CN1105397A - Plating method combined unelectrolysis and electric plating - Google Patents
Plating method combined unelectrolysis and electric plating Download PDFInfo
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- CN1105397A CN1105397A CN 94101775 CN94101775A CN1105397A CN 1105397 A CN1105397 A CN 1105397A CN 94101775 CN94101775 CN 94101775 CN 94101775 A CN94101775 A CN 94101775A CN 1105397 A CN1105397 A CN 1105397A
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Abstract
The electroplating technique for forming a metal film on the surface of cylindrical and corrugated workpieces, having the same lustre, appearance, anticorrosion nature and uniform adhesion as the plated planar workpiece features pre-treating the surface of workpiece before plating, non-electrolysis plating to the treated surface to make metal ions be educed from all the surface of workpiece to form a metallic film, electroplating the workpiece, and refining electrically.
Description
The present invention relates to the solution and coating method of electroless plating and plating and usefulness, relate in more detail when the processed raw material to different shape carries out plating, carry out pre-treatment, the condition of surface of this raw material is ready to, earlier metal ion is separated out on whole of this stock chart, lining then by electroless plating, form metallic membrane, then electroplate, carry out the solution and coating method that final precision work is handled then by known method.
It is remote to carry out galvanized history, though its purposes is divided into corrosion protection, decorates and use and industrial classification, no matter that class, used coating is all a lot, and platinum plating, gold and silver, copper, nickel, chromium, lead, tin etc. are arranged.
For example nickel plating has use single nickel salt-ammonium chloride-boric acid plating bath, at 20-30 ℃, with 0.5-1A/dm
2, carry out tarnish and electroplate, and carry out gloss plating etc. by single nickel salt-nickelous chloride-boric acid-brightening agent plating bath.
Recently, in various special solvent plating baths, electroplate, when carrying out different shape forming the strike plating method of flash plating film on the processed raw material surface, internal surface in tubular stock, the perhaps crooked depths of waveform shape raw material etc., produce the mobile variation of local current, and the insufficient position that switches on.Therefore cause the adherence of coating variation, metal ion can not fully be separated out, and makes this part can not form metallic film, the remaining situation that causes the matrix former state to expose.Because above-mentioned such position contacts with treatment solution in back step operation.The stripping of matrix impels the electroplate liquid deterioration, causes defectives such as matrix corrosion, and this just causes the remarkable variation of products appearance and solidity to corrosion certainly, and produce the defectiveness goods and increase, thus the low inferior fatal shortcoming of product percent of pass.
The objective of the invention is a kind of like this coating technology of exploitation, to eliminate the shortcoming of above-mentioned prior art, make cylindric and have on the processed raw material of special shapes such as waveform shape of curvature portion, form identical with common flat plate stock glossy, outward appearance is good, solidity to corrosion is good, tack is good even metallic film.
The applicant is for eliminating each shortcoming of prior art, by various experimental studies and go out the result, before electroplating, carry out electroless plating (electroless plating), precipitating metal on the whole faces in table, the lining of special special-shaped raw material, form after the even metal film, adopt common plating and precision work to handle again, obtained eliminating fully the result of existing each shortcoming, finish purpose of the present invention thereby reach.
The invention provides the solution and coating method of a kind of electroless plating and plating and usefulness, it is characterized in that: to tabular, cylindric, when the processed raw material of different shapes such as waveform shape carries out coating, carrying out pre-treatment earlier is ready to the condition of surface of processed raw material, under the situation of not using electric energy, pass through replacement(metathesis)reaction, metal ion in the aqueous metal salt is evenly precipitate into the table of above-mentioned processed raw material, in all surfaces on, to form metallic film, after having carried out this electroless plating, doing sensitization as required handles, then carry out common plating, do precision work at last and handle.
Above-mentioned processed raw material is with aluminium and alloy thereof, copper and close or iron and alloy thereof for well, in addition, the composition of above-mentioned electroless plating solution with three kinds of metal-salt and reductive agent and buffer reagents for well.
For example under the situation of the electroless plating (chemical plating) of nickel, as having of metal-salt: single nickel salt, nickelous chloride etc., as reductive agent is inferior sodium phosphate, Sodium Thiosulfate etc., have as buffer reagent in addition: sodium-acetate, boric acid, lactic acid, tartrate, Trisodium Citrate, sodium succinate etc., other also has the situation that contains various brightening agents.
In addition,, determine the composition of suitable plating bath, use acidic bath in the occasion of iron and alloy thereof etc. usually, then use alkali plating solution in nonmetal occasion as plastics by pilot study according to the material of processed raw material.
Secondly, about the concentration of metal ion, the plating bath of electroless plating is different with electroplate liquid, owing to metal ion is to be provided by this metal-salt, so be a important factor on the plating solution maintenance to the concentration adjustment of this metal-salt.
In addition, in the mother liquor of the important meals salt of formation plating bath reductive agent being arranged, naturally is important in the precipitation process of this metal.For example metal-salt with nickel salt reductive agent represent with following formula with the occasion of hypophosphite:
In the occasion of actually operating, the equivalence ratio of the two is not as above-mentioned reaction formula (1), and some differences are arranged.
As mentioned above, mainly use organic acid, also contain stablizer and brightening agent as buffer reagent.Mentioned reagent naturally and understandably has best ratio, is necessary it is fully adjusted in the coating operation.
In addition, the pH in the plating bath relevant with thickness of coating and tack is changed, the time, temperature etc. are necessary fully to control.
As mentioned above, in the occasion of electroless plating, the replenishing of reagent, the relation of the long-pending and plating bath capacity of finished surface, and bath life etc. is important on safeguarding, no longer narration.
Method of the present invention is in plating process, replaced strike plating method in the past, and to carry out electroless plating before the electroplating processes as feature, according to this scheme, metallic film can not only be formed and at the enterprising electroplating of this face on the whole faces of substrate, and the comprehensive outward appearance of goods is good, and solidity to corrosion improves simultaneously.
That is to say, after before plating, implementing the electroless plating processing, reached with strike plating and can not form film in the depths of fillet shape and processed raw material inner face of waveform shape and crooked position, in other words be exactly precipitating metal all on the whole faces with the plating bath contact part, owing to form metallic film, in back step operation, prevented the stripping of matrix in plating bath, in addition owing to improved energising, make distribution of current homogenizing more, the hiding power of electroplated film disk and tack are improved.
After above-mentioned electroless plating is handled, carry out sensitization as required and handle, electroplate according to the described known technology of above-mentioned prior art content then.
Embodiments of the invention below are described.
Embodiment
Embodiment 1
Fig. 1 shows the general flowchart according to method of the present invention Nickel Plating Treatment technology on aluminum substrate, by this figure the present invention is described.
At first carrying have the tabular aluminum substrate of waveform that joggling part divides under 60 ℃ in ア Le ヮ リ-Application 101(trade(brand)name) 50g/l(phosphoric acid salt 20g/l, carbonate 25g/l, tensio-active agent 5g/l) dipping carried out the alkali degreasing processing in 10 minutes during the degreasing that solution is formed was bathed, water cleans, follow under 40 ℃ in ァ Le サ ラ Application PRE(trade(brand)name) 300g/l(phosphoric acid 300g/l, additive 40g/l, nitric acid 200g/l) after dipping carried out etch handle for 90 second during the etch that bath is formed was bathed, water cleans, follow under 22 ℃ in サ Block ス -Zn-111(trade(brand)name) 500g/l(sodium hydroxide 140g/l, after dipping carried out zincate processing (tack is improved) in 30 seconds during the zincate that the bath of metallic zinc (38g/l) is formed was handled and bathed, water cleans, in the bath of nitric acid 500cc/l, flood again and carry out the zincate lift-off processing 20 seconds, carry out above-mentioned zincate once more and handle (22 ℃, 30 seconds), handle according to the following electroless plating that carries out then.
Consisting of of electroless plating body lotion: ト ッ Block ニ ュ ロ Application BL-M(trade(brand)name) 100cc/l, ト ッ Block ニ ュ ロ Application BL-l(trade(brand)name) 60cc/l(nickel salt 20g/l, hypophosphite 20g/l, additive (stablizer, brightening agent etc.) 20g/l).The bath temperature remains on 90 ℃ and carries out electroless plating processing in 13 minutes, makes the nickel plating film that forms thick 3 μ on whole faces of above-mentioned aluminum substrate.
Resulting product to straight crooked depths has plated film completely.
Then, because this nickel pellicular front is easy to unstable stateization, in order to improve tack, carrying out earlier the sensitization in 60 seconds in 10% sulfuric acid liquid handles, then will be by single nickel salt 280g/l, nickelous chloride 45g/l, boric acid 40g/l, brightening agent 1,15ml/l, brightening agent 2,0.75mg/l, the plating bath that the bath of pH4.2 is formed remains on 50 ℃, at cathode current density 3A/dm
2, anodic current density 1.5A/dm
2Condition under use pneumatic blending, carry out electroplating in 25 minutes, on the surface of aluminum substrate, form the nickel plating film of about 13 μ of thickness, then washing.
Resultant goods are not only at foraminate whole planar section, and all form uniform nickel plating film until the depths of curved part.
Then carry out chromium plating, plate as essence with this, thereby obtain end article by following condition.
The above is carried out after aluminum substrate after nickel is electroplated fully washes, reclaim with chromium and bathe actively, change processing 20 seconds, washing then, with anhydrous chromic acid 250g/l, trivalent chromium 1.6g/l, the chromium plating body lotion that the bath of sulfuric acid 2.3g/l is formed remains on 45 ℃, with cathode current density (DK) 20A/dm
2Condition electroplating processes 2 minutes, make the chromium thin film that forms 0.3 μ.Fully washing has been till chromium ion has been can not check in inspection, in 55 ℃ of dryings 6 minutes, obtains end article then.
Resulting product is glossy, and the color outward appearance that is chromium is fine, and tack and solidity to corrosion are good.
Embodiment 2
Pre-treatment → electroless plating → the electroplating technology that carries out is similarly to Example 1 handled, and obtains being formed with the aluminum substrate of gloss film, and this matrix is carried out white metal precision work by following condition, handles as precision work with this.
At first fully washing keeps then by stannous pyrophosphate 20g/l, cobalt chloride 20g/l, and potassium pyrophosphate 250g/l, brightening agent 10ml/l, the white metal plating bath that the bath of pH8.7 is formed are at 50 ℃, with cathode current density (DK) 0.7A/dm
2Condition under electroplating processes 3 minutes, the glossiness tin-cobalt that forms thickness and be 0.3 μ closes film, fully after the washing, carry out 30 second chromate treating, remake and improve solidity to corrosion and lucigenin processing treatment, again in 55 ℃ of drying treatment 8 minutes.
The end article solidity to corrosion of gained is good, though have the tone with the chromium color similarity, presents the good appearance of the uniqueness different with the chromic acid layer.
Embodiment 3
Carry out pre-treatment → electroless plating → electroplating technology according to the method identical, obtain being formed with the aluminum substrate of gloss nickel plating film, this matrix is deceived alloy precision work by following condition handle as precision work with embodiment 1.
After washing in advance, with stannous pyrophosphate 10g/l, cobalt chloride 30g/l, potassium pyrophosphate 320g/l, brightening agent 20ml/l, the black alloy plating bath that the bath of pH8.7 is formed remains on 50 ℃, is 10A/dm in cathode current density (DK)
2Condition under handled 2 minutes, make it to form black tin-cobalt-base alloy coating of thick 0.3 μ.Fully after the washing, carry out 30 second chromate treating, improve solidity to corrosion again and handle, 55 ℃ dry 6 minutes down.
Gained end article solidity to corrosion is good, presents unique fine appearance of black.
The present invention is as above-mentioned.Prior art can not reach the cylinder inner face and the crooked depths of ripple formboard forms metallic film, and among the present invention, with whole faces of the plating bath contact site of electroless plating on the precipitating metal ion, owing to form metallic film, matrix stripping and inner corrosion and variable color in bath in the back step operation have been prevented fully.Owing to the raising of energising property, distribution of current is homogenizing more in addition, thus improved the hiding power and the tack of electroplated film disk, thus significantly improved solidity to corrosion.
Have again,, can on the processed matrix face of different shape, be formed with gloss, outward appearance is good, solidity to corrosion is good even metallic film,, plate in vain and deceive smart plating such as plating, its effect is improved more again by carrying out chromium plating if use method of the present invention.
Method of the present invention also is applicable to the occasion of the various metals of plating on various processed raw materials, no longer narration.
Use method of the present invention on aluminum feedstock, to carry out the general flowchart of Nickel Plating Treatment technology among Fig. 1.
Claims (2)
1, the solution and coating method of electroless plating and plating and usefulness, it is characterized in that, in processed raw material coating to different shapes such as tabular, cylindric, waveform shapes, earlier processed raw material being carried out pre-treatment is ready to, under not using galvanized situation, pass through the replacement(metathesis)reaction of the metal ion in the aqueous metal salt then, carry out forming on the whole faces in table, lining at above-mentioned processed raw material the electroless plating of the metallic film of evenly separating out, carrying out sensitization then as required handles, carry out common plating again, do precision work at last and handle.
2, the solution and coating method of the described electroless plating of claim 1 and plating and usefulness, it is characterized in that, above-mentioned processed raw material is aluminium and aluminium alloy, copper and copper alloy, or iron and iron alloy, the plating bath of above-mentioned electroless plating is made up of for three kinds metal-salt, reductive agent and the buffer reagent that contains stablizer, brightening agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94101775 CN1105397A (en) | 1994-01-13 | 1994-01-13 | Plating method combined unelectrolysis and electric plating |
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| Application Number | Priority Date | Filing Date | Title |
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| CN 94101775 CN1105397A (en) | 1994-01-13 | 1994-01-13 | Plating method combined unelectrolysis and electric plating |
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| CN1105397A true CN1105397A (en) | 1995-07-19 |
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| CN 94101775 Pending CN1105397A (en) | 1994-01-13 | 1994-01-13 | Plating method combined unelectrolysis and electric plating |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347339C (en) * | 2002-01-30 | 2007-11-07 | 关东化学株式会社 | Non-electrolysis gold plating solution |
| CN102528025A (en) * | 2012-01-31 | 2012-07-04 | 南昌航空大学 | Method for preparing core-shell type copper-based alloy powder capable of resisting high-temperature oxidization |
| CN105567066A (en) * | 2016-02-04 | 2016-05-11 | 宁波格莱美厨具有限公司 | High-temperature-resistant abrasion-resistant non-stick pan coating, preparation method and non-stick pan with same |
| CN107119267A (en) * | 2017-06-29 | 2017-09-01 | 昆山福仕电子材料工业有限公司 | Surface of ceramic body chemical solution nickel plating process |
-
1994
- 1994-01-13 CN CN 94101775 patent/CN1105397A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100347339C (en) * | 2002-01-30 | 2007-11-07 | 关东化学株式会社 | Non-electrolysis gold plating solution |
| CN102528025A (en) * | 2012-01-31 | 2012-07-04 | 南昌航空大学 | Method for preparing core-shell type copper-based alloy powder capable of resisting high-temperature oxidization |
| CN105567066A (en) * | 2016-02-04 | 2016-05-11 | 宁波格莱美厨具有限公司 | High-temperature-resistant abrasion-resistant non-stick pan coating, preparation method and non-stick pan with same |
| CN107119267A (en) * | 2017-06-29 | 2017-09-01 | 昆山福仕电子材料工业有限公司 | Surface of ceramic body chemical solution nickel plating process |
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