CN102605360B - Chemical silvering solution based on imidazolium ionic liquid and silvering method - Google Patents
Chemical silvering solution based on imidazolium ionic liquid and silvering method Download PDFInfo
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- CN102605360B CN102605360B CN201110309598.9A CN201110309598A CN102605360B CN 102605360 B CN102605360 B CN 102605360B CN 201110309598 A CN201110309598 A CN 201110309598A CN 102605360 B CN102605360 B CN 102605360B
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Abstract
The invention relates to a chemical silvering solution based on an imidazolium ionic liquid system. The chemical silvering solution contains chlorinated imidazolium ionic liquid, silver salt and water. The volume ratio of chlorinated imidazolium ionic liquid to water equals to (1:9)-(9:1), namely, the volume percentage of the chlorinated imidazolium ionic liquid is 10%-90%, and the concentration range of the silver salt is 0.001-0.1mol/L. A very stable complex can be formed by the chlorinated imidazolium ionic liquid and silver ion, so that the chemical silvering solution provided by the invention does not need to be added with cyanide and is very stable. Thus, the chemical silvering solution is environment-friendly, and meanwhile, the potential safety hazard caused by on-site production is eliminated.
Description
Technical field
The present invention relates to a kind of chemical silvering solution and silver-coating method, particularly a kind of chemical silvering solution and silver-coating method based on imidazole salts ionic liquid.
Background technology
Good weld because silver has, the advantage such as weather-proof and conduction, so adopt chemical silvering to be widely used the printed circuit-board industry of the protection method of copper base material.At present, conventional copper base chemical silvering has two kinds of methods: the first is autocatalysis chemical silvering method.This method makes chemical silvering solution liquid in metastable state, extremely unstable because needs use reductive agent, and require base metallization surface to have metal sensitizing layer (conventional is Pd/Sn sensitizing layer), production cost is improved greatly, and then hinder its widespread use in industrial production.Meanwhile, in order to increase the stability of silver plating liquid, in some chemical silvering solution, add potassium cyanide as complexing agent, well-known, potassium cyanide is highly toxic substance, is in the use or in environment protection, all has a lot of problems.Second method is displacement chemical silver plating method, and this method utilizes copper different from silver-colored metal activity, directly using copper as reductive agent, by the replacement(metathesis)reaction of copper and silver ions, realizes the object of copper electroplate.Silver-plated for substitution method, usually use Silver Nitrate as silver-colored source, the aqueous solution plating solution of Silver Nitrate is extremely unstable, often needs now with the current.Simultaneously, the silver plating solution of copper base substitution method needs the nitric acid that working concentration is higher conventionally, carrying out in silver-plated also corroding copper substrate, later stage welding is had a negative impact, the electron device industry that this is more and more higher for integrated level, size is more and more less is unacceptable.
In order to improve above-mentioned deficiency, the human hairs such as Gu Changdong understand using choline chloride 60 base ionic liquid as solvent at the plating solution (application number 201010231683.3) of copper substrate surface plating porous nano silver, but, the solvent of this plating solution is formed by choline chloride 60 base ionic liquid and ethylene glycol mixture, under anhydrous like this plating solution environment, slightly inadequate with the process matching of chemical silvering.
Summary of the invention
The object of this invention is to provide that a kind of and existing Electroless Silver Plating matches, the formula of the chemical plating liquid of the substrate surface such as copper, nickel or nickel-phosphor alloy of low cost, greenization, base material after plating has higher erosion resistance and weldability, is enough to meet printed circuit board and the requirement of connector surface-treated.
The technical scheme that realizes above-mentioned purpose is that chemical silvering solution is made up of imidazolium chloride salt ionic liquid, silver salt and water.The composition of imidazolium chloride salt ionic liquid and water is: imidazolium chloride salt ionic liquid: water (volume ratio)=1: 9-9: 1, the volumn concentration that is imidazolium chloride salt ionic liquid is 10%-90%, and the concentration range of silver salt is 0.001-0.1mol/L.Because imidazolium chloride salt ionic liquid and silver ions can form highly stable complex compound, so chemical silvering solution of the present invention is without adding prussiate and very stable.
The structural formula of the imidazolium chloride salt ionic liquid in chemical silvering solution of the present invention is as follows:
Wherein R
1for methyl, R
2can be ethyl or butyl, for choosing of imidazolium chloride salt ionic liquid in chemical plating liquid, can choose R
2for ethyl, butyl or both mixtures.
The volumn concentration of chemical silvering Chlorine in Solution imidazole salts ionic liquid of the present invention is 10%-90%, when the ratio of ionic liquid is lower than 10% time, can cause the solubleness of silver salt in this mixing solutions to reduce, thereby cause plating solution unstable, otherwise in the time that the ratio of imidazolium chloride salt ionic liquid and water is greater than 90%, because imidazolium chloride salt ionic liquid and silver-colored complexing action can cause the plating time elongated, plating prompt drop is low.Chemical silvering Chlorine in Solution imidazole salts ionic liquid optimum volume ratio percentage composition of the present invention is 30%-80%.
Silver salt in the present invention in chemical silvering solution can be chosen one or both the mixture in silver chloride, Sulfuric acid disilver salt, Silver Nitrate and silver acetate.The add-on of silver salt is 0.001-0.1mol/L.When the concentration of silver salt is during lower than 0.001mol/L, because silver salt concentration is too low, can cause plating prompt drop low, otherwise in the time that the add-on of silver salt is greater than 0.1mol/L, the stability of plating solution is by variation, the optimum concentration range of silver salt is 0.01-0.05mol/L.
The invention has the beneficial effects as follows: chemical silvering solution of the present invention can match with existing Electroless Silver Plating, low cost, greenization, base material after plating has higher erosion resistance and weldability, is enough to meet printed circuit board and the requirement of connector surface-treated.Because imidazolium chloride salt ionic liquid and silver ions can form highly stable complex compound, so chemical silvering solution of the present invention is without adding prussiate and very stable, so this chemical silvering solution is very friendly to environment, also eliminate the potential safety hazard that situ production is brought simultaneously.
Specific embodiment
The preparation of embodiment 1 1L chemical plating liquid
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CH
2cH
2cH
2cH
3) be example, its compound method describes.After getting above-mentioned imidazolium chloride salt ionic liquid 800mL and fully mixing with the deionized water of 200mL, add silver chloride, the concentration that makes silver chloride is 0.1mol/L.Use the Electroless Silver Plating of chemical silvering solution of the present invention to be: first copper-clad plate to be placed in to skim soln (NaOH 10g/L, the Na of 60 DEG C
2cO
320g/L, Na
3pO
412H
2o 5g/L, OP-10 emulsifying agent 1g/L) in, 5min after washing; Be placed in again the etching solution ((NH under room temperature
3)
2s
2o
850g/L, H
2sO
4100ml/L), 1min after washing, to remove the oxide film of copper foil surface; Copper-clad plate through pre-treatment is placed in to the chemical silvering solution 2min after washing of the present invention of 50 DEG C, and removes immediately surface water mark, use hot blast drying.Stability, thickness of coating and the weldability of plating solution the results are shown in table 1.
The preparation of embodiment 2 1L chemical plating liquids
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CHCH
3cH
2cH
3) be example, its compound method describes.After getting above-mentioned imidazolium chloride salt ionic liquid 900mL and fully mixing with the deionized water of 100mL, add silver chloride, the concentration that makes silver chloride is 0.05mol/L.The operating procedure of chemical silvering is referring to embodiment 1, the stability of plating solution, thickness of coating and weldability the results are shown in table 1.Use and cover nickel plate as base material in this embodiment.
The preparation of embodiment 3 1L chemical plating liquids
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CHCH
3cH
2cH
3) be example, its compound method describes.After getting above-mentioned imidazolium chloride salt ionic liquid 300mL and fully mixing with the deionized water of 700mL, add silver chloride, the concentration that makes silver chloride is 0.01mol/L.The operating procedure of chemical silvering is referring to embodiment 1, the stability of plating solution, thickness of coating and weldability the results are shown in table 1.
The preparation of embodiment 4 1L chemical plating liquids
With imidazolium chloride salt ionic liquid (R
1=-CH
3, R
2=-CH
2cH
3) be example, its compound method is described.After getting above-mentioned imidazolium chloride salt ionic liquid 100mL and fully mixing with the deionized water of 900mL, add silver chloride, the concentration that makes silver chloride is 0.001mol/L.The operating procedure of chemical silvering is referring to embodiment 1, the stability of plating solution, thickness of coating and weldability the results are shown in table 1.
The preparation of comparative example 1 1L chemical plating liquid
20g Silver Nitrate is dissolved in the deionized water of 500ml, slowly adds ammoniacal liquor, generate precipitation, continue to add ammoniacal liquor until resolution of precipitate; Separately 100g Seignette salt is dissolved in the deionized water of 500mL; At room temperature, the silver ammino solution configuring is slowly added in potassium sodium tartrate solution, the cumulative volume that obtains chemical silvering solution is 1L.The operating procedure of chemical silvering is referring to embodiment 1, the stability of plating solution, thickness of coating and weldability the results are shown in table 1.
Stability, weldability and the thickness of coating of the plating solution of embodiment 5 embodiment 1-4, comparative example 1
Method for estimating stability is: get plating solution 2mL and be placed in quartz colorimetric utensil, use spectrophotometer to scan from 200-400nm, measure the absorbancy (A of the plating solution of just having prepared near 300nm
0), configure after the absorbancy (A) of 1,3,7,10,15 day, calculate absorbance situation over time, be designated as absorbancy rate of descent %=(A
0-A)/A
0, the results are shown in Table 1.
After silver plate to be plated is silver-plated, the measuring method of silver thickness is: first with chloroazotic acid, silver layer is dissolved, then, with the concentration of silver ions in Solution by Atomic Absorption Spectrophotometry, finally calculate thickness of coating by concentration of silver ions.The thicker weldability of coating is stronger.
Weldability testing method after silver plate electroplate to be plated is: the tin ball of Sn/0.5Cu is placed on silver-plated backing material plate, in the molten tin bath of 260 DEG C, heats 10s, judge and calculate the expansion size of tin ball, be designated as the rate of spread, the results are shown in Table 1.The rate of spread be greater than 85% for qualified, and the rate of spread more weldability is stronger.
The stability of table 1 silver plating liquid and the performance of silvering
(*: plating time is 20min)
Can find out by embodiment 1-4 and comparative example 1, use chemical silvering solution of the present invention can reach the object of chemical silvering within a short period of time, and there is good weldability.
Taking above-mentioned foundation desirable embodiment of the present invention as enlightenment, by above-mentioned description, relevant staff can, not departing from the scope of this invention technological thought, carry out various change and amendment completely.The technical scope of this invention is not limited to the content on specification sheets, must determine its technical scope according to claim scope.
Claims (3)
1. the application of a chemical silvering solution, it is characterized in that: described chemical silvering solution is made up of imidazolium chloride salt ionic liquid, silver salt and water, wherein, silver salt is silver chloride, the volumn concentration of imidazolium chloride salt ionic liquid is 10%-90%, the concentration range of silver salt is 0.001-0.1mol/L, and described chemical silvering solution is for silver-plated on copper, nickel or nickel-phosphor alloy sheet material.
2. the application of chemical silvering solution claimed in claim 1, is characterized in that: the volumn concentration of imidazolium chloride salt ionic liquid is 30%-80%, and the concentration range of silver salt is 0.01-0.05mol/L.
3. the application of chemical silvering solution claimed in claim 1, is characterized in that: the structural formula general formula of imidazolium chloride salt ionic liquid is,
In formula, R
1for CH
3, R
2for CH
2cH
3or CH
2cH
2cH
2cH
3.
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| CN106086834B (en) * | 2016-08-22 | 2018-11-13 | 西安建筑科技大学 | A method of preparing high corrosion-resistant Ni-P chemical deposits by adding ionic liquid |
| CN109338343B (en) * | 2018-09-26 | 2020-09-25 | 长沙理工大学 | Chemical silver plating solution and silver plating method |
| CN109560439A (en) * | 2018-11-12 | 2019-04-02 | 中国科学院电工研究所 | A kind of preparation method of high-temperature superconductor belt lacing |
| CN111620365A (en) * | 2019-02-28 | 2020-09-04 | 中国科学院化学研究所 | High-concentration silver halide solution, preparation method thereof and regeneration method of silver halide |
| CN115261833A (en) * | 2022-08-05 | 2022-11-01 | 深圳市天熙科技开发有限公司 | Chemical silver plating solution for printed circuit board, preparation method and chemical silver plating method |
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| CN101353184B (en) * | 2008-09-05 | 2010-09-01 | 重庆大学 | Method for degrading azoic dye waste water |
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| DE2052787A1 (en) * | 1969-10-30 | 1971-05-06 | Western Electric Co | Process for non-electrolytic gold plating |
| CN1786268A (en) * | 2005-12-15 | 2006-06-14 | 复旦大学 | Self assembly chemical silver plating method on non metal material surface |
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