CN101092723A - Electroplating solution without cyanogen for plating silver - Google Patents
Electroplating solution without cyanogen for plating silver Download PDFInfo
- Publication number
- CN101092723A CN101092723A CN 200710009207 CN200710009207A CN101092723A CN 101092723 A CN101092723 A CN 101092723A CN 200710009207 CN200710009207 CN 200710009207 CN 200710009207 A CN200710009207 A CN 200710009207A CN 101092723 A CN101092723 A CN 101092723A
- Authority
- CN
- China
- Prior art keywords
- silver
- cyanogen
- plating solution
- free silver
- plating
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
This invention provides a cyanide-free silver-electroplating solution, which comprises: silver-containing organic or inorganic salt 1-200 g/L, purin coordination agent 1-800 g/L, supporting electrolyte 1-200 g/L, pH regulator 0-550 g/L, and additive system. The preparation method comprises: uniformly mixing the above components to prepare the cyanide-free silver-electroplating solution, and adjusting the temperature to 10-60 deg.C. Compared with the traditional formula, the cyanide-free silver-electroplating solution in this invention has such advantages as low or no toxicity, and high stability. Silver ions have a very low displacement rate with copper, nickel, iron, aluminum, chrome, titanium and alloy matrices. The work piece to be plated does not need preliminary silver plating or silver dipping. The silver-electroplating layer has such advantages as high adhesiveness and high shinness, and can be used in decorative and functional electroplating fields.
Description
Technical field
The invention belongs to the silver-plated technical field of electrochemistry, be specifically related to a kind of cyanogen-free silver-plating solution.
Background technology
Silvered film has very high electroconductibility, luminous reflectanc, and to the chemical stability height of organic bronsted lowry acids and bases bronsted lowry, and relative other precious metals of its price are more cheap, have been widely used in fields such as ornament, tableware and electronic products.Up to now, electrosilvering technology both domestic and external still adopts mostly has the cyanogen silver plating process to electroplate silver layer, mainly is because this bath stability is good, and covering power and degree of depth ability are better, and the coating crystallization is careful, and outward appearance is silvery white.But prussiate is a severe toxicity; very harmful to human body and environment; require to possess good exhaust equipment and wastewater treatment condition during production; along with the reinforcement of countries in the world environmental protection consciousness and the appearance of relevant policies; having cyanogen to electroplate becomes backward industry gradually, becomes the technology that restriction is declared, principle is eliminated.The 32nd command of former State Economic and Trade Commission issue on June 2nd, 2002 is listed the 23rd of " eliminating outmoded production capacity the catalogue of technology and product " (the 3rd batch) in " containing cyanogen electroplates ", orders for the end of the year 2003 within a certain time and eliminates.On December 26th, 2003, catalogue (exposure draft) is instructed in National Development and Reform Committee's announcement industry restructuring, and " containing cyanogen electroplates " ranks " out of category " the 182nd.Therefore, the galvanizer authors are devoted to not contain CN always
-The research of non-cyanide silver coating, non-cyanide silver coating technology such as successively proposed that thiosulphate is silver-plated, sulphite is silver-plated, sulphosalicylic acid is silver-plated and imino-diacetic sulfonate is silver-plated, some patents, for example U.S. Pat P4247372, USP4478691, USP4246077, USP4126524 etc. have also been applied for simultaneously; Japanese Patent JP7039945; Also have European patent EP 0705919, EP1416065, EP1418251 etc. in addition.Compare with cyaniding plant of silver, still there is a lot of shortcomings in non-cyanide silver coating, and subject matter has: (1) bath stability problem.The stability of many non-cyanide plating silvering solutions is all bad, no matter is alkali plating solution or acidic bath or neutrality, has the bath stability problem to some extent, makes troubles for management and operation, and cost is also increased to some extent.(2) the plating bath cost is higher.Therefore, using the enterprise of non-cyanide silver coating technology at present only is minority unit.In the case, the Application and Development of a kind of toxicity non-cyanide silver coating technology low or nontoxic, that cost suits relatively is a major subjects that becomes field of electroplating.
In the document and industry technical process reported at present, pre-silver-plated is metallic surface electrosilvering necessary procedure before.This is because the standard potential of copper, iron is all negative than silver, and therefore, when steel part, copper and alloy components thereof entered silver plating liquid, the plating piece surface can form the displacement silver layer.It not only has a strong impact on the bonding force of silvering and substrate, and the iron that produces in the replacement process and cupric ion also can pollute plating bath.In the case, if the non-cyanide silver coating system is slow to metal replacement speed such as copper, iron, before substrates such as copper, iron are silver-plated, need not silver-plated in advance, so such bath system has not only possessed the characteristics of nontoxic or low toxicity, and simplified the electroplating technology flow process, simultaneously reduce the Electroplating Production cost to a certain extent, thereby helped the practical application of non-cyanide silver coating system in electroplating industry.For this kind silver plating process, we are referred to as non-preplating type non-cyanide silver-plating technology.
Summary of the invention
The purpose of this invention is to provide a kind of cyanogen-free silver-plating solution, this plating solution raw materials is easy to get, and preparation is simple, and good stability; Toxicity is extremely low or nontoxic; Plating piece need not pre-silver-plated or soaks silver, and binding force of cladding material is good and bright, can satisfy multi-field application such as decorative electroplating and functional plating.
Cyanogen-free silver-plating solution of the present invention, it is characterized in that: the mass concentration of each component of composition of raw materials of described electroplate liquid is: the inorganic salt or the organic salt 1～200g/L that contain silver, purine class coordination agent 1～800g/L, supporting electrolyte 1～200g/L, plating bath pH regulator agent 0～550g/L and electroplating additive system.
The preparation method of cyanogen-free silver-plating solution of the present invention is: each component is mixed according to described composition of raw materials, make cyanogen-free silver-plating solution; Solution temperature is adjusted to 10～60 ℃.
Remarkable advantage of the present invention is: adopt purine compound and derivative thereof to form coordination compound as coordination agent and silver ions, plating bath is highly stable, toxicity reduces widely than cyaniding plant of silver.Compare with traditional cyanogen silver plating process prescription that has, this non-cyanide silver coating plating bath toxicity is extremely low or nontoxic, and bath stability is good; Simultaneously, the replacement rate of monometallic such as silver ions and copper, nickel, aluminium, iron, chromium, titanium and alloy substrates is very slow in the plating bath, plating piece need not pre-silver-plated or soaks silver, and binding force of cladding material is good and bright, can satisfy multi-field application such as decorative electroplating and functional plating.
With reference to preferred embodiment, the present invention is described in further detail.
Embodiment
Prepare non-cyanide silver coating plating bath of the present invention according to above-mentioned composition of raw materials and preparation method.
The preferred Silver Nitrate of inorganic salt that contains silver, organic salt preferable methyl sulfonic acid silver.
Purine class coordination agent is purine compound and derivative thereof, and its general formula is
In the formula, R
1, R
2, R
3Independent separately, can be identical or different, be hydrogen, alkyl, alkoxyl group, hydroxyl, amino, nitro, carboxyl or sulfonic group, wherein said moieties contains 1 to 6 carbon atom.
Purine class coordination agent can also be purine compound and derivative or corresponding isomer.
Coordination agent purine compound and derivative thereof are one or more in uric acid, VITAMIN B4, guanine, xanthine, xanthoglobulin and the corresponding purine derivative.
Supporting electrolyte is KNO
3, KNO
2, in KOH, KF and the corresponding sodium salts one or more.
Described plating bath OH
-Concentration range is 10
-8To 10mol/L, KOH, NaOH, ammoniacal liquor, HNO are adopted in the agent of plating bath pH regulator
3, HNO
2With among the HF one or more.
The electroplating additive system is a polymine, epoxy amine polycondensate, one or more in selenium prussiate or the thiocyanide.A kind of cyanogen-free silver-plating solution according to claim 8 is characterized in that: described polymine molecular-weight average is 100～1000000, and concentration is 50～10000mg/L; Described epoxy amine polycondensate molecular-weight average is 100～1000000, and its general molecular formula is NH-CH
2-CH (OH)-CH
2
nOH, concentration is 50～10000mg/L; Described selenium prussiate is KSeCN or NaSeCN, and concentration is 0.01～500mg/L; Described thiocyanide is KSCN or NaSCN, and concentration is 0.01～2000mg/L.
Use the plating step of non-cyanide silver coating plating bath of the present invention to be: earlier alkali dissolution to be dissolved in water, wherein, under the condition of agitation, slowly add silver ions source thing then, add required supporting electrolyte at last with the complexing agent dissolving.In electroplating process, plating bath is maintained 10～60 ℃.Then, will invest on the negative electrode that belongs to the circuit integral part, negative electrode together with in the appended matrix immersion plating liquid, and will be passed to electric current in circuit, and institute's galvanization and conduction time require to determine according to reality through pretreated metal base.
With reference to preferred embodiment, the present invention is described in further detail.
Embodiment 1
Following compounds is dissolved in the deionized water preparation non-cyanide silver coating plating bath
AgNO
3 17g/L
Uric acid 134g/L
KNO
3 20g/L
KOH 168g/L
Polymine 1g/L
KSeCN 2mg/L
10 ℃～60 ℃ of preparation temperature
Use this non-cyanide silver coating plating bath to carry out electroplating operations according to the plating step in the embodiment.
Embodiment 2
Following compounds is dissolved in the deionized water preparation non-cyanide silver coating plating bath
AgNO
3 17g/L
Guanine 129g/L
KNO
3 20g/L
KOH 139g/L
Polymine 1.5g/L
KSeCN 2mg/L
10 ℃～60 ℃ of preparation temperature
Use this non-cyanide silver coating plating bath to carry out electroplating operations according to the plating step in the embodiment.
Embodiment 3
Following compounds is dissolved in the deionized water preparation non-cyanide silver coating plating bath
AgNO
3 17g/L
VITAMIN B4 108g/L
KNO
3 20g/L
KOH 153g/L
Polymine 1g/L
KSCN 5mg/L
10 ℃～60 ℃ of preparation temperature
Use this non-cyanide silver coating plating bath to carry out electroplating operations according to the plating step in the embodiment.
Embodiment 4
Following compounds is dissolved in the deionized water preparation non-cyanide silver coating plating bath
AgNO
3 17g/L
Xanthine 124g/L
KNO
3 20g/L
KOH 129g/L
Epoxy amine polycondensate 2g/L
10 ℃～60 ℃ of preparation temperature
Use this non-cyanide silver coating plating bath to carry out electroplating operations according to the plating step in the embodiment.
Embodiment 5
Following compounds is dissolved in the deionized water preparation non-cyanide silver coating plating bath
AgNO
3 17g/L
Xanthoglobulin 110g/L
KNO
3 20g/L
KOH 168g/L
Epoxy amine polycondensate 2g/L
KSeCN 2mg/L
10 ℃～60 ℃ of preparation temperature
Use this non-cyanide silver coating plating bath to carry out electroplating operations according to the plating step in the embodiment.
Claims (10)
1. cyanogen-free silver-plating solution, it is characterized in that: the mass concentration of each component of composition of raw materials of described electroplate liquid is: the inorganic salt or the organic salt 1～200g/L that contain silver, purine class coordination agent 1～800g/L, supporting electrolyte 1～200g/L, plating bath pH regulator agent 0～550g/L and electroplating additive system.
2. a kind of cyanogen-free silver-plating solution according to claim 1 is characterized in that: the described preferred Silver Nitrate of inorganic salt that contains silver, organic salt preferable methyl sulfonic acid silver.
3. a kind of cyanogen-free silver-plating solution according to claim 1 is characterized in that: described purine class coordination agent is purine compound and derivative thereof, and its general formula is
In the formula, R
1, R
2, R
3Independent separately, can be identical or different, be hydrogen, alkyl, alkoxyl group, hydroxyl, amino, nitro, carboxyl or sulfonic group, wherein said moieties contains 1 to 6 carbon atom.
4. according to claim 1 or 3 described a kind of cyanogen-free silver-plating solutions, it is characterized in that: described purine class coordination agent is purine compound and derivative or corresponding isomer.
5. a kind of cyanogen-free silver-plating solution according to claim 4 is characterized in that: described coordination agent purine compound and derivative thereof are one or more in uric acid, VITAMIN B4, guanine, xanthine, xanthoglobulin and the corresponding purine derivative.
6. a kind of cyanogen-free silver-plating solution according to claim 1 is characterized in that: described supporting electrolyte is KNO
3, KNO
2, in KOH, KF and the corresponding sodium salts one or more.
7. a kind of cyanogen-free silver-plating solution according to claim 1 is characterized in that: described plating bath OH
-Concentration range is 10
-8To 10mol/L, KOH, NaOH, ammoniacal liquor, HNO are adopted in the agent of plating bath pH regulator
3, HNO
2With among the HF one or more.
8. a kind of cyanogen-free silver-plating solution according to claim 1 is characterized in that: described electroplating additive system is a polymine, epoxy amine polycondensate, one or more in selenium prussiate or the thiocyanide.
9. a kind of cyanogen-free silver-plating solution according to claim 8 is characterized in that: described polymine molecular-weight average is 100～1000000, and concentration is 50～10000mg/L; Described epoxy amine polycondensate molecular-weight average is 100～1000000, and its general molecular formula is NH-CH
2-CH (OH)-CH
2
nOH, concentration is 50～10000mg/L; Described selenium prussiate is KSeCN or NaSeCN, and concentration is 0.01～500mg/L; Described thiocyanide is KSCN or NaSCN, and concentration is 0.01～2000mg/L.
10. a kind of cyanogen-free silver-plating solution according to claim 1, it is characterized in that: the preparation method of described cyanogen-free silver-plating solution is: each component is mixed according to described composition of raw materials, make cyanogen-free silver-plating solution, solution temperature is adjusted to 10 ℃～60 ℃.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710009207A CN100585019C (en) | 2007-07-13 | 2007-07-13 | Cyanogens-free electroplating solution for plating silver |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710009207A CN100585019C (en) | 2007-07-13 | 2007-07-13 | Cyanogens-free electroplating solution for plating silver |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101092723A true CN101092723A (en) | 2007-12-26 |
| CN100585019C CN100585019C (en) | 2010-01-27 |
Family
ID=38991154
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN200710009207A Expired - Fee Related CN100585019C (en) | 2007-07-13 | 2007-07-13 | Cyanogens-free electroplating solution for plating silver |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100585019C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838828A (en) * | 2010-03-25 | 2010-09-22 | 福州大学 | Cyanogen-less gold plating solution |
| CN106567109A (en) * | 2016-11-15 | 2017-04-19 | 惠州市力道电子材料有限公司 | Electroplate liquid for cyanide-free silver plating and electroplating method of electroplate liquid |
| CN110528031A (en) * | 2019-08-06 | 2019-12-03 | 国网山东省电力公司电力科学研究院 | Based on the more first coordination systems of EDTA without cyanogen brush plating liquor and preparation method thereof |
| CN114908387A (en) * | 2022-05-31 | 2022-08-16 | 重庆立道新材料科技有限公司 | Brightener for cyanide-free high-speed silver plating |
-
2007
- 2007-07-13 CN CN200710009207A patent/CN100585019C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101838828A (en) * | 2010-03-25 | 2010-09-22 | 福州大学 | Cyanogen-less gold plating solution |
| CN101838828B (en) * | 2010-03-25 | 2011-11-30 | 福州大学 | Cyanogen-less gold plating solution |
| CN106567109A (en) * | 2016-11-15 | 2017-04-19 | 惠州市力道电子材料有限公司 | Electroplate liquid for cyanide-free silver plating and electroplating method of electroplate liquid |
| CN106567109B (en) * | 2016-11-15 | 2021-04-09 | 惠州市力道电子材料有限公司 | Cyanide-free silver plating electroplating solution and electroplating method thereof |
| CN110528031A (en) * | 2019-08-06 | 2019-12-03 | 国网山东省电力公司电力科学研究院 | Based on the more first coordination systems of EDTA without cyanogen brush plating liquor and preparation method thereof |
| CN114908387A (en) * | 2022-05-31 | 2022-08-16 | 重庆立道新材料科技有限公司 | Brightener for cyanide-free high-speed silver plating |
| CN114908387B (en) * | 2022-05-31 | 2024-02-09 | 重庆立道新材料科技有限公司 | Brightening agent for cyanide-free high-speed silver plating |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100585019C (en) | 2010-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101260549B (en) | Non-preplating type non-cyanide silver-plating electroplate liquid | |
| CN101665963B (en) | Environmental non-cyanide plating solution for silver-plating | |
| CN102277601B (en) | Cyanogen-free silver-plating electroplating liquid containing auxiliary complexing agent | |
| CN102268701B (en) | Non-cyanide bright silver electroplating bath and preparation method thereof | |
| CN101838828B (en) | Cyanogen-less gold plating solution | |
| CA1183656A (en) | Electroless gold plating | |
| CN102691081B (en) | A kind of plating silver solution and electro-plating method | |
| CN103806060A (en) | Electroplating method of improving binding force of silver coating and matrix | |
| CN1473207A (en) | Method for electroless nickel plating | |
| CN105088293A (en) | Novel cyanide-free silver plating electroplating liquid and electroplating technology | |
| CN102037162A (en) | Pd and Pd-Ni electrolyte baths | |
| CN103046091A (en) | Plating solution and plating method of cyanide-free plating silver | |
| CN101092724A (en) | Non-cyanogen type electroplating solution for plating silver | |
| CN105463524A (en) | Electroplating method of cyanide-free silver electroplating liquid | |
| CN113416989B (en) | Silver plating process and silver plated part | |
| CN102560571A (en) | Cyanide-free silver plating stable electroplating solution and preparation method thereof, and silver plating method | |
| CN100585019C (en) | Cyanogens-free electroplating solution for plating silver | |
| CN102383154A (en) | Cyanide-free gold-plating electroplating solution | |
| CN102995081A (en) | Cyanide-free bright silver plating electroplating solution | |
| CN1249270C (en) | Palladium plating solution | |
| CN102220610B (en) | Non-cyanide copper-tin alloy plating solution | |
| US3637474A (en) | Electrodeposition of palladium | |
| CN101781782B (en) | Cyanide-free high-speed silver plating electroplating solution | |
| US4913787A (en) | Gold plating bath and method | |
| CN103540970B (en) | A kind of method of non-cyanide silver coating |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20100127 Termination date: 20120713 |