CN1536100A - Environment-protecting catalytic liquor for chemically-plating copper, nikel and phosphorus three-element alloy and its preparation method - Google Patents
Environment-protecting catalytic liquor for chemically-plating copper, nikel and phosphorus three-element alloy and its preparation method Download PDFInfo
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- CN1536100A CN1536100A CNA031141242A CN03114124A CN1536100A CN 1536100 A CN1536100 A CN 1536100A CN A031141242 A CNA031141242 A CN A031141242A CN 03114124 A CN03114124 A CN 03114124A CN 1536100 A CN1536100 A CN 1536100A
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Abstract
The present invention relates to a liquid catalyst for treating surface of metal and plating copper-nickel-phosphorus three-element alloy on the special alloy. Said liquid catalyst is made up by using nickel sulfate, copper sulfate, sodium hypolinoleate, sodium citrate and ammonium acetate. Said invention also provides its preparation method, its process is simple, operation is convenient, said process does not pollute environment, and its coat is compact, and has high hardness, high wear resistance and high corrosion resistance.
Description
The present invention relates to the chemical catalysis effect, more particularly relate to a kind of ternary alloy catalytic liquid and preparation method thereof that is used on the special alloy of metallic surface.
Chemical plating nickel-phosphorus alloy has excellent solidity to corrosion and wear resisting property, has obtained using widely in engineering.But, to the component of some complex shape, service condition harshness, only adopt protection and the strengthening material of single electroless nickel alloy as the surface, be difficult to obtain good result of use sometimes.For adapting to performance demands under the relevant application conditions, in the chemical nickel plating phosphorus solution, add mantoquita, can produce the Ni-Cu-P ternary alloy.With Ni-P alloy phase ratio, chemical plating Ni-Gu-P ternary alloy layer has higher solidity to corrosion and electroconductibility.Therefore, be applied to chemical mechanical equipment, as on the part of pump, compressor as the anticorrosion antiwear tectum, can also be plated on metal or nonmetallic surface to increase electric conductivity.Also be widely used at aspects such as scrappy of electronics, precision instrument and instrument in addition.
Up to now, the processing that is used for the metallic surface has the whole bag of tricks, and as mechanical treatment, physics and chemical treatment, and there are various defectives in the chemical treatment metallic surface, as complex process, troublesome poeration, expensive device, raw material is expensive, the cost height, the plating piece surface is inhomogeneous, contaminate environment etc.
The object of the invention is to avoid above-mentioned weak point of the prior art, and provides a kind of technology simple, and easy to operate, catalytic liquid free from environmental pollution and preparation method thereof is used for the metallic surface special alloy.
Purpose of the present invention can reach by following measure: catalytic liquid is in 1000 parts water, contain by raw material and formed: single nickel salt 0.114mol/L-0.19mol/L with following weight ratio, copper sulfate 0.002mol/L-0.006mol/L, the sour sodium 0.142mol/L-0.236mol/L in inferior Asia, Trisodium Citrate 0.364mol/L-0.204mol/L, ammonium acetate 0.30mol/L-0.5mol/L;
Its preparation method:
(1) in coating bath, with 60 ℃ of warm water dissolving single nickel salts, the ammonium acetate stirring and dissolving of total amount 3/10;
(2) with other 3/10 60 ℃ of warm water dissolving copper sulfate, Trisodium Citrate, be stirred to dissolving fully after, pour into while stirring in (1);
(3) with 50 ℃ of warm water dissolving sodium hypophosphites of other 3/10, fully dissolve after-filtration, pour into while stirring before use in (1) and (2) mixed solution, dilute with 1/10 remaining water;
(4) transfer pH value to 6.5-8.5 with 25% ammonia soln.
Various raw material effects and the key issue that solved among the present invention:
1, single nickel salt
Single nickel salt (NiSO
46H
2O) concentration is to the influence of nickel, copper, phosphorus percentage composition in sedimentation velocity and the coating.The concentration of single nickel salt is big to the sedimentation velocity influence from 0.114mol/L to 0.152mol/L, but the influence from 0.152mol/L to 0.190mol/L is less.Along with the increase of concentration of nickel sulfate, the Ni percentage composition increases in the coating, and Cu, P percentage composition descend, and the downtrending of Cu content is bigger.
2, copper sulfate
Copper sulfate (CuSO
45H
2O) concentration is to the influence of sedimentation velocity.Along with concentration of copper sulfate increases, sedimentation velocity descends, and is slow from 0.002mol/L to 0.004mol/L downtrending, big to 0.006 downtrending from 0.004mol/L.Coating composition changes situation about occurring with concentration of copper sulfate in the plating bath, and Ni, P change slowly, and the Cu variation tendency is big.
3, sodium hypophosphite
Sodium hypophosphite (NaH
2PO
2H
2O) concentration is to sedimentation velocity and coating Ni, Cu, the influence of P percentage composition degree.Sodium hypophosphite is to the influence of sedimentation velocity, when sodium hypophosphite concentration is low influence less, it is big that sodium hypophosphite concentration influences trend when big.Influence to Ni, Cu, P in the coating is to Ni, P influence slowly, and influence changes bigger to Cu.
4, Trisodium Citrate
Sodium citrate concentration is to the influence of sedimentation velocity V, and sodium citrate concentration increases, and sedimentation velocity descends.Percentage composition influence to Ni, Cu, P in the coating changes bigger.
5, bath temperature
Bath temperature is to the influence of sedimentation velocity.Along with the rising of temperature, sedimentation velocity is pressed index law and is risen.This is consistent with general chemical reaction velocity and temperature relation, promptly meets Arrhenius law, and promptly reaction velocity constant and variation of temperature are closed and be:
K＝Ze-
△E/RT
Or
K in the formula---velocity constant;
Z---pre-exponential factor;
△ E---Apparent activation energy.
The inverse of logarithmic value and temperature by sedimentation velocity (thereby is tried to achieve the apparent activation energy △ E=47000kJ/mol of chemical plating Ni-Gu-P total reaction.
Plating temperature is influence to Coating composition.Along with the rising of temperature, the Ni composition slowly descends, and the P composition rises, and the Cu composition is with " △ " deformationization.
6, pH value
When pH value＜8.50, increase with the pH value, sedimentation velocity rises at straight line, and sedimentation speed increases hardly when ph＞8.50 above j.This is because when pH＜8.50, in bath system, increase with the pH value, free effectively nickel ion, copper ion concentration descends, the mixed oxidization ability drop of its Ni, Cu, the reducing power of sodium hypophosphite then sharply increases with the increase of pH value, total effect be that the sedimentation velocity straight line of electroless ni-cu-p alloy increases.In pH＜8.50 o'clock, because the pH value of plating bath is to regulate with ammoniacal liquor, free Ni, Cu ionic concn and amino molecule complexing in the plating bath, generation coordination ion [Ni (NH)
3]
6Cu (NH
3)
4Deng, effectively ionic concn reduces, and sedimentation velocity reduces.
The pH value of plating bath is to the influence of Coating composition.Increase with the pH value, the NiCu in the coating slightly increases, and the increase of pH value helps the carrying out that react.Influence to phosphorus content in the coating obviously descends.This phenomenon is consistent with general chemical plating Mi-P alloy, and the pH value increases, and is unfavorable for this reaction.
Now do further to analyze with regard to the weave construction and the advantage of electroless plating Ni-Cu-P alloy layer
1, differential thermal analysis
With regard to copper and mickel, their atomic radius only differs from 2.5%, it is 1 that valence electron number differs, and be all face-centred cubic structure, therefore they are easy to form unlimited solid-liquid body, and concerning nickel and phosphorus, the maxima solubility of phosphorus in nickel is 0.17%, phosphorus in the Ni-Cu-P coating has substantially exceeded the solubility limit of phosphorus in nickel, illustrates that the phosphorus super saturated solid solution is in the lattice of nickel.Therefore, the structure of plated state electroless plating Ni-Cu-P alloy layer is the supersaturation substitutional solid solution in the nickel lattice of copper, phosphorus atom.
The Ni-based supersaturated solid solution of cupric, phosphorus, it on thermodynamics a kind of unsure state, sosoloid will decompose during heating, in order to determine the crystallization process of Ni-Cu-P alloy layer weave construction, the plated state alloy is analyzed on differential thermal analyzer as can be seen, and amorphous deposit has a tangible exothermic peak in crystallization process.Rising, crystallization temperature with copper content increase gradually, illustrate that the adding of copper has not only increased the thermostability of chemical Ni-P plating amorphous layer.And help to stop diffusion and prevent crystallization.
2, X-ray diffraction analysis
Sample for avoiding oxidation, adopts protective atmosphere at constant temperature thermal treatment 2h such as 200,250,350,400 ℃.Sample under the plated state ° locates to present broad " steamed bun bag " shape diffraction peak in 2 θ=44.8 with X-ray diffraction analysis as can be known, and image does not change in the time of 200 ℃, illustrates that coating is non-crystallized under this temperature, still is non-crystalline state.After 300 ℃ of thermal treatments, " steamed bun bag " shape top comes to a point, but the peak do not disperse, and illustrating has under this temperature from non-crystalline state to the trend that crystalline state transforms, and promptly begins crystallization.
The permanent thermal treatment 2h of 350 ℃ of temperature, " steamed bun bag " shape becomes sharp-pointed and the dispersive diffraction peak is learnt according to the X ray data analysis at this moment, and Ni is arranged in the coating
3P, Cu
3P-compound and Ni elemental crystal form.Behind 400 ℃ of constant temperature thermal treatment of comparatively high temps 2h, Ni in its diffraction image
3P and Cu
3The diffraction peak that the P phase is produced is more sharp-pointed, and diffracted intensity increases, and this shows that lattice distortion this moment reduces the Ni that separates out
3P and Cu
3P quite grows up.
In a word, the crystalline structure of plated state Ni-Cu-P alloy layer is copper, the supersaturated solid solution of phosphorus atom in the nickel lattice, is the amorphous undefined structure.The lattice distortion of this sosoloid is bigger, is in the higher metastable condition of energy, therefore, when comparatively high temps thermal treatment, can change to the more stable weave construction of thermodynamics.
The performance of electroless ni-cu-p alloy and advantage
1, hard energy
Coating hardness is with the Changing Pattern of thermal treatment temp.The changes in hardness rule of Ni-Cu-P coating is similar substantially to Ni-P coating, and along with the raising of temperature, coating is transformed to crystalline state by non-crystalline state, and its hardness increases, promptly along with Ni
3P, Cu
3Separating out of P phase, coating hardness strengthens, and reaches maximum value in the time of 400 ℃.Along with temperature increases again, crystallization is progressively complete, Ni
3P, Cu
3Phase-plate such as P, Ni goes out, aggegation, and its hardness descends.
In from plated state to whole heat-treatment temperature range, the hardness value of Ni-Cu-P coating all is lower than Ni-P coating.This shows in the Ni-P alloy behind the adding copper, does not only make the nickel crystal obtain further solution strengthening, and simultaneously, the precipitation strength effect of Cu3P phase particle is also than Ni
3P phase matter is low.
2, porosity
Adopt and paste the porosity that filter paper method is measured the alloy layer of different compositions and different thickness, the result is shown in table 1-1.From table as can be seen, the Ni-Cu-P alloy layer is thick more, and porosity is more little, and the porosity of the alloy layer that phosphorus content is close depends primarily on the alloy layer copper content.Copper content is high more, and the alloy layer porosity is more little.
Table 1-1 Coating composition is to the influence of coating porosity
| Coating copper content/% (weight) | ????0.00 | ????8.48 | ????13.58 | ????26.86 | ????38.20 |
| Coating phosphorus content/% (weight) | ????5.83 | ????5.68 | ????3.91 | ????3.89 | ????1.61 |
| A 3 μ m thick layer porosity/cm -2 | ????26 | ????11 | ????7 | ????3 | ????0 |
| A 3 μ m thick layer porosity/cm -2 | ????36 | ????16 | ????14 | ????5 | ????2 |
3, solidity to corrosion
(1) in sulphuric acid soln
Alloy layer is at 10%H
2SO
4The relation of corrosion weight loss and dipping time in the solution, even in the harsh chemical corrosion environment of acidity, the solidity to corrosion of Ni-Cu-P alloy layer is still good more than Ni-P alloy degree layer; For the Ni-Cu-P alloy layer, under the close situation of phosphorus content, the coating copper content is high more, and solidity to corrosion is good more.In addition, find also by experiment that under this condition, the light of coating is after identical time corrosion, the loss of gloss of alloy layer weakens with the increase of its copper content.
(2) in sodium hydroxide solution
The Ni-Cu-P alloy layer of electroless plating and Ni-P alloy, Icr18Ni9Ti stainless steel are at 28 ℃, carry out the etch resistant properties test in the 50%NaOH corrosive medium, by test-results as can be seen, passivation phenomenon all takes place in three kinds of materials, but the passivation zone of transition has only appearred in Ni-P coating and Icr18Ni9Ti stainless steel, stable passivation region do not occur.
Therefore, in the 50%NaOH corrosive medium, corrosion stability the best of plated state electroless plating Ni-Cu-P alloy layer, the Ni-P alloy takes second place, and the 1Cr18Ni9Ti stainless steel is the poorest.The add-on of good solidity to corrosion of plated state electroless plating Ni-Cu-P and copper differs closely, and in this corrosion system, copper plays the anode unpolarizing, and the adding of amount of copper can promote the negative electrode passivation, generates stable passive film.
4, electric conductivity
The electric conductivity of coating is very important.Generally speaking, the copper content of coating is high more, and electric conductivity is also high more.The microhardness of coating is also relevant with electric conductivity and copper content, yet can not obtain the highest while electric conductivity of hardness is again the highest coating.
5, bonding force
Binding force of cladding material is one of key property of coating, and it is the prerequisite of giving the coating use properties, and therefore, the bonding force that improves coating has crucial meaning to its engineering application.Test-results shows that under suitable bottom composition and certain underlayer thickness, the double-deck coating of Ni-Cu-P/Ni-P has single-more excellent plated state bonding force of Ni-P coating, thereby shows, double-deck electroless plating is a kind of effective way of raising binding force of cladding material.
The factor that influences binding force of cladding material is a lot, but under the identical situation of processing condition such as pre-treatment, the character of coating internal stress then is the principal element that influences binding force of cladding material with size, internal stress with determination of x-ray coating, the even tensile stress of internal stress that shows plated state Ni-Cu-P and Ni-P coating, wherein the internal stress of Ni-Cu-P coating is+298MPa, and the internal stress of Ni-P coating is+348MPa, thus the bonding force of Ni-Cu-P coating higher be to have relatively low internal stress because of it.Because the size of internal stress is main relevant with the coefficient of expansion of coating, thereby can infer that the coefficient of expansion of Ni-Cu-P coating is little than Ni-P coating.
The key point of this catalytic liquid
Because the deposition potential calibration of copper is easy to replace the negative iron atom of current potential, and preferentially forms displacement copper at working-surface.Therefore, seek out the Ni-Cu-P alloy layer, at first should suppress to replace the generation of copper reaction.In addition,, be to realize the codeposition of nickel, cupric ion, also must make the deposition potential of copper in the plating bath, nickel two metal ions approaching from the codeposition Analysis on Mechanism of alloy.Obviously, both purposes are consistent, promptly all need reduce the deposition potential of copper, because the standard potential of nickel and iron is very close, so, as long as can make the deposition potential of copper, nickel two metal ions close, just not only can suppress to replace the generation of copper reaction, and can also realize the codeposition of copper, nickel ion.For this reason, in chemical plating fluid, add mantoquita and network agent Trisodium Citrate alive, can obtain the Ni-Cu-P alloy layer of good appearance quality.
The present invention is in the plating piece catalytic process, and it is quite big to the sedimentation velocity influence of plating that concern is to stablize pH value.If pH value is too high, then the hypophosphite reaction that is oxidized to phosphite is accelerated, and catalysis to change into chemical reaction be emitted response, make the very fast inefficacy of catalytic liquid.PH value is too low, and reaction then can't be carried out, even stops.Before the plating, best pH value should be 7.5.
Another key issue of the present invention is a temperature, and temperature is too high, and sedimentation velocity is accelerated, and makes the catalytic liquid instability; Temperature is too low, and sedimentation velocity slows down, and produces to become rusty, even does not plate.Therefore, in the plating process, necessarily keep relative working temperature, will prevent especially that catalytic liquid is local takes place overheatedly, in order to avoid cause adverse consequencess such as the serious self-decomposition of catalytic liquid or coating layering, optimum temps should be 80 ± 2 ℃ during plating.
The present invention has following advantage compared to existing technology:
1, do not need the applying direct current source device, plating piece does not have conductive contact, and is energy-conservation, free from environmental pollution.
2, coating densification, hole is few, all can get the alloy layer of uniform any surface finish at the internal surface in blind hole, pipe fitting, deep hole and slit.
3, be not subjected to that electric force lines distribution is uneven to be influenced,, can obtain the uniform coating of thickness yet, have good " emulation ", the not secondary ground finish of plating back geometrical shape and complicated special-shaped material plating piece.
4, have high rigidity and high-wearing feature.
5, have good erosion resistance, can keep out the etch of salt, alkali, ammonia and seawater.
6, technology is simple, and is easy to operate, do not need expensive and special equipment, and raw material is easily purchased inexpensive, and plating bath can recycle continuously.
Fig. 1 is the process flow sheet of catalytic treatment of the present invention:
The preliminary treatment of ternary alloy three-partalloy catalysis is the same with the preliminary treatment of plating, is a very important link, with later catalytic treatment quality direct relation is arranged. Degreasing and rust removal is not thorough, can cause that coating adhesion is poor, rough surface and be easy to come off. Particularly the quality of the performances such as the smooth program of coating, adhesion, wear-resisting erosion resistance is closely related especially with the quality of plating pre-treatment quality. Only have when occur between coating and matrix molecular separating force in conjunction with the time, the combination of coating and matrix is only firmly. Molecular separating force and intermetallic power only have that very little distance is interior just to be showed. Therefore, if matrix surface has very thin oil film or oxide-film, also can hinder the effect of molecular separating force and intermetallic power, thereby remove quite up hill and dale the lip-deep greasy dirt of each plated product, rust stain, oxide-film.
In Pre-treatment before plating technique, processing method commonly used has following several:
1, mechanical treatment: mechanical lapping and polishing are the mechanical processing process that leveling is processed to product surface---for various defectives such as the burr of removing the surface, sand holes, bubble, cut, corrosion trace, oxide-films, to improve the flatness on surface, to guarantee the finish quality of plating piece.
2, oil removal treatment: in order to guarantee the finish product strong bonded of good quality and coating and matrix is arranged, must before plating, remove the greasy dirt on plating piece surface. Deoiling method mainly is divided into alkaline solution oil removing and Solvent degreasing, and the alkaline solution oil removing is convenient and easy.
3, processing of rust removing: the metallic article surface derusting is commonly used chemical method. Chemical method rust cleaning is to carry out pickling with acid solution to process, and makes the rusty scale of product surface by chemical action, produces bubble hydrogen and mechanical stripping effect and be removed in the etch process.
4, activation process: activation process refers to low concentration strong acid the plating piece short time be soaked before plating, and then hot water cleans, and removes the oxide-film on plating piece surface, so that coating and matrix strong bonded.
Pretreated technic index is as follows:
(1), the light oil plating piece that gently becomes rusty adopts the two-in-one one-step method of pickling degreasing and derusting derust (normal temperature 3-8 minute) of deoiling.
(2) heavy oil heavily becomes rusty and then at first uses alkaline degreasing (water temperature 60-80 ℃, time 5-10 minute).
(3) the laggard hot water that enters to flow of oil removing rust cleans (water temperature 50-87 ℃, time 1-3 minute).
Six, example:
Under have with regard to an embodiment, the invention will be further described for the combined process flow process:
Embodiment 1
With a kind of coating bath of doing in three kinds in stainless steel, enamel or the plastics, with 60 ℃ of warm water dissolving single nickel salt 0.152mol, ammonium acetate 0.52mol of 300ml, solution stirring dissolving (1); With 60 ℃ of warm water dissolvings of 300 grams copper sulfate 0.004mol Trisodium Citrate 0.136mol, fully stir and make it dissolving thoroughly, be mixed solution (2) after filtration, (2) are poured in (1) mixed solution, generate the mixed solution of (1) and (2); With 50 ℃ of warm water dissolvings of 300 grams sodium hypophosphite 0.236mol, fully stir and make it thorough dissolving.Pour in the mixed solution of (1) and (2) after before use sodium hypophosphite liquid being filtered, the above-mentioned solution of remaining 100 gram dilutions is transferred PH to 7.5 with 25% ammoniacal liquor, is catalytic liquid.
The beaker that fills catalytic liquid is put in the water-bath of temperature regulating device and heated up, constant temperature transfers to 100 ℃, when treating that catalytic liquid rises to 80 ℃, will the plating piece after pre-treatment and activation put in the plating bath and get final product, controlled temperature and pH value are 7.5 closely, stir plating piece, sedimentation velocity 8-12 micron/hour, generally, pull plating piece out and be finished product through 30-60 minute.
Claims (4)
- Environmental-protecting chemical nickel plated copper phosphorus ternary alloy catalytic liquid and preparation method thereof, it is characterized in that: catalytic liquid is in 1000 parts water, contain by raw material and formed: single nickel salt 0.114mol/L-0.19mol/L with following concentration, copper sulfate 0.002mol/L-0.006mol/L, the sour sodium 0.142mol/L-0.236mol/L in inferior Asia, Trisodium Citrate 0.364mol/L-0.204mol/L, ammonium acetate 0.30mol/L-0.5mol/L;Its preparation method:(1) in coating bath, with 60 ℃ of warm water dissolving single nickel salts, the dissolving of acetic acid stirring ammonium of total amount 3/10;
- (2) with other 3/10 60 ℃ of warm water dissolving copper sulfate, Trisodium Citrate, be stirred to dissolving fully after, pour into while stirring in (1);
- (3) with 50 ℃ of warm water dissolving sodium hypophosphites of other 3/10, fully dissolve after-filtration, pour into while stirring before use in (1) and (2) mixed solution, dilute with 1/10 remaining water;
- (4) transfer pH value to 6.5-8.5 with 25% ammonia soln.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031141242A CN1536100A (en) | 2003-04-07 | 2003-04-07 | Environment-protecting catalytic liquor for chemically-plating copper, nikel and phosphorus three-element alloy and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA031141242A CN1536100A (en) | 2003-04-07 | 2003-04-07 | Environment-protecting catalytic liquor for chemically-plating copper, nikel and phosphorus three-element alloy and its preparation method |
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| CN100411740C (en) * | 2005-10-14 | 2008-08-20 | 中国电子科技集团公司第十八研究所 | Carried catalyst chemical plating method for hydrolyzing hydroborates to produce hydrogen |
| CN100353136C (en) * | 2006-01-20 | 2007-12-05 | 北京建筑工程学院 | Anti-corrosion copper condensing heat exchanger utilizing smoke heat energy, and manufacturing method thereof |
| CN101906626A (en) * | 2010-07-23 | 2010-12-08 | 中国矿业大学 | Scale-resisting ernary amorphous alloy and preparation method thereof |
| CN101906626B (en) * | 2010-07-23 | 2012-05-23 | 中国矿业大学 | Scale-resisting ernary amorphous alloy and preparation method thereof |
| TWI564432B (en) * | 2011-12-07 | 2017-01-01 | 富智康（香港）有限公司 | Aluminum article and method for making same |
| CN105970198A (en) * | 2016-06-30 | 2016-09-28 | 武汉鑫拓力工程技术有限公司 | Method for preparing multicomponent alloy clad layer spherical cap for support |
| CN105970198B (en) * | 2016-06-30 | 2018-08-03 | 武汉鑫拓力工程技术有限公司 | A kind of preparation method of multi-elements alloying coating spherical crown for bearing |
| CN110484899A (en) * | 2019-09-19 | 2019-11-22 | 东莞市通科电子有限公司 | A kind of chemical nickel-plating liquid and its nickel plating technology for electronic component pin nickel plating |
| CN113106431A (en) * | 2021-04-27 | 2021-07-13 | 山西智软科技有限公司 | Storage medium for heat assisted magnetic recording and preparation method thereof |
| CN113106431B (en) * | 2021-04-27 | 2023-03-28 | 深圳市优讯佳电子科技有限公司 | Storage medium for heat assisted magnetic recording and preparation method thereof |
| CN113802114A (en) * | 2021-09-16 | 2021-12-17 | 深圳市大正瑞地科技有限公司 | Lead-free environment-friendly chemical nickel solution and chemical nickel plating process using same |
| CN113802114B (en) * | 2021-09-16 | 2024-02-02 | 深圳市大正瑞地科技有限公司 | Lead-free environment-friendly chemical nickel solution and chemical nickel plating process using same |
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