CN1563489A - Method of silver plating layer in fine structure deposited from non aqueous solution and application - Google Patents
Method of silver plating layer in fine structure deposited from non aqueous solution and application Download PDFInfo
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- CN1563489A CN1563489A CN 200410013009 CN200410013009A CN1563489A CN 1563489 A CN1563489 A CN 1563489A CN 200410013009 CN200410013009 CN 200410013009 CN 200410013009 A CN200410013009 A CN 200410013009A CN 1563489 A CN1563489 A CN 1563489A
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Abstract
This invention relates to a method and its application for utilizing non-aqueous solution to deposit fine structure silver cladder which utilizes the displacement reaction mechanism of Ag or more active plated material in alcohol base organic solution to plate Ag taking the polar organic solution as the master solution of a plating liquor and added with Ag complex compound to contact Ag plating solvent with the plated substrate to increase the binding force of the cladder.
Description
(1) technical field:
The present invention relates to a kind of electrochemical surface technology, especially relate to the method for a kind of non-aqueous solution deposition fine structure silver plating.
(2) background technology:
Silver-plated be a kind of common, have many uses and the sufacing of less expensive.Silver belongs to precious metal.Because physics, machinery and the chemical property of the uniqueness of argent, it is very strong ornamental and functional to make product with metal silver surface and component have.Especially it had very high electroconductibility and thermal conductivity make it in each field of electricity purposes very widely be arranged.
Silver-plated have various technology, totally can be divided into metallurgy, chemistry, physics, machinery and synthetic method.Wherein synthetic method can have electrochemical deposition method, physical vapor deposition, chemical vapour deposition, machine-alloying etc.Most widely used silver impregnation method is an electrochemical deposition method at present, and it is silver-plated that electrochemical deposition method can also be divided into electrosilvering, catalysis silver-plated (also claiming electroless plating of silver) and substitution method.Prussiate is that the solution system of main formula still is the important prescription of electrosilvering industry member at present.For fear of the danger of prussiate, scientific and technical personnel have proposed many non-cyaniding solution systems, breathe out quinoline acid solution etc. as thiosulfuric acid solution, sulphosalicylic acid solution, imino-diacetic ammonium sulphonate solution, pyrrole.The silver-plated main body solution of catalysis is silver nitrate solution, adopt the interpolation catalyzer can make the silver ions in the solution constantly continue to deposit at the plating body surface, various technology is wherein arranged, as being the prescription of reductive agent with glucose, being the prescription of reductive agent, being the prescription of reductive agent with formaldehyde, being prescription of reductive agent etc. with the dimethylin borine with tartrate.Replacement ag plating has cyaniding solution system and non-cyaniding solution system, and main body solution still is the cyaniding solution system at present, and the research of non-cyaniding solution system never is interrupted.
Replacement ag plating (also claiming immersion silver) is a kind of silver-coating method simple to operate, lower-cost.But because the displacement plating is the electrochemical deposition technique that is based upon on the general displacement chemical reaction basis, if do not obtain technology controlling and process, the result of replacement(metathesis)reaction generally is the uneven settling of structure that obtains tissue looseness.Silver-plated on more active metal with plating and electroless-plating, because the driving of electromotive force, silver ions in the solution also is easy to deposit out with substitute mode, the silver layer of this tissue looseness can make the bonding force of the silvering of resulting product descend, and therefore how controlling replacement coating in these two kinds of coating operations is a technology of technology.
Because substitute mode can only be to obtain silver at exposed surface, so will obtain very thin silvering or save silver-colored consumption, this is a kind of very suitable reaction in theory.In order to obtain to have the silvering of suitable weave construction, need fill a prescription and technology controlling and process.The existing technology of replacement ag plating remains based on cyaniding water solution system and non-cyaniding water solution system, is main water solution system but the silver-plated technology of existing non-cyaniding water solution system still is inferior to prussiate.The research of exploring and seek new solution system is current emphasis.
(3) summary of the invention:
The invention solves the problem that has uncontrollable silvered film internal structure in organic solution now, a kind of bonding force that can improve silvered film is provided, make the internal structure of coating be able to the method for the non-aqueous solution deposition fine structure silvering of all even miniaturizations.
Technical scheme of the present invention is as follows: a kind of method of non-aqueous solution deposition fine structure silvering, it is to utilize silver and carry out silver-plated than the active mechanism by the replacement(metathesis)reaction of plating material in alcohol radical organic solution of silver, it is characterized in that: to have the main body solution that polar organic solution is the plating bath solvent, in main body solution, add the silver complex compound that can form ligand, silver-plated solvent is contacted with quilt plating base material with silver ions.
Therefore the present invention makes that owing to all free silver ions in the solution all enter the ligand kernel loose sedimental separating out avoided.The formation meeting of silver ions ligand obviously changes the current potential that silver is separated out.Because the electroconductibility of organic solvent is lower than water, the current potential that silver ions is separated out also descends usually, and the silver ions ligand has improved the current potential that silver is separated out, and makes this replacement(metathesis)reaction not produce disadvantageous effect because having adopted organic solvent.On the contrary, because the content of free oxygen is very low usually in the organic solvent, this just makes that side reaction of replacement ag plating reaction is reduced, thereby the content of oxide compound in the silver of acquisition is descended, and makes the glossiness of silvering improve simultaneously, and weather resistance improves.In order to improve silver-plated quality, in solution, can also add and improve the dispersed and mobile material of electroconductibility.Adopt additive that the internal structure of silvering is effectively controlled, it is the approach that the plating effect is increased substantially, can assert according to the silver plated result of study of displacement in the raising organic solution: adopting the interpolation silver complex compound is a kind of fruitful approach, the result will make the bonding force of coating be improved, and make the internal structure of coating be able to all even miniaturization.
(4) embodiment:
The present invention utilizes silver and carries out silver-plated than the active mechanism by the replacement(metathesis)reaction of plating material in alcohol radical organic solution of silver, to have the main body solution that polar organic solution is the plating bath solvent, in main body solution, add the silver complex compound that can form ligand, silver-plated solvent is contacted with quilt plating base material with silver ions.The plating bath solvent adopts alcohol radical organic solution, and the pure and mild polyvalent alcohol in unit, the pure and mild alcohol mixture of single kind can be arranged, and the volume of alcoholic solvent accounts for more than 50% of total liquor capacity.Silver complex compound comprises the compound that can form complex compound with the chemical combination body of silver element or silver; Comprising: citric acid, succsinic acid, ammonium chloride, quadrol, alcohol acid, ammonia, trolamine, lactic acid, oxysuccinic acid, Padil, tartrate, tetra-sodium, ethylenediamine tetraacetic acid (EDTA), oxoethanoic acid, contain one or more coordination compoundes in solution.The amount of the coordination compound that adopts is controlled according to the attribute of silver element and ligand compound body formation complex compound, and the mol ratio of compound and silver ions is 1: 2～6: 1.Had different current potentials by the plating material with silver, silver ions is reduced under electromotive force drives and it is silver-plated to carry out, and the metal that quilt is plated is chemically than the more active metal of silver.In silver-plated solvent, can also drop into minor amounts of additives, comprise the material and the tensio-active agent that improve dispersed and mobile material, change and regulator solution potential of hydrogen of electroconductibility, water, ketone etc. are wherein arranged, to increase the bonding force of silvering and matrix.Silver-plated solvent is added gas to be stirred or ultrasonic stirring.Should be with comprising electronic industry, power industry, measurement instrument industry, materials processing industry, electrode process industry, electroplating industry, adnornment industry, semi-conductor and information
Technical field.
This novel organic silver plated preparation process is generally: the 1) pre-treatment of base material.2) dissolving of coordination compound in alcohol-based solvent, coordination compound is not as the criterion there not to be the free silver ions in the solution with the mol ratio of silver.3) silver element in organic solution with the reaction of coordination compound, promptly add the process of argentiferous thing.4) in solution, add the material that improves electroconductibility dispersiveness and flowability.5) in solution, add alkali or acid potential of hydrogen with regulator solution.6) plated the plating of base material in solution.7) plating aftertreatment.
When base material input alcohol based sols carried out silver-plated operation, the relative solution of base material should have change in location, produced the silver ions dilution thereby can avoid being plated substrate surface, added gas stirring or ultrasonic stirring and can not obtain better effect than not adding stirring.
Below be described in detail two examples of implementation of the present invention:
Embodiment 1:
Preparation nanostructured metal silvering on the copper base material.Concrete steps are: (1) thick 0.37 micron area is 5cm
2Be used for Copper Foil that electronic devices and components use through cleaning with industrial acetone, dry up, top layer impurity is removed in etch in 5% sulphuric acid soln.(2) with 10 milliliters dissolve with ethanol solution citric acid.With the water-soluble solution of Silver Nitrate.In ethanol liquid, drip silver nitrate solution, make the silver content in the solution reach 50ppm.The mol ratio of control citric acid and silver ions is 2: 1.(3) in above-mentioned solution, add a little quaternary amine alkali, limpid to solution.(4) immersion plating of copper base material is taken out then in this plating bath under intensive stirs immersion plating 1-2 minute, cleans up in industrial acetone, dries up.After testing, on the Copper Foil through the plating processing, the lining thickness of silver reaches 30-80nm.Silver-colored particle size in its silver layer is 20-40nm.Change the coating that the plating condition can obtain to have meticulousr crystalline-granular texture.
Embodiment 2:
The argent decorative coating that preparation has nanostructure on titanium.Concrete steps are: (1) dissolves tartrate with 10 milliliters butanol solution.Simultaneously with the water-soluble solution of Silver Nitrate.In ethanol liquid, drip silver nitrate solution, make the silver content in the solution reach 100ppm.The mol ratio of control tartrate and silver ions is 2: 1.(2) in above-mentioned solution, add a little ammoniacal liquor, get the top clear solution, add 20% methyl alcohol, become plating bath.The area of (3) 1 micron thickness is 2cm
2Be used to increase industrially pure titanium plate that electric conductivity uses through cleaning with industrial acetone, dry up, etch is 10 seconds in 2% hydrofluoric acid solution, removes surface oxides.(4) immediately with the immersion plating of plating base material in this plating bath, under hyperacoustic stirring immersion plating 1-2 minute, take out then, in industrial acetone, clean up, dry up.After testing, on the titanium through the plating processing, the lining thickness of silver reaches 40-100nm.The silver plated part of titanium shows very beautiful outward appearance.
Additive can make the internal structure of silvering be effectively controlled, it is the approach that the plating effect is increased substantially, can assert according to the silver plated result of study of displacement in the raising organic solution: adopting the interpolation silver complex compound is a kind of fruitful approach, the result will make the bonding force of coating be improved, and make the internal structure of coating be able to all even miniaturization.
Claims (8)
1. the method for non-aqueous solution deposition fine structure silvering, it is to utilize silver and carry out silver-plated than the active mechanism by the replacement(metathesis)reaction of plating material in alcohol radical organic solution of silver, it is characterized in that: to have the main body solution that polar organic solution is the plating bath solvent, in main body solution, add the silver complex compound that can form ligand, silver-plated solvent is contacted with quilt plating base material with silver ions.
2. the method for non-aqueous solution deposition fine structure silvering according to claim 1, it is characterized in that: the plating bath solvent adopts alcohol radical organic solution, the pure and mild polyvalent alcohol in unit, the pure and mild alcohol mixture of single kind can be arranged, and the volume of alcoholic solvent accounts for more than 50% of total liquor capacity.
3. the method for non-aqueous solution deposition fine structure silvering according to claim 1 is characterized in that: silver complex compound comprises the compound that can form complex compound with the chemical combination body of silver element or silver; Comprising: citric acid, succsinic acid, ammonium chloride, quadrol, alcohol acid, ammonia, trolamine, lactic acid, oxysuccinic acid, Padil, tartrate, tetra-sodium, ethylenediamine tetraacetic acid (EDTA), oxoethanoic acid, contain one or more coordination compoundes in solution.
4. the method for non-aqueous solution deposition fine structure silvering according to claim 3, it is characterized in that: the amount of the coordination compound of employing is controlled according to the attribute of silver element and ligand compound body formation complex compound, and the mol ratio of compound and silver ions is 1: 2～6: 1.
5. the method for non-aqueous solution deposition fine structure silvering according to claim 1, it is characterized in that: plated material and have different current potentials with silver, that silver ions is reduced under electromotive force drives and carry out silver-platedly, the metal that is plated is chemically than the more active metal of silver.
6. the method for non-aqueous solution deposition fine structure silvering according to claim 1, it is characterized in that: in silver-plated solvent, can also drop into minor amounts of additives, comprise the material and the tensio-active agent that improve dispersed and mobile material, change and regulator solution potential of hydrogen of electroconductibility.
7. the method for non-aqueous solution deposition fine structure silvering according to claim 1 is characterized in that: in silver-plated process, silver-plated solvent is added gas stir or ultrasonic stirring.
8. the application of the method for a non-aqueous solution deposition fine structure silvering is characterized in that: should be with comprising electronic industry, power industry, measurement instrument industry, materials processing industry, electrode process industry, electroplating industry, adnornment industry, semi-conductor and areas of information technology.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN 200410013009 CN1288278C (en) | 2004-04-09 | 2004-04-09 | Method of silver plating layer in fine structure deposited from non aqueous solution and application |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410013009 CN1288278C (en) | 2004-04-09 | 2004-04-09 | Method of silver plating layer in fine structure deposited from non aqueous solution and application |
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| CN1563489A true CN1563489A (en) | 2005-01-12 |
| CN1288278C CN1288278C (en) | 2006-12-06 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366368C (en) * | 2006-03-23 | 2008-02-06 | 福州大学 | Non aqueous solution homogeneous phase reduction preparation method of nano-metallic silver |
| WO2015027886A1 (en) * | 2013-08-26 | 2015-03-05 | Byd Company Limited | Silver plating solution and method of silver plating by chemical replacement |
-
2004
- 2004-04-09 CN CN 200410013009 patent/CN1288278C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100366368C (en) * | 2006-03-23 | 2008-02-06 | 福州大学 | Non aqueous solution homogeneous phase reduction preparation method of nano-metallic silver |
| WO2015027886A1 (en) * | 2013-08-26 | 2015-03-05 | Byd Company Limited | Silver plating solution and method of silver plating by chemical replacement |
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| Publication number | Publication date |
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| CN1288278C (en) | 2006-12-06 |
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