CN104018193A - Non-cyanide bright electroplated silver composite additive and application method thereof in non-cyanide silver electroplating system - Google Patents
Non-cyanide bright electroplated silver composite additive and application method thereof in non-cyanide silver electroplating system Download PDFInfo
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Abstract
The invention relates to a non-cyanide bright electroplated silver composite additive and an application method thereof in a non-cyanide silver electroplating system, and belongs to the technical field of silver electroplating. The electroplated silver composite additive is characterized in that the combination of an inorganic additive and an organic additive is adopted, so that the adding quantity of the additive is wide in range; the solution electroplating performance and the coating electroplating performance of the non-cyanide silver electroplating system are obviously improved due to the addition of the corresponding combined additive. The non-cyanide bright electroplated silver composite additive cannot be decomposed in storage and application processes because of having extremely high stability, and can be used for effectively accelerating the electrolytic deposition speed of a silver electroplating layer without influencing the current efficiency of a cathode at the same time. Thus, the density range of a permissible working current is effectively enlarged; the silver electroplating layer with excellent performance can be obtained; the non-cyanide silver electroplating system in which the additive is added is suitable for production requirements in different fields; the silver electroplating carried out by virtue of cyanides can be completely replaced with the non-cyanide silver electroplating system in the industrial production and the application field. As a result, the environmental friendliness of a silver electroplating process is realized.
Description
Technical field
The invention belongs to electrosilvering technical field, relate to a kind of electrosilvering combined additive and the using method in non-cyanide silver electroplating system thereof.
Background technology
Silvered film is a kind of cheap price that has, there is very high conduction, thermal conductivity simultaneously, extremely strong light reflective, weldability preferably, and high temperature resistant, wear resistance, and the metal plating of chemical stability to most bronsted lowry acids and bases bronsted lowry, therefore silvered film is widely used in every profession and trade field, comprise the aspect such as the industrial circles such as jewellery, commemorative coin, electronics, instrument, instrument, Aeronautics and Astronautics and connector plating.
Before more than 100 years, the advantages such as since Britain Elkington brother has applied for the patent of prussiate electrosilvering first, prussiate electrosilvering system is simple with its solution composition, use cost is low, bath stability is reliable, current efficiency is high, dispersive ability and covering power good, careful glossy, the coating properties excellence of coating crystallization are still widely used in the every field in daily life.The production and application of prussiate electrosilvering system is the argent plating technic of low cost, high repayment economically, but very unfortunately, prussiate electrosilvering system exists serious problem---prussiate severe toxicity.Prussiate is a kind of highly toxic substance, pollutes the environment, endangers the producer's health, and the wastewater treatment difficulty that contains prussiate is large, cost is high.Along with scientific and technical progress and the development of economic society; in the achievement that the mankind bring in enjoyment scientific-technical progress; also brought increasing harm to environment; the environmental problem that we face is also increasingly serious; conventional electroplating industry is one of high pollution industry; along with the reinforcement gradually of people's environmental protection consciousness, demand and cry to Green Electroplating and even Green Chemistry are more and more higher.
In order to solve the harm problem of prussiate to aspects such as environment and human body health, worldwide plating practitioner has carried out the technical study of non-cyanide silver electroplating widely.Just had the detailed record about non-cyanide silver electroplating from 1913, apart from the present T&B.From the sixties in 20th century, various countries investigator more deeply with extensive, also has more novel process to be seen in report to the research of non-cyanide silver electroplating, has occurred successively the report of non-cyanide silver electroplating technical study on various periodicals and books.Be mainly and find suitable coordination agent about the research work of non-cyanide silver electroplating, substitute the coordination of cyanide ion in electrosilvering to reach, so far, the silver ions coordination agent of the organic or inorganic that the non-cyanide silver electroplating system of having studied or studying is used approximately has tens kinds, but current used non-cyanide silver coating system ubiquity bath stability poor, see the problems such as light easily lost efficacy, tolerates that cold and hot exchange capacity is poor, coating performance is lower, the processing condition harshness, the temperature window that allow are narrow, current density range is narrow.Thereby in the non-cyanide silver electroplating coordination agent research of being correlated with, relevant investigators have also carried out the research work such as electrosilvering additive, in the hope of by this plating solution that is used for promoting non-cyanide silver electroplating system, the coating performance that adds on a small quantity the additive that plays great function.For different non-cyanide silver electroplating systems, additive used is not universality, therefore need to carry out distinctive additive research for different non-cyanide silver electroplating systems, to promoting on the whole plating solution, the coating performance of done non-cyanide silver electroplating system, thereby real in technique with complete in theory the application of substitute electrosilvering system in daily industrial production, thoroughly eliminate the healthy injury that bring of hypertoxic prussiate to environment and the mankind.Therefore, use non-cyanide silver electroplating system to replace prussiate electrosilvering system etc. completely from the viewpoint of safety, environmental protection and at field of industrial production, develop a kind of nontoxic, stable, interpolation effect that can be used for non-cyanide silver electroplating system obviously, the combined additive of the non-cyanide silver electroplating system of plating solution, the obvious lifting of quality of coating is to have very important technology using value and far-reaching historic significance.
Summary of the invention
The present invention is intended to by disclosed non-cyanide silver electroplating system (CN102168290A, CN103397355A) research of electrosilvering additive and the optimization of cyanideless electro-plating silver process in, determine that one or more can be applied to the additive of above-mentioned non-cyanide silver electroplating system, to reach the object of improving plating solution performance and quality of coating, increase the range of application of electroplating technology, make every effort to the coating consistent with prussiate system silvered film performance by the use acquisition of non-cyanide silver electroplating, thereby by the plating solution of done non-cyanide silver electroplating system and coating performance good be applied to industrial production and practice in every field, meet the requirement of relevant industries to electrosilvering performance, substitute electrosilvering is in the use in related application field completely.
Non-cyanide silver electroplating combined additive of the present invention is the combination of organic additive and inorganic additives, in whole combined additive, the mass ratio of organic additive and inorganic additives is at 1:5 ~ 55:1, the preparation of combined additive is used ultrapure water, stand-by by preserving after the additive dissolving constant volume of respective concentration.The unique distinction of electrosilvering combined additive of the present invention has been to use the combination of inorganic additives and organic additive, the scope of the add-on of additive is wider, and adding of respective combination additive can obviously promote non-cyanide silver electroplating system plating solution performance and coating performance.Non-cyanide silver electroplating combined additive of the present invention has high stability, in preservation and use procedure, does not decompose; in effectively promoting silvered film electrodeposition rate, do not affect cathode efficiency; thereby can effectively expand allowed working current density scope; can obtain the silvered film of excellent performance; ensure to add non-cyanide silver electroplating system after additive to go for the production requirement of different field; realize the object at industrial production and the complete substitute electrosilvering of Application Areas, realize the environmental protection of electrosilvering technique.
The using method of electrosilvering combined additive provided by the invention in non-cyanide silver electroplating system, comprises the steps:
One, additive preparation: take successively inorganic additives and the organic additive of respective amount, use ultrapure water to be mixed with settled solution, stand-by by preserving after the additive constant volume of respective concentration;
Two, electrosilvering plating solution preparation:
First carry out the preparation of electrosilvering plating solution, electrosilvering combined additive of the present invention is applicable to pre-silver-plated and the silver-plated system of fast electric, and therefore the process for preparation of plating solution is divided into two kinds:
The preparation of silvered film bath system in the middle of preplating: see described in CN102168290A, plating solution is formulated by 50 ~ 200g/L hydantoin derivatives, 50 ~ 200g/L auxiliary complexing agent, 65 ~ 125g/L potassium hydroxide, 50 ~ 150g/L salt of wormwood and 8 ~ 30g/L Silver Nitrate, controls the pH value of plating solution between 9 ~ 14.
The plating solution preparation of flash plate silver plating solution system: see described in CN103397355A, plating solution is formulated by 50 ~ 450g/L hydantoin derivatives, 10 ~ 300g/L auxiliary complexing agent, 35 ~ 325g/L potassium hydroxide, 35 ~ 300g/L salt of wormwood and 5 ~ 105g/L Silver Nitrate, controls the pH value of plating solution between 9 ~ 14.
Plating solution adds combined additive, the adjustment bath temperature of requirement after having prepared, carry out the operation of electrosilvering, carries out electrosilvering technique under direct current electrode position condition.In described electrosilvering technique, need to add additive 0.1～175ml/L.
Three, electrosilvering: carry out the operation of electrosilvering at copper matrix surface.
The concrete steps of substrate pretreatment are: the HCl solution acid pickling of anode electrolysis oil removing, 1:1 and distilled water, ultrapure water washing;
Silvered film bath system in the middle of preplating: matrix is placed in to the middle silvered film bath system of the preplating that contains high coordination agent, low main salt, silvered film in the middle of short period of time preplating under little current condition, wherein: pre-silver-plated employing continuous current plating mode, current density is 0.2 ~ 2A/dm
2, the distance of negative electrode and positive electrode is 2 ~ 15cm, temperature is 35 ~ 75 DEG C, electroplating time 1 ~ 5min;
Flash plate silver plating solution system: after pre-silver-plated, matrix carries out ultrapure washing, then directly enter in the coating bath that contains flash plate silver plating solution system, carry out fast electric silver-plated, complete after plating, from electroplate liquid, take out sample, use distilled water clean surface, cold air drying, wherein: the mode that adopts continuous current to electroplate when flash plate, current density is 0.5 ~ 8A/dm
2, the distance of negative electrode and positive electrode is 2 ~ 25cm, temperature is 25 ~ 85 DEG C, electroplating time 1 ~ 90min.
Electrosilvering combined additive of the present invention is not containing highly toxic substance, additive stability is high, and ensure that the stability of plating solution is constant after adding, in the process storing and use, additive does not decompose in plating solution, through additive after continuous current plating repeatedly without decomposition, can obviously promote the electrodeposition rate of silvered film, do not affect cathode efficiency, thereby can effectively expand allowed working current density scope, in very wide temperature range, in current density range, all can obtain having specular gloss, the silvered film of excellent performance, ensure to add non-cyanide silver electroplating system after additive to go for the production requirement of different field, realize the object of complete substitute electrosilvering, realize the environmental protection of silver plating process.
Brief description of the drawings
Fig. 1 is in embodiment two, and pre-silver plating process does not contain the SEM test pattern of the silvered film obtaining under the processing condition of electrosilvering additive;
Fig. 2 is in embodiment two, and pre-silver plating process adds the SEM test pattern of the silvered film obtaining under the processing condition of electrosilvering additive;
Fig. 3 is in embodiment six, and high speed electrodeposition silver process does not contain the SEM test pattern of the silvered film obtaining under the processing condition of electrosilvering additive;
Fig. 4 is in embodiment six, and high speed electrodeposition silver process adds the SEM test pattern of the silvered film obtaining under the processing condition of electrosilvering additive.
Embodiment
Below in conjunction with accompanying drawing, technical scheme of the present invention is further described; but do not limit to so; every technical solution of the present invention is modified or is equal to replacement, and not departing from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment one: electroplate in order to solve prussiate the pollution problem that long-term existence is brought, the matrix that the electroplating technology in present embodiment adopts is copper sheet, and its electrosilvering technological operation is as follows:
One, the preparation of combined additive: non-cyanide bright electrosilvering combined additive is the composition of inorganic additives and organic additive, the ratio that is 1:5 ~ 55:1 according to mass ratio by both dissolves it after mixing completely, then use volumetric flask constant volume, obtain the solution of electrosilvering combined additive, it is the ultrapure water preparation of 18M Ω/cm that the solution of institute's additive preparation adopts resistivity.It is to realize the consistence of plating solution, coating performance and prussiate electrosilvering system that body series does electrosilvering combined additive main purpose.
Two, electrosilvering plating solution preparation:
First carry out the preparation of electrosilvering plating solution, electrosilvering combined additive of the present invention is applicable to pre-silver-plated and the silver-plated system of fast electric, and therefore the process for preparation of plating solution is divided into two kinds:
1, the plating solution of silvered film bath system preparation in the middle of preplating: see described in CN102168290A, plating solution is formulated by 50 ~ 200g/L hydantoin derivatives, 50 ~ 200g/L auxiliary complexing agent, 65 ~ 125g/L potassium hydroxide, 50 ~ 150g/L salt of wormwood and 8 ~ 30g/L Silver Nitrate, controls the pH value of plating solution between 9 ~ 14.
2, the plating solution of flash plate silver plating solution system preparation: see described in CN103397355A, plating solution is formulated by 50 ~ 450g/L hydantoin derivatives, 10 ~ 300g/L auxiliary complexing agent, 35 ~ 325g/L potassium hydroxide, 35 ~ 300g/L salt of wormwood and 5 ~ 105g/L Silver Nitrate, controls the pH value of plating solution between 9 ~ 14.
Plating solution adds combined additive, the adjustment bath temperature of requirement after having prepared, carry out the operation of electrosilvering, carries out electrosilvering technique under direct current electrode position condition.
Three, add additive: form the demand to additive amount according to different plating solutions, measure a certain amount of electrosilvering combined additive, join in the electrosilvering plating solution of having prepared, stand-by after stirring.
Four, electrosilvering: carry out the operation of electrosilvering at copper matrix surface.
The concrete steps of substrate pretreatment are: the HCl solution acid pickling of anode electrolysis oil removing, 1:1 and distilled water, ultrapure water washing;
Silvered film bath system in the middle of preplating: matrix is placed in to the middle silvered film bath system of the preplating that contains high coordination agent, low main salt, silvered film in the middle of short period of time preplating under little current condition, wherein: pre-silver-plated employing continuous current plating mode, current density is 0.2 ~ 2A/dm
2, the distance of negative electrode and positive electrode is 2 ~ 15cm, temperature is 35 ~ 75 DEG C, electroplating time 1 ~ 5min;
Flash plate silver plating solution system: after pre-silver-plated, matrix carries out ultrapure washing, then directly enter in the coating bath that contains flash plate silver plating solution system, carry out fast electric silver-plated, complete after plating, from electroplate liquid, take out sample, use distilled water clean surface, cold air drying, wherein: the mode that adopts continuous current to electroplate when flash plate, current density is 0.5 ~ 8A/dm
2, the distance of negative electrode and positive electrode is 2 ~ 25cm, temperature is 25 ~ 85 DEG C, electroplating time 1 ~ 90min.
By experimental study, determine the combination that in present embodiment, electrosilvering combined additive used is organic additive and inorganic additives.
Inorganic additives is mainly some metal ions, metallic compound, the mixture of one or more in nonmetallic ion or nonmetallic compound, wherein, inorganic metal additive comprises Co, Mn, La, Ni, Al, Cu, Sb, Cd, Ca, the mixture of one or more in the ion of the element such as Cr and Ba or its compound, inorganic non-metallic additive is mainly Te, the mixture of one or more in the ion of Se and S or its compound, these inorganic additivess add outward appearance bright property and microscopic appearance and the grain-size that can effectively improve silvered film, organic additive comprises the compound of some chains or heterocycle shape and their polymkeric substance, is mainly some organic additives that easily adsorb or be easily reduced, and comprises the sulfurous organic compounds such as thiocarbamide, butynediol, glyoxaline compound, pyridine compounds and their, organic phosphoric acid compound, organic sulfonate, polymine, quadrol, o-benzoic sulfimide, tetraethylene pentamine, soluble tartrate, 2,2-dipyridyl, the bipyridyliums compounds such as 4,4-dipyridyl, polyvinyl alcohol, polyacrylamide, thiazolinyl dithio propane sulfonic acid sodium, aliphatic amine polyoxyethylene ether, fatty alcohol-polyoxyethylene ether, sodium polydithio-dipropyl sulfonate, phenyl dithiopropane sodium sulfonate, cetyl trimethylammonium bromide, aliphatic amide oxyethyl group sulfonated bodies, NBT, succimide, polyoxyethylene glycol, unsaturated fatty acids, VITAMIN B4, xanthoglobulin, cytosine(Cyt), uridylic, asccharin, Vanillin, tartrate, piperonylaldehyde, thymus pyrimidine, guanine, uric acid, adenosine, Theobromine, hydroxyethylethylene diamine tri-acetic acid, 3-hydroxyl-2-pyridine carboxylic acid, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, the mixture of one or more in the organism such as cetyl diphenyl ether sodium disulfonate and 2-pyridine carboxylic acid, electrosilvering organic additive be added in improving plating solution and silvered film performance time, can improve the wettability of plating solution, make coating more even, light, can promote the current density upper limit of electrosilvering or the current density range interval of expansion work, make non-cyanide silver electroplating system obtain well behaved silvered film in comparatively broad current density range, promote the electrodeposition rate of electrosilvering, improve the production efficiency of electrosilvering.
Embodiment two: what present embodiment was different from embodiment one is, described electrosilvering combined additive consists of: use polyoxyethylene glycol 0.25g/L, 2,2-dipyridyl 10g/L, polymine 0.1g/L, tartrate 0.5g/L, nitrate of baryta 0.1g/L, lanthanum nitrate 0.05g/L, Sodium Selenite 1.25g/L preparation non-cyanide silver electroplating combined additive, in pre-silver plating process, the consumption of the additive in plating solution is 1 ~ 45ml/L.Fig. 1 is the SEM figure that does not contain the electrosilvering coating of additive, and Fig. 2 is the SEM figure that adds the silvered film after silver-plated additive.As shown in Figure 2, obtain macroscopic view after using the additive that provides of present embodiment to electroplate and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment three: what present embodiment was different from embodiment two is, described electrosilvering combined additive consists of: use succimide 5g/L, PA 1.5g/L, uridylic 3g/L, Sodium dodecylbenzene sulfonate 1g/L, Potassium Selenocyanate 1.0g/L, mangaic acid copper 0.1g/L to be mixed with electrosilvering combined additive, in high speed electrodeposition silver process, the consumption of additive is 2 ~ 25ml/L.After plating, obtain macroscopic view and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment four: what present embodiment was different from embodiment two is, described electrosilvering combined additive consists of: use xanthoglobulin 4.5g/L, piperonylaldehyde 1.5g/L, thiocarbamide 1.5g/L, hydroxyethylethylene diamine tri-acetic acid 3g/L, cadmium nitrate 0.5g/L, Sulfothiorine 0.25g/L preparation electrosilvering combined additive, in high speed electrodeposition silver process, the consumption of additive is 5 ~ 35ml/L.After plating, obtain macroscopic view and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment five: what present embodiment was different from embodiment two is, consisting of of described electrosilvering combined additive: use Vanillin 2g/L, polymine 1g/L, cytosine(Cyt) 5g/L, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 0.8g/L, butter of antimony 0.15g/L, potassium tellurite 1.5g/L preparation electrosilvering combined additive, the consumption of additive is 1 ~ 25ml/L in pre-silver plating process.After plating, obtain macroscopic view and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment six: what present embodiment was different from embodiment two is, described electrosilvering additive consists of: use 2,2-dipyridyl 4g/L, hydroxyethylethylene diamine tri-acetic acid 5g/L, polyoxyethylene glycol 10g/L, soluble tartrate 1.8g/L, uridylic 1g/L, cetyl diphenyl ether sodium disulfonate 1g/L, tin anhydride 0.75g/L, lanthanum nitrate 0.15g/L preparation electrosilvering combined additive, in high-speed silver plating technique, the consumption of additive is 0.5 ~ 55ml/L.Fig. 3 is the SEM figure that does not contain the electrosilvering coating of additive, and Fig. 4 is the SEM figure that adds the silver-plated coating after silver-plated additive.As shown in Figure 4, obtain macroscopic view after using the additive that provides of present embodiment to electroplate and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment seven: what present embodiment was different from embodiment two is, consisting of of described electrosilvering combined additive: use hydroxyethylethylene diamine tri-acetic acid 5g/L, Vanillin 3g/L, antimonypotassium tartrate 0.75 g/L, Sodium Selenite 0.25g/L, butynediol 1.5g/L, Sodium dodecylbenzene sulfonate 0.75g/L preparation electrosilvering combined additive, in high speed electrodeposition silver process, the consumption of combined additive is 3 ~ 55ml/L.After plating, obtain macroscopic view and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment eight: what present embodiment was different from embodiment two is, described electrosilvering additive consists of: use adjacent benzenesulfonimide 1g/L, piperonylaldehyde 1g/L, polyvinyl alcohol 1.25g/L, sodium lauryl sulphate 1g/L, selenium Zassol 0.15g/L, Sulfothiorine 0.8g/L preparation electrosilvering combined additive, in pre-silver plating process, the consumption of combined additive is 1 ~ 25ml/L.After plating, obtain macroscopic view and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment nine: what present embodiment was different from embodiment two is, described electrosilvering combined additive consists of: use NBT 1g/L, Sodium Selenite 1.75g/L, lanthanum nitrate 0.15g/L, hydroxyethylethylene diamine tri-acetic acid 3g/L, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate 1g/L, tetraethylene pentamine 1.5 g/L preparation electrosilvering combined additives, in high speed electrodeposition silver process, the consumption of combined additive is 1 ~ 50ml/L.After plating, obtain macroscopic view and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Embodiment ten: what present embodiment was different from embodiment two is, described electrosilvering combined additive consists of: use quadrol 2g/L, 4,4-dipyridyl 1.25g/L, Vanillin 1g/L, Sodium Selenite 0.5g/L, hydroxyethylethylene diamine tri-acetic acid 1.75g/L, cetyl diphenyl ether sodium disulfonate 1g/L preparation electrosilvering combined additive, in high speed electrodeposition silver process, the consumption of combined additive is 1 ~ 65ml/L.After plating, obtain macroscopic view and present the evenly silvered film of smooth, SEM observation microscopic crystalline even compact, flawless, AFM observation coating leveling ability excellence of specular gloss, outward appearance.
Claims (10)
1. a non-cyanide bright electrosilvering combined additive, is characterized in that described combined additive is the combination of organic additive and inorganic additives, and the mass ratio of organic additive and inorganic additives is at 1:5 ~ 55:1.
2. non-cyanide bright electrosilvering combined additive according to claim 1, is characterized in that described inorganic additives is one or more the mixture in metal ion, metallic compound, nonmetallic ion or nonmetallic compound.
3. non-cyanide bright electrosilvering combined additive according to claim 2, is characterized in that described metal ion is one or more the mixture in the ion of Co, Mn, La, Ni, Al, Cu, Sb, Cd, Ca, Cr and Ba element.
4. non-cyanide bright electrosilvering combined additive according to claim 2, is characterized in that described metallic compound is one or more the mixture in the compound of Co, Mn, La, Ni, Al, Cu, Sb, Cd, Ca, Cr and Ba element.
5. non-cyanide bright electrosilvering combined additive according to claim 2, is characterized in that described nonmetallic ion is one or more the mixture in Te, Se and S ion.
6. non-cyanide bright electrosilvering combined additive according to claim 2, is characterized in that described nonmetallic compound is one or more the mixture in Te, Se and S compound.
7. non-cyanide bright electrosilvering combined additive according to claim 1, is characterized in that described organic additive is sulfurous organic compound, butynediol, glyoxaline compound, pyridine compounds and their, organic phosphoric acid compound, organic sulfonate, polymine, quadrol, o-benzoic sulfimide, tetraethylene pentamine, soluble tartrate, 2,2-dipyridyl, the bipyridyliums compounds such as 4,4-dipyridyl, polyvinyl alcohol, polyacrylamide, thiazolinyl dithio propane sulfonic acid sodium, aliphatic amine polyoxyethylene ether, fatty alcohol-polyoxyethylene ether, sodium polydithio-dipropyl sulfonate, phenyl dithiopropane sodium sulfonate, cetyl trimethylammonium bromide, aliphatic amide oxyethyl group sulfonated bodies, NBT, succimide, polyoxyethylene glycol, unsaturated fatty acids, VITAMIN B4, xanthoglobulin, cytosine(Cyt), uridylic, asccharin, Vanillin, tartrate, piperonylaldehyde, thymus pyrimidine, guanine, uric acid, adenosine, Theobromine, hydroxyethylethylene diamine tri-acetic acid, 3-hydroxyl-2-pyridine carboxylic acid, disodium 4-dodecyl-2,4 '-oxydibenzenesulfonate, Sodium dodecylbenzene sulfonate, sodium laurylsulfonate, the mixture of one or more in cetyl diphenyl ether sodium disulfonate and 2-pyridine carboxylic acid organism.
8. the using method of the non-cyanide bright electrosilvering combined additive described in the arbitrary claim of claim 1-7 in non-cyanide silver electroplating system, is characterized in that described method steps is as follows:
One, additive preparation: take successively inorganic additives and the organic additive of respective amount, both are dissolved in solution and are mixed with settled solution after mixing, stand-by by preserving after the additive constant volume of respective concentration;
Two, electrosilvering plating solution preparation:
The preparation of silvered film bath system in the middle of preplating: plating solution is formulated by 50 ~ 200g/L hydantoin derivatives, 50 ~ 200g/L auxiliary complexing agent, 65 ~ 125g/L potassium hydroxide, 50 ~ 150g/L salt of wormwood and 8 ~ 30g/L Silver Nitrate, controls the pH value of plating solution between 9 ~ 14;
The plating solution preparation of flash plate silver plating solution system: plating solution is formulated by 50 ~ 450g/L hydantoin derivatives, 10 ~ 300g/L auxiliary complexing agent, 35 ~ 325g/L potassium hydroxide, 35 ~ 300g/L salt of wormwood and 5 ~ 105g/L Silver Nitrate, controls the pH value of plating solution between 9 ~ 14;
Plating solution has been prepared the rear combined additive that adds respectively 0.1～175ml/L;
Three, electrosilvering:
Silvered film bath system in the middle of preplating: matrix is placed in to the middle silvered film bath system of preplating, silvered film in the middle of short period of time preplating under little current condition, wherein: pre-silver-plated employing continuous current plating mode, current density is 0.2 ~ 2A/dm
2, the distance of negative electrode and positive electrode is 2 ~ 15cm, temperature is 35 ~ 75 DEG C, electroplating time 1 ~ 5min;
Flash plate silver plating solution system: after pre-silver-plated, matrix carries out ultrapure washing, then directly enter in the coating bath that contains flash plate silver plating solution system, carry out fast electric silver-plated, complete after plating, from electroplate liquid, take out sample, use distilled water clean surface, cold air drying, wherein: the mode that adopts continuous current to electroplate when flash plate, current density is 0.5 ~ 8A/dm
2, the distance of negative electrode and positive electrode is 2 ~ 25cm, temperature is 25 ~ 85 DEG C, electroplating time 1 ~ 90min.
9. the using method of non-cyanide bright electrosilvering combined additive according to claim 8 in non-cyanide silver electroplating system, the solution employing resistivity that it is characterized in that described additive preparation is the ultrapure water preparation of 18M Ω/cm.
10. the using method of non-cyanide bright electrosilvering combined additive according to claim 8 in non-cyanide silver electroplating system, it is characterized in that described matrix needs to carry out pre-treatment before plating, the concrete steps of substrate pretreatment are as follows: the HCl solution acid pickling of the oil removing of employing anode electrolysis, 1:1 and distilled water, ultrapure water washing.
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| CN107385440A (en) * | 2017-08-09 | 2017-11-24 | 无锡市恒利弘实业有限公司 | One kind is in steel substrate surface without cyanogen Composite Coatings La TiO2The electro-plating method of Ag layers |
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| CN107841771A (en) * | 2017-10-25 | 2018-03-27 | 厦门大学 | It is a kind of based on the non-cyanide plating silvering solution composition of complexing ligands system and its application |
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| CN104773794A (en) * | 2015-04-30 | 2015-07-15 | 湖南富莱明节能环保科技有限公司 | Composite additive for electrolysis |
| CN105112952A (en) * | 2015-09-21 | 2015-12-02 | 无锡清杨机械制造有限公司 | Electroplating solution for non-cyanide silver electrodeposition, and electroplating method |
| CN105463524A (en) * | 2015-12-23 | 2016-04-06 | 苏州市金星工艺镀饰有限公司 | Electroplating method of cyanide-free silver electroplating liquid |
| CN106086956A (en) * | 2016-07-30 | 2016-11-09 | 哈尔滨工业大学 | Alkaline non-cyanide electrodepositing zinc-nickel alloy additive and application thereof |
| CN106086956B (en) * | 2016-07-30 | 2019-03-01 | 哈尔滨工业大学 | Alkaline non-cyanide electrodepositing zinc-nickel alloy additive and its application |
| CN106757207A (en) * | 2016-11-29 | 2017-05-31 | 江苏澳光电子有限公司 | A kind of method for pcb board chemical nickel plating palldium alloy |
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| CN107419326A (en) * | 2017-04-12 | 2017-12-01 | 广州市双石金属制品有限公司 | A kind of vacuum ion plating electrochemistry removing plating formula of liquid |
| CN107460532A (en) * | 2017-04-12 | 2017-12-12 | 广州市双石金属制品有限公司 | A kind of vacuum ion plating electrochemistry removing plating formula of liquid |
| CN107419326B (en) * | 2017-04-12 | 2018-12-07 | 广州市双石金属制品有限公司 | A kind of vacuum ion plating electrochemistry removing plating formula of liquid |
| CN107385440A (en) * | 2017-08-09 | 2017-11-24 | 无锡市恒利弘实业有限公司 | One kind is in steel substrate surface without cyanogen Composite Coatings La TiO2The electro-plating method of Ag layers |
| CN107299368B (en) * | 2017-08-09 | 2019-12-10 | 无锡市恒利弘实业有限公司 | Electroplating method for cyanide-free composite plating of RE-TiO 2 -Ag layer on surface of steel substrate |
| CN107299368A (en) * | 2017-08-09 | 2017-10-27 | 无锡市恒利弘实业有限公司 | One kind is in steel substrate surface without cyanogen Composite Coatings RE TiO2Ag layers of electro-plating method |
| CN107899572A (en) * | 2017-10-24 | 2018-04-13 | 安徽省福泰精细化工有限责任公司 | A kind of preparation method for the catalyst for electrolytic silver for being used to produce formaldehyde |
| CN107899572B (en) * | 2017-10-24 | 2020-10-16 | 安徽省福泰精细化工有限责任公司 | Preparation method of electrolytic silver catalyst for producing formaldehyde |
| CN107841771A (en) * | 2017-10-25 | 2018-03-27 | 厦门大学 | It is a kind of based on the non-cyanide plating silvering solution composition of complexing ligands system and its application |
| CN109504990A (en) * | 2018-12-11 | 2019-03-22 | 湖北工程学院 | A kind of weakly acidic pH Brush Plating silver plating liquid and its preparation process, application method |
| CN110016700A (en) * | 2019-05-06 | 2019-07-16 | 嘉兴学院 | A kind of silver-plated active substrate of Surface enhanced Raman spectroscopy and preparation 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 |
| CN111235609A (en) * | 2020-03-10 | 2020-06-05 | 国网浙江省电力有限公司电力科学研究院 | Cyanide-free silver plating solution, silver plating layer and preparation method thereof |
| CN111235609B (en) * | 2020-03-10 | 2021-06-08 | 国网浙江省电力有限公司电力科学研究院 | Cyanide-free silver plating solution, silver plating layer and preparation method thereof |
| CN112103476A (en) * | 2020-09-23 | 2020-12-18 | 厦门大学 | Lithium-free negative electrode material of dual-ion battery, preparation method and dual-ion battery |
| CN114059112A (en) * | 2021-08-04 | 2022-02-18 | 中国科学院宁波材料技术与工程研究所 | Cyanide-free silver plating electroplating solution and application thereof |
| CN113638019A (en) * | 2021-08-13 | 2021-11-12 | 安徽师范大学 | Thick silver electroplated copper-based workpiece and manufacturing method thereof |
| CN113862736A (en) * | 2021-10-22 | 2021-12-31 | 深圳市潮尊珠宝首饰有限公司 | Electrogilding liquid for cyanide-free sulfite system and application thereof |
| CN113862736B (en) * | 2021-10-22 | 2024-01-26 | 深圳市潮尊珠宝首饰有限公司 | Cyanide-free sulfite system electro-gold plating solution and application thereof |
| CN114808052A (en) * | 2022-04-02 | 2022-07-29 | 武汉材料保护研究所有限公司 | Cyanide-free conversion method of cyanide silver plating solution |
| CN114808052B (en) * | 2022-04-02 | 2024-03-15 | 中国机械总院集团武汉材料保护研究所有限公司 | Cyanide-free conversion method for cyanide silver plating solution |
| CN116837429A (en) * | 2023-08-29 | 2023-10-03 | 宁波德洲精密电子有限公司 | Electroplating solution suitable for lead frame tinning |
| CN116837429B (en) * | 2023-08-29 | 2023-11-10 | 宁波德洲精密电子有限公司 | Electroplating solution suitable for lead frame tinning |
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