier behind dissolving Tutofusin tris or its hydrochloride; Join in the chlorauric acid solution at the following Tutofusin tris of condition of stirring or its hydrochloride, add asccharin or its esters and water then, mix; Bath temperature maintains 20～60 ℃; Then, the metal base of handling well is placed on the negative electrode of circuit integral part, negative electrode is placed electroplate liquid together with attached substrate; And passing to direct current, size of current of being led to and time will require to decide according to reality.
Be the preferred embodiment of the invention below, the present invention is described in further detail.
Embodiment 1
When a kind of cyanogen-less gold plating solution is electroplated below the use, select nickel electrode as negative electrode, platinized platinum is as anode.Temperature being transferred to preset value, stir with whisking appliance simultaneously, is 0.05A/dm in current density
2～0.5 A/dm
2The following plating.
The composition of gold plating liquid is following:
| Hydrochloro-auric acid | 10.2 g/L |
| Tutofusin tris | 21.8 g/L |
| Soluble saccharin | 1.6 g/L |
| Polymine | 0.6 g/L |
| Current density | 0.05 A/dm 2 |
| pH | 7.0 |
| Temperature | 20 ℃ |
Use this cyanogen-less gold plating solution to carry out galvanic deposit according to the plating step in the embodiment, plated gold on the nickel as a result, gained Gold plated Layer light is careful, and thickness of coating can satisfy the requirement of decorative coating.
Embodiment 2
Use the method identical gold-plated, change composition, pH, the temperature of gold plating liquid with embodiment 1.
The composition of gold plating liquid is following:
| Hydrochloro-auric acid | 10.2 g/L |
| Tri(Hydroxymethyl) Amino Methane Hydrochloride | 28.4 g/L |
| Soluble saccharin | 18.3 g/L |
| Polymine | 0.6 g/L |
| Current density | 0.05 A/dm 2 |
| pH | 7.5 |
| Temperature | 25 ℃ |
Use this cyanide-free gold plating solution to carry out galvanic deposit according to the plating step in the embodiment, plated gold on the nickel as a result, gained Gold plated Layer light is careful, and thickness of coating can satisfy the requirement of decorative coating.
Embodiment 3
Use the method identical gold-plated, change composition, pH, the temperature of gold plating liquid with embodiment 1.
The composition of gold plating liquid is following:
| Hydrochloro-auric acid | 10.2 g/L |
| Tri(Hydroxymethyl) Amino Methane Hydrochloride | 28.4 g/L |
| Soluble saccharin | 30.8 g/L |
| Polymine | 1.0 g/L |
| Current density | 0.3 A/dm 2 |
| pH | 8.0 |
| Temperature | 40 ℃ |
Use this cyanide-free gold plating solution to carry out galvanic deposit according to the plating step in the embodiment, plated gold on the nickel as a result, gained Gold plated Layer light is careful, and thickness of coating can satisfy the requirement of decorative coating.
Embodiment 4
Use the method identical gold-plated, change composition, pH, the temperature of gold plating liquid with embodiment 1.
The composition of gold plating liquid is following:
| Hydrochloro-auric acid | 3.4 g/L |
| Tutofusin tris | 7.3 g/L |
| Asccharin | 9.2 g/L |
| Piperazine | 0.8 g/L |
| Current density | 0.05 A/dm 2 |
| pH | 8.5 |
| Temperature | 35 ℃ |
Use this cyanide-free gold plating solution to carry out galvanic deposit according to the plating step in the embodiment, plated gold on the nickel as a result, gained Gold plated Layer light is careful, and thickness of coating can satisfy the requirement of decorative coating.
Embodiment 5
Use the method identical gold-plated, change composition, pH, the temperature of gold plating liquid with embodiment 1.
The composition of gold plating liquid is following:
| Hydrochloro-auric acid | 6.8 g/L |
| Tutofusin tris | 14.5 g/L |
| Asccharin | 18.3 g/L |
| Vinylpyrrolidone polymer | 1.0 g/L |
| Current density | 0.1 A/dm 2 |
| pH | 8.0 |
| Temperature | 30 ℃ |
Use this cyanide-free gold plating solution to carry out galvanic deposit according to the plating step in the embodiment, plated gold on the nickel as a result, gained Gold plated Layer light is careful, and thickness of coating can satisfy the requirement of decorative coating.
Claims (7)
1. cyanogen-less gold plating solution, it is characterized in that: the prescription of said cyanogen-less gold plating solution comprises following component: the mineral acid of gold, main complexing agent, auxiliary complex-former; Said main complexing agent is an alkane compound, and auxiliary complex-former is a non-nutritive sweetener.
2. a kind of cyanogen-less gold plating solution according to claim 1 is characterized in that: the mass concentration of said component is: mineral acid 1～30 g/L of gold, main complexing agent 5～90 g/L, auxiliary complex-former 1～100 g/L.
3. a kind of cyanogen-less gold plating solution according to claim 1 is characterized in that: the mineral acid of said gold is a hydrochloro-auric acid.
4. a kind of cyanogen-less gold plating solution according to claim 1 is characterized in that: described alkane compound is Tutofusin tris or its hydrochloride, and described non-nutritive sweetener is asccharin or its esters.
5. a kind of cyanogen-less gold plating solution according to claim 1 is characterized in that: add electroplating additive in the prescription of said cyanogen-less gold plating solution.
6. a kind of cyanogen-less gold plating solution according to claim 5 is characterized in that: said electroplating additive is polymine, piperazine or Vinylpyrrolidone polymer.
7. a kind of cyanogen-less gold plating solution according to claim 1 is characterized in that: the operational condition of described cyanogen-less gold plating solution is: pH is 7～9, and current density is 0.05 A/dm
2～0.5 A/dm
2, temperature is 20～60 ℃.
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| CN2011103697339A CN102383154A (en) | 2011-11-21 | 2011-11-21 | Cyanide-free gold-plating electroplating solution |
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|---|---|---|---|
| CN2011103697339A CN102383154A (en) | 2011-11-21 | 2011-11-21 | Cyanide-free gold-plating electroplating solution |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418166A (en) * | 2015-11-30 | 2016-03-23 | 苏州市金星工艺镀饰有限公司 | Cyanide-free gold-plated electroplating liquid and method for electroplating ceramic surface with dense gold thin film through pulses |
| CN106521575A (en) * | 2016-11-15 | 2017-03-22 | 惠州市力道电子材料有限公司 | Electroplating liquid of cyanide-free soft gold plating and electroplating method of electroplating liquid |
| CN106757200A (en) * | 2016-11-15 | 2017-05-31 | 惠州市力道电子材料有限公司 | The electroplate liquid and its electro-plating method of a kind of hard gold of non-cyanide plating |
| CN108350575A (en) * | 2015-12-18 | 2018-07-31 | 罗门哈斯电子材料有限责任公司 | Golden electroplating solution |
| CN110184631A (en) * | 2019-06-04 | 2019-08-30 | 广东达志环保科技股份有限公司 | A kind of cyanogen-less gold plating solution and preparation method thereof and electroplating technology |
| CN111663158A (en) * | 2020-06-19 | 2020-09-15 | 深圳市尚美金品有限公司 | Preparation method of high-temperature-resistant cyanide-free hard gold |
| CN114108040A (en) * | 2020-08-25 | 2022-03-01 | 周大福珠宝文化产业园(武汉)有限公司 | Cyanide-free gold plating solution and gold electroforming part manufactured by cyanide-free electroplating process |
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| US6565732B1 (en) * | 1999-10-07 | 2003-05-20 | Tanaka Kikinzoku Kogyo K.K. | Gold plating solution and plating process |
| CN101899688A (en) * | 2010-07-24 | 2010-12-01 | 福州大学 | Cyanide-free gold plating solution for plating gold |
| CN101906649A (en) * | 2010-08-11 | 2010-12-08 | 哈尔滨工业大学 | Cyanogens-free gold plating solution and method for plating gold by adopting same |
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2011
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| US6565732B1 (en) * | 1999-10-07 | 2003-05-20 | Tanaka Kikinzoku Kogyo K.K. | Gold plating solution and plating process |
| CN101899688A (en) * | 2010-07-24 | 2010-12-01 | 福州大学 | Cyanide-free gold plating solution for plating gold |
| CN101906649A (en) * | 2010-08-11 | 2010-12-08 | 哈尔滨工业大学 | Cyanogens-free gold plating solution and method for plating gold by adopting same |
Non-Patent Citations (1)
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| 谭谦: "无氰化学镀金工艺的研究", 《中国优秀硕士学位论文全文数据库(工程科技I辑)》, no. 022009, 15 February 2009 (2009-02-15), pages 015 - 17 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105418166A (en) * | 2015-11-30 | 2016-03-23 | 苏州市金星工艺镀饰有限公司 | Cyanide-free gold-plated electroplating liquid and method for electroplating ceramic surface with dense gold thin film through pulses |
| CN108350575A (en) * | 2015-12-18 | 2018-07-31 | 罗门哈斯电子材料有限责任公司 | Golden electroplating solution |
| CN106521575A (en) * | 2016-11-15 | 2017-03-22 | 惠州市力道电子材料有限公司 | Electroplating liquid of cyanide-free soft gold plating and electroplating method of electroplating liquid |
| CN106757200A (en) * | 2016-11-15 | 2017-05-31 | 惠州市力道电子材料有限公司 | The electroplate liquid and its electro-plating method of a kind of hard gold of non-cyanide plating |
| CN110184631A (en) * | 2019-06-04 | 2019-08-30 | 广东达志环保科技股份有限公司 | A kind of cyanogen-less gold plating solution and preparation method thereof and electroplating technology |
| CN111663158A (en) * | 2020-06-19 | 2020-09-15 | 深圳市尚美金品有限公司 | Preparation method of high-temperature-resistant cyanide-free hard gold |
| CN111663158B (en) * | 2020-06-19 | 2021-08-13 | 深圳市华乐珠宝首饰有限公司 | Preparation method of high-temperature-resistant cyanide-free hard gold |
| CN114108040A (en) * | 2020-08-25 | 2022-03-01 | 周大福珠宝文化产业园(武汉)有限公司 | Cyanide-free gold plating solution and gold electroforming part manufactured by cyanide-free electroplating process |
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Application publication date: 20120321 |