CN101665963B - Environmental non-cyanide plating solution for silver-plating - Google Patents
Environmental non-cyanide plating solution for silver-plating Download PDFInfo
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Abstract
An environmental non-cyanide plating solution for silver-plating contains silver ion source, amino acid compound and derivative thereof used as complexant, auxiliary complexant and plating additive. The component ratio and the process condition are as follows: the contents of silver salt, amino acid compound and derivative thereof, auxiliary complexant and plating additive are separately 0.01-1mol/L, 0.01-10mol/L, 0.002-2mol/L and 0.001-2.0g/L, the pH value of silver-plating solution is 6-14 and the temperature of the silver-plating solution is 10-70 DEG C. Compared with the traditional cyanide-containing formulation for silver-plating, the environmental plating solution for silver-plating is characterized by clean plating; meanwhile the replacement rate between silver ions in the plating solution and active metal such as copper, copper alloy and the like and alloy base is extremely slow, the one-step electroplating method is adopted for silver-plating, pre-plating and soaking processes of silver are not needed, and the coating is bright with good binding force.
Description
Technical field
The present invention relates to the silver-plated technical field of a kind of electrochemistry, relate to a kind of prescription of the environmental non-cyanide plating solution for silver-plating in order to the cyanide silver plating solution that substitutes severe toxicity specifically
Technical background
Silvering has 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.But the prussiate severe toxicity, very harmful to human body and environment.Along with the reinforcement of countries in the world environmental protection consciousness and the appearance of relevant policies, having cyanogen to electroplate becomes the technology that restriction is declared, principle is eliminated.
Compare with the cyanogen silver plating process is arranged, the research of non-cyanide silver coating technology is the thing of nearly decades.Non-cyanide silver coating is with inorganic or organic compound, replaces the Synergist S-421 95 of prussiate as silver ions, so that improve the cathodic polarization degree of plating bath, thereby has the galvanic deposit characteristic that is similar to the cyanogen Synergist S-421 95 when making the silver reduction.Up to now, although both at home and abroad galvanizer author has carried out a large amount of research to non-cyanide silver coating, going back none, can to replace prussiate fully silver-plated.Roughly there is following problem: the easy variable color of (1) silvered film.Silver has good chemical stability in most of organic acids, strong acid and salts solution, but in the air that contains halogenide, sulfide, the very fast variable color of silver surface.This is all silver-plated ubiquitous problems (comprising cyaniding plant of silver technology), so generally will plate aftertreatment.(2) binding force of cladding material is poor.Silver-plated product generally is a copper and copper alloy, because the standard potential of copper is much more negative than silver, when copper and alloy part thereof enter plating bath, before the energising replacement(metathesis)reaction is not taking place promptly, the surface forms displacement layer, the bonding force of it and matrix is poor, also has the copper contaminating impurity plating bath of part simultaneously, often adopts pre-silver plated mode just can avoid the generation of this type of problem.(3) bath stability is relatively poor, and the life-span is shorter.Major cause has: 1. the Synergist S-421 95 mating capability is not enough in the plating bath, Ag under the condition of illumination and heat
+Ion is easy to be reduced into silver-colored simple substance; 2. the character of Synergist S-421 95 self.A lot of Synergist S-421 95s can be rotten under electroplating technical conditions, as the hydrolysis of succimide under alkaline condition.(4) the plating bath cost is higher, and industrial utility value is not high.Employed Synergist S-421 95 of non-cyanide silver coating and additive cost an arm and a leg, and buy difficulty, though its sulculus experiment plating bath and coating performance all near cyaniding plant of silver, if be applied to actual production, producer is difficult to be accepted.
In silver-colored electroplating process, the body material of silver-plated part generally all is a copper and copper alloy spare, also has iron and steel silver plated as matrix, makes prime coat but plate layer of copper usually earlier.When activity metallic matrixes such as copper and alloy components thereof enter silver plating liquid, comprise cyanide silver plating solution and non-cyanide plating silvering solution, the displacement silver layer that the surface of plating piece forms not only has a strong impact on the bonding force of coating and matrix, and the iron that produces in the replacement process and cupric ion also can pollute plating bath.Therefore, plating piece enters before the silver plating liquid in traditional silver plating process, must carry out pre-silvered film.Obviously, conventional process flow has not only further improved electroplating cost, and time-consuming.One step type is silver-plated can simplify the silver plating process flow process, saves electroplating time, thereby may reduce running cost, helps the practical application of non-cyanide silver coating system in electroplating industry.
Summary of the invention
Purpose of the present invention just provides a kind of environmental non-cyanide plating solution for silver-plating that does not contain prussiate, this electroplate liquid contains silver ions source thing, amino acids or derivatives thereof, auxiliary complexing agent and electroplating additive, and their proportionings in no cyanogen silver plating solution form and processing condition are:
Silver salt 0.01~1mol/L
Amino acids or derivatives thereof 0.01~10mol/L
Auxiliary complexing agent 0.002~2mol/L.
Electroplating additive 0.001~2.0g/L
Silver plating liquid pH 6~14
10~70 ℃ of silver plating liquid temperature.
The excellent mixture that is meant one or more arbitrary proportions in glycine, α-Bing Ansuan, Beta-alanine, halfcystine, Gelucystine, network propylhomoserin, Histidine, methionine(Met), anthranilic acid, aspartic acid, L-glutamic acid, thionamic acid, ammonia oxalic acid, nitrilotriacetic acid(NTA), diethyl pentetic acid, N-hydroxyethyl-ethylenediamine nitrilotriacetic or the aromatic nucleus amino acid of described coordination agent amino acids or derivatives thereof.
Described auxiliary is meant succimide, glycolylurea, 5, the mixture of one or more arbitrary proportions in 5-T10, uridylic, cytosine(Cyt) or the xanthoglobulin.
Described electroplating additive is meant the mixture of one or more arbitrary proportions in soluble metal compound, nonionogenic tenside, polyamine compound, sulfocompound or the nitrogen heterocyclic.Wherein soluble metal compound is meant the inorganic acid salt oxide compound of Bi, Co, Cd, Cu, Se or Sb or the mixture of one or more arbitrary proportions in the oxyhydroxide; Nonionogenic tenside is meant the mixture of one or both arbitrary proportions in polyoxyethylene glycol (molecular weight is 100~100000) or the epoxy amine polycondensate (molecular weight is 100~100000); Polyamine compound is meant the mixture of one or both arbitrary proportions in polymine (molecular weight is 100~100000) or the polyvinylamine (molecular weight is 100~100000); Nitrogen heterocyclic is meant Yi Yansuan, imidazoles, benzoglyoxaline, benzotriazole, 2 hydroxy pyrimidine, 2, the mixture of one or more arbitrary proportions in 2-dipyridyl, uridylic, uric acid, VITAMIN B4 or the guanine; Sulfocompound is meant Na
2S
2O
3, K
2S
2O
3, one or more arbitrary proportions in thiocarbamide, ethyl thiourea, aminothiazole, benzothiazole, mercaptobenzothiazole, mercaptobenzimidazole, thio-diethylene glycol or the thiosalicylic acid mixture.
The present invention compares the remarkable advantage that is produced with background technology:
(1) adopts amino acids and derivative thereof to form coordination compound, replaced prussiate fully, eliminated in the electroplating process prussiate harm of human body and environment has been realized the cleaning plating as coordination agent and silver ions;
(2) replacement rate of ripple metal base alive such as silver ions and copper, copper alloy is very slow in the plating bath, and plating piece need not pre-silver-plated or soaks silver, can implement the one step type silver plating process, has simplified the silver plating process flow process, has reduced manufacturing cost;
(3) low, the wide material sources of the raw materials cost of this non-cyanide plating solution for silver-plating, coating is in conjunction with reliable, and bath stability performance height can satisfy the electroplating industry demand well.
Embodiment
Embodiment 1
Press 0.15mol/L AgNO
3, 0.6mol/L Beta-alanine, 0.1mol/L uridylic and 0.002g/L polymine form each material be dissolved in the deionized water, is mixed with the environment-friendly silver electroplate liquid, regulating silver plating liquid pH value is 13, the plating solution for silver-plating temperature is 15 ℃.Copper or brass plating piece being immersed in the plating solution for silver-plating, adopt step electrochemical plating, is 0.2A/dm with the current density
2The copper plating piece implement is electroplated, when being plated to silver thickness and being 3 μ m till.Gained silver layer light is good with basal body binding force.
Embodiment 2
Press 0.15mol/L AgNO
3, 0.5mol/L Gelucystine, 0.1mol/L Yi Yansuan, 0.05g/L polymine and 0.05g/L phenylpropyl alcohol triazole form each material be dissolved in the deionized water, is mixed with the environment-friendly silver electroplate liquid, regulating silver plating liquid pH value is 10, the plating solution for silver-plating temperature is 40 ℃.Copper or brass plating piece being immersed in the plating solution for silver-plating, adopt step electrochemical plating, is 0.2A/dm with the current density
2The copper plating piece implement is electroplated, when being plated to silver thickness and being 3 μ m till.Gained silver layer light is good with basal body binding force.
Embodiment 3
Press 0.1mol/L AgSO
3CH
3, 0.5mol/L ammonia oxalic acid, 0.1mol/L5,5-T10,0.95g/L polymine and 0.05g/L 10ppm Sb composition are dissolved in each material in the deionized water, be mixed with the environment-friendly silver electroplate liquid, regulating silver plating liquid pH value is 8, and the plating solution for silver-plating temperature is 40 ℃.The brass plating piece being immersed in the plating solution for silver-plating, adopt step electrochemical plating, is 0.2A/dm with the current density
2The copper plating piece implement is electroplated, when being plated to silver thickness and being 3 μ m till.Gained silver layer light is good with basal body binding force.
Embodiment 4
Press 0.1mol/L AgNO
3, 0.5mol/L L-glutamic acid, 0.1mol/L uric acid, 0.01g/L polyoxyethylene glycol and 2.0g/L2, the 2-dipyridyl is formed each material is dissolved in the deionized water, is mixed with the environment-friendly silver electroplate liquid, regulating silver plating liquid pH value is 6, the plating solution for silver-plating temperature is 65 ℃.Copper or brass plating piece being immersed in the plating solution for silver-plating, adopt step electrochemical plating, is 0.2A/dm with the current density
2The copper plating piece implement is electroplated, when being plated to silver thickness and being 3 μ m till.Gained silver layer light is good with basal body binding force.
Claims (2)
1. non-cyanide plating solution for silver-plating, the composition proportioning and the processing condition that it is characterized in that not having in the cyanogen silver plating solution are:
Silver salt 0.01~1mol/L; Coordination agent amino acids or derivatives thereof is meant one or more in Gelucystine, network propylhomoserin, Histidine, anthranilic acid, aspartic acid, L-glutamic acid, thionamic acid, ammonia oxalic acid, nitrilotriacetic acid(NTA), diethyl pentetic acid, N-hydroxyethyl-ethylenediamine nitrilotriacetic or the aromatic nucleus amino acid, and content is 0.01~10mol/L; Auxiliary is meant succimide, glycolylurea, 5, and the mixture of one or more arbitrary proportions in 5-T10, uridylic, cytosine(Cyt) or the xanthoglobulin, content are 0.002~2mol/L; Electroplating additive is meant the mixture of the multiple arbitrary proportion in soluble metal compound, nonionogenic tenside, polyamine compound, sulfocompound or the nitrogen heterocyclic, and content is 0.001~2g/L; Silver plating liquid pH is 6~14; 10~70 ℃ of silver plating liquid temperature.
2. non-cyanide plating solution for silver-plating according to claim 1 is characterized in that described electroplating additive is meant:
A. described nonionogenic tenside is meant that molecular weight is that 100~100000 polyoxyethylene glycol or molecular weight are the mixture of one or both arbitrary proportions in 100~100000 the epoxy amine polycondensate;
B. described polyamine compound is meant that molecular weight is that 100~100000 polymines or molecular weight are the mixture of one or both arbitrary proportions in 100~100000 the polyvinylamine;
C. described sulfocompound is meant Na
2S
2O
3, K
2S
2O
3, one or more arbitrary proportions in thiocarbamide, ethyl thiourea, aminothiazole, benzothiazole, mercaptobenzothiazole, thio-diethylene glycol or the thiosalicylic acid mixture;
D. described nitrogen heterocyclic is meant imidazoles, benzoglyoxaline, benzotriazole, 2 hydroxy pyrimidine, 2, the mixture of one or more arbitrary proportions in 2-dipyridyl, uric acid, VITAMIN B4 or the guanine.
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Cited By (1)
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US20150184307A1 (en) * | 2012-07-31 | 2015-07-02 | Daiwa Fine Chemicals Co., Ltd. (Laboratory) | Silver electroplating solution |
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2009
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Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20150184307A1 (en) * | 2012-07-31 | 2015-07-02 | Daiwa Fine Chemicals Co., Ltd. (Laboratory) | Silver electroplating solution |
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