CN101736327B - Palladium-free plastic chemical plating method for generating reductant film - Google Patents
Palladium-free plastic chemical plating method for generating reductant film Download PDFInfo
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- CN101736327B CN101736327B CN2010100192323A CN201010019232A CN101736327B CN 101736327 B CN101736327 B CN 101736327B CN 2010100192323 A CN2010100192323 A CN 2010100192323A CN 201010019232 A CN201010019232 A CN 201010019232A CN 101736327 B CN101736327 B CN 101736327B
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Abstract
The invention discloses a palladium-free plastic chemical plating method for generating reductant film. Reduction film-forming agent firstly generates a reductant film, and then nickel in waste liquid is reduced. The method of the invention has low cost, firm clad layer and simple technical process and can be suitable for palladium-free activation methods of different plastic base materials. The cost of compound activator used by the method of the invention is greatly lowered than that of palladium chloride activator adopted at present, and the properties such as radiance, the binding force and the like of the final plastic chemical plating are favorable.
Description
Technical field
The present invention relates to a kind of method of plastic chemical plating, particularly a kind of method that generates the palladium-free plastic chemical plating of reductant film.
Background technology
The widespread use of plastics, for people's life brings great convenience. but because the wear resisting property of plastics own is poor, non-conductive, yielding, its application has been subjected to certain restriction. and adopt the method for electroless plating for satisfied in particular cases to the requirement of plastics performance, plate layer of metal at frosting, improve the performance and the processing characteristics of plastics, make the range of application of plastics more extensive, the method for metallization of plastic surface is a lot, and the most frequently used method is an electroless plating at present.
The general technology process of electroless plating is on plastics: matrix oil removing-alligatoring-sensitization-activation-dispergation-electroless plating.Before several steps be surface treatment before the electroless plating, this is desired by the singularity of plastic basis material (as non-conductive, surperficial catalytically inactive is with the binding force of cladding material difference etc.).Reactivation process wherein is a very crucial step, and can the quality of activation effect is directly connected to electroless plating carry out, and whether coating is even, and whether coating and basal body binding force be up to standard etc.So-called activation is exactly to form the metallic particles with catalytic activity that one deck is discrete, be evenly distributed at matrix surface, thereby brings out follow-up electroless plating.
Electroless plating starts from chemical nickel plating at first, chemical nickel plating on non-conductor, and the general catalyzer that will on matrix, form one deck electroless plating earlier, traditional technology is to adopt PdCl
2-SnCl
2Activation-sensitizing.This process treatment process complexity, the PdCl2 of use costs an arm and a leg, and also has toxicity, makes its application be subjected to certain restriction.In order to save precious metal, reduce production costs, researcher has dropped into very big energy to the research of non-noble metal activating solution, obtained certain achievement, and there are many patent documentations to send out, but no-palladium activating technology is used in industrial production and is also had a lot of problems, and generally speaking not as good as precious metal, desired activation temperature is higher, the time is long etc. as activation effect.Up to the present, also there is not base metal activating process large-scale application in industrial production.
Palladium activation method in the electroless plating activating process is used early, and technology is also very ripe, has brought into play crucial effect in electroless plating industry.But compare with the palladium activation method of costliness, no-palladium activating technology cost is low, pollution is little, but still has many problems, as: the activation effect that has can not satisfy industrial needs not as palladium; The technology that has is too complicated, and the industrial production feasibility is not high.The ultimate principle of no-palladium activating is to generate the nickel Catalytic Layer on plastic basis material, utilizes the autocatalysis ability of nickel and realizes electroless plating.Japan has at first reported the activation solution that contains chitosan or its extension composition in the electron opaque material surface coated, utilizes the sequestering action of chitosan to palladium metal, forms active center on the collective surface.And the main technique of no-palladium activating liquid all is to form the nickel ion film on plastics collective surface earlier at present, collective is put in the reductive agent again.Such as Chinese patent application CN101067206A ABS plastic surface non-palladium activating treatment new technology and Chinese patent application CN101381865A: a kind of Xylo-Mucine huge legendary turtle is closed the surface of plastic matrix palladium-free activation process of absorbed Ni, its ultimate principle all is so, and just sequestrant is different different with some technologies.
Openly the patent and the patent application document of no-palladium activating technology have three at present, are respectively the surface of plastic matrix palladium-free activation process (CN101381865A) that the surperficial non-palladium activating treatment new technology (CN101067206A) of frosting no-palladium activating recipe for chemical nickel plating and technology (CN1772950C), a kind of ABS plastic, a kind of Xylo-Mucine huge legendary turtle are closed absorbed Ni.Below compare explanation respectively.
Patent CN1772950C is when activation, earlier plastic substrate is put into the nickelous acetate alcoholic solution, the sodium borohydride alcoholic solution is poured in the nickelous acetate alcoholic solution to activate again, and its ageing certain hour is got final product.Utilize sodium borohydride reduction to produce active nickel at normal temperatures, replace palladium activatory activation method with nickel and have cryogenic advantage.But there is certain deficiency in this invention aspect the recycling of activation solution.
Patent application CN101067206A and CN101381865A form the nickel ion film earlier on surface of plastic matrix, this method efficiently solves the solution recycling problem of patent CN1772950C.But see on the whole that the method for nickel ion film is some complexity also.Patent application CN101067206A will dispose complicated macromolecule film former earlier and carry out film forming, and the absorbed Ni ion reduces at last again, and operation, slightly complicated are also waited with oven dry in the centre.The patent application of CN101381865A has realized that effectively film forming and absorbed Ni ionic carry out simultaneously, has reduced operation steps, but but wants dry 30min～60min.
Summary of the invention
The objective of the invention is to overcome the defective of prior art, a kind of method that generates the palladium-free plastic chemical plating of reductant film is provided, utilization is reduced into film and generates reductant film earlier, again the nickel in the waste liquid is reduced, the inventive method is with low cost, coating is firm, and technical process is simple, applicable to the palladium-free activation process of different plastic basis materials; A kind of multiplicity reactivation liquid that the inventive method is used, its cost will be significantly less than the Palladous chloride activation solution of present employing, excellent propertys such as the luminance brightness of simultaneously final plastic chemical plating, bonding force.
The object of the invention is achieved through the following technical solutions:
A kind of method that generates the palladium-free plastic chemical plating of reductant film may further comprise the steps:
(1) will through electrochemical deoiling and roughening treatment plastic basis material oven dry, put into and be reduced in the film, leave standstill 15s～30s, the plastic basis material surface forms liquid membrane;
(2) base material is air-dry: above-mentioned film forming plastic basis material is air-dry, form solid film until surface of plastic matrix;
(3) generate active center: the plastic basis material after air-dry is put in the plating wastewater reaction 5～10s;
(4) electroless plating: the plastic basis material that step (3) is obtained takes out cleaning, puts into plating in the plating bath again.
The commonly used processing condition in described electrochemical deoiling, alligatoring and electroless plating selected technology field all can, preferred following condition:
Described electrochemical deoiling is that plastic basis material is put into temperature is that 50～70 ℃ the yellow soda ash and the mixing solutions of tertiary sodium phosphate soak 2～5min, and wherein the quality volumetric concentration of yellow soda ash is that the quality volumetric concentration of 25g/L, tertiary sodium phosphate is 25g/L.
Described alligatoring is that the plastic basis material behind the electrochemical deoiling is put into temperature is that 65～70 ℃ the chromic anhydride and the mixing solutions of the vitriol oil soak 10min, and wherein the quality volumetric concentration of chromic anhydride is 200g/L, and the volumetric concentration of the vitriol oil is 8000mL/L.
Described electroless plating is that the plastic basis material after handling is put into 65～72 ℃ of temperature, PH is that 5 plating bath carries out plating, wherein electroplate liquid formulation: single nickel salt 30g/L, inferior sodium phosphate 27g/L, Trisodium Citrate 20g/L, lactic acid 9g/L, Sodium dodecylbenzene sulfonate 0.0025g/L.
The described film that is reduced into is to prepare according to the following steps:
(1) be to be mixed into solvent in 1: 1～7: 3 by volume with methyl alcohol and ethanol;
(2) add sodium hydroxide, stir and make its dissolving;
(3) biphenyl, silane coupling agent and the sodium borohydride that adds again slowly stirs and makes its dissolving,
The add-on of above-mentioned substance is sodium hydroxide: 10g/L～20g/L with the ratio of solvent volume, biphenyl: 2g/L～5g/L, silane coupling agent: 5mL/L～8mL/L, sodium borohydride: 15～25g/L.
Weightmeasurement ratio 〉=the 3g/L of nickel compound in the described plating wastewater.
Described silane coupling agent comprises silane coupling agent KH-560.
The present invention is with respect to advantage and beneficial effect that prior art had:
1, no palladium technology.Palladium is as a kind of rare precious metal, and the characteristic of itself has just determined the limitation of palladium activation method to a great extent.The palladium activation at first is the cost that has greatly increased electroless plating, though Palladous chloride has long work-ing life, its high expense has improved the technology cost inevitably; Next is exactly to adopt the palladium activation method to consume a large amount of rare metal palladiums.
2, simplify the technical process of plastic chemical plating, greatly reduced the technology cost.At present usually the plastic chemistry depositing process that adopts is oil removing-alligatoring-sensitization-activation-dispergation-electroless plating, this technology stable higher, still but more complicated.The inventive method dispense with sensitization and dispergation, and need not any expensive device.
3, adopt plating wastewater to carry out corresponding activation.The plastics of the surface being coated reductive agent need not to drop in the plating bath, might cause labile factor to plating bath like that.We only need put into sample in the waste liquid that still contains nickel ion, just can restore one deck nickel metal particle at frosting well.
4, normal-temperature operation.Whole reactivation process of the present invention all is to realize at normal temperatures, simple and easy, easy row.
5, soak time is short.Whole reactivation process of the present invention just can be finished in the short period of time, and its natural air drying speed is crucial soon.
Description of drawings
Fig. 1 is whole technical process (wherein dashed rectangle is an activating process) of plastic chemical plating of the present invention;
Fig. 2 is surperficial metallurgical microscopic * 800 of embodiment 1 plastics;
Fig. 3 is surperficial metallurgical microscopic * 800 of embodiment 2 plastics
Embodiment
Streak test:
Form staggered grid in 10 road in length and breadth at a distance of 1mm quarter at sample surfaces, through a pull-up of 3M epistasis adhesive plaster, 5 times of magnifying glasses are observed down, do not have phenomenons such as decortication, foaming as coating, and it is qualified to be considered as.
High temperature impact method check binding force of cladding material:
This method is proposed by West Germany plastic electroplating worker association: be incubated 1h in 80 ± 5 ℃ high-temperature-hot-water, take out the back and soak 30s being no more than the cold water of putting into 5 ± 5 ℃ in the time of 30s, change over to again and be incubated 1h in the high-temperature-hot-water, through three loop cycles, do not have defectives such as bubble, decortication, a wrinkle as coating, it is qualified promptly to be considered as.
The luminance brightness test:
The appearance method judging criterion
One-level (minute surface light): coating surface is as bright as a sixpence, can clearly find out facial face and eyebrow.
Secondary (light) coating surface light can be found out facial face, but eyebrow some is fuzzy
Three grades (half light): coating surface is light a little a bit, does not see face.
Level Four (not having light): the coating surface tarnish, do not see face.
Surface Microstructure:
Adopt the metallography microscope visualizer that the coating surface microscopic pattern is observed, magnification is * 800.
Embodiment 1
It is that 50 ℃ the yellow soda ash and the mixing solutions of tertiary sodium phosphate soak 2min that the ABS plastic base material is put into temperature, carries out oil removing, and wherein the quality volumetric concentration of yellow soda ash is that the quality volumetric concentration of 25g/L, tertiary sodium phosphate is 25g/L; The plastic basis material behind the electrochemical deoiling being put into temperature is that 65 ℃ the chromic anhydride and the mixing solutions of the vitriol oil soak 10min again, carries out alligatoring, and wherein the quality volumetric concentration of chromic anhydride is 200g/L, and the volumetric concentration of the vitriol oil is 8000mL/L; To put into through the ABS plastic base material of oil removing and roughening treatment and be reduced into 15s in the film, this is reduced into film is in methyl alcohol and ethanol are 7: 3 composite solvents by volume, add respectively with the ratio of solvent volume be the sodium hydroxide of 20g/L, the falling agent biphenyl of 5g/L, sodium borohydride and the 5mL/L silane coupling agent KH-560 of 25g/L.Plastic basis material is film formation time 15s in being reduced into film, then natural air drying 10min.Then it is immersed into and contains NiSO
4Among the 5s, take out to clean and drop into plating 8min in the plating bath in the plating wastewater of 5g/L.Resulting coating luminance brightness is a secondary, and by metallography microscope observation (see figure 1), coating is smooth, and in conjunction with fine and close, bonding force is good.
Embodiment 2
It is that 70 ℃ the yellow soda ash and the mixing solutions of tertiary sodium phosphate soak 5min that the ABS plastic base material is put into temperature, carries out oil removing, and wherein the quality volumetric concentration of yellow soda ash is that the quality volumetric concentration of 25g/L, tertiary sodium phosphate is 25g/L; The plastic basis material behind the electrochemical deoiling being put into temperature is that 70 ℃ the chromic anhydride and the mixing solutions of the vitriol oil soak 10min again, carries out alligatoring, and wherein the quality volumetric concentration of chromic anhydride is 200g/L, and the volumetric concentration of the vitriol oil is 8000mL/L; To put into through the ABS plastic base material of oil removing and roughening treatment and be reduced into 30s in the film, this is reduced into film is in methyl alcohol and ethanol are 7: 3 composite solvents by volume, add respectively with the ratio of solvent volume be the sodium hydroxide of 10g/L, the falling agent biphenyl of 2g/L, sodium borohydride and the 5mL/L silane coupling agent KH-560 of 15g/L.Base material is film formation time 30s in being reduced into film, then natural air drying 10min.Then it is immersed into and contains NiSO
410s in the plating wastewater of 5g/L takes out to clean and drops into plating 8min in the plating bath.Resulting coating luminance brightness is a secondary, is better than embodiment 1, and by metallography microscope observation (see figure 2), coating is smooth, and in conjunction with fine and close, bonding force is good.
Embodiment 3
It is that 70 ℃ the yellow soda ash and the mixing solutions of tertiary sodium phosphate soak 5min that the ABS plastic base material is put into temperature, carries out oil removing, and wherein the quality volumetric concentration of yellow soda ash is that the quality volumetric concentration of 25g/L, tertiary sodium phosphate is 25g/L; The plastic basis material behind the electrochemical deoiling being put into temperature is that 70 ℃ the chromic anhydride and the mixing solutions of the vitriol oil soak 10min again, carries out alligatoring, and wherein the quality volumetric concentration of chromic anhydride is 200g/L, and the volumetric concentration of the vitriol oil is 8000mL/L; To put into through the ABS plastic base material of oil removing and roughening treatment and be reduced into 20s in the film, this is reduced into film is in methyl alcohol and ethanol are 1: 1 composite solvent by volume, add respectively with the ratio of solvent volume be the sodium hydroxide of 15g/L, the falling agent biphenyl of 2g/L, sodium borohydride and the silane coupling agent KH-5605mL/L of 20g/L.Base material is film formation time 20s in being reduced into film, then natural air drying 10min.Then it is immersed into and contains NiSO
410s in the plating wastewater of 5g/L takes out to clean and drops into plating 8min in the plating bath.Resulting coating luminance brightness is a secondary, and by metallography microscope observation, coating is smooth, and in conjunction with fine and close, bonding force is good.
Embodiment 4
It is that 60 ℃ the yellow soda ash and the mixing solutions of tertiary sodium phosphate soak 3min that the ABS plastic base material is put into temperature, carries out oil removing, and wherein the quality volumetric concentration of yellow soda ash is that the quality volumetric concentration of 25g/L, tertiary sodium phosphate is 25g/L; The plastic basis material behind the electrochemical deoiling being put into temperature is that 70 ℃ the chromic anhydride and the mixing solutions of the vitriol oil soak 10min again, carries out alligatoring, and wherein the quality volumetric concentration of chromic anhydride is 200g/L, and the volumetric concentration of the vitriol oil is 8000mL/L; To put into through the ABS plastic base material of oil removing and roughening treatment and be reduced into 15s in the film, this is reduced into film is in methyl alcohol and ethanol are 7: 3 composite solvents by volume, add respectively with the ratio of solvent volume be the sodium hydroxide of 20g/L, the falling agent biphenyl of 5g/L, sodium borohydride and the 5mL/L silane coupling agent KH-560 of 25g/L.Base material is film formation time 15s in being reduced into film, then natural air drying 10min.Then it is immersed into and contains NiSO
4Among the 5s, take out to clean and drop into plating 8min in the plating bath in the plating wastewater of 5g/L.Resulting coating luminance brightness is a secondary, and by metallography microscope observation (see figure 1), coating is smooth, and in conjunction with fine and close, bonding force is good.Resulting coating luminance brightness is three grades, and by metallography microscope observation, coating is smooth, and in conjunction with fine and close, bonding force is good.
Embodiment 5
Change plastic basis material, it is that 50 ℃ the yellow soda ash and the mixing solutions of tertiary sodium phosphate soak 2min that the PVC plastic basis material is put into temperature, carries out oil removing, and wherein the quality volumetric concentration of yellow soda ash is that the quality volumetric concentration of 25g/L, tertiary sodium phosphate is 25g/L; The plastic basis material behind the electrochemical deoiling being put into temperature is that 65 ℃ the chromic anhydride and the mixing solutions of the vitriol oil soak 10min again, carries out alligatoring, and wherein the quality volumetric concentration of chromic anhydride is 200g/L, and the volumetric concentration of the vitriol oil is 8000mL/L; To put into through the ABS plastic base material of oil removing and roughening treatment and be reduced into 15s in the film, this is reduced into film is in methyl alcohol and ethanol are 6: 3 composite solvents by volume, add respectively with the ratio of solvent volume be the sodium hydroxide of 20g/L, the falling agent biphenyl of 3g/L, sodium borohydride and the 8mL/L silane coupling agent KH-560 of 25g/L.Base material is film formation time 15s in being reduced into film, then natural air drying 10min.Then it is immersed into and contains NiSO
4Among the 6s, take out to clean and drop into plating 8min in the plating bath in the plating wastewater of 5g/L.Resulting coating luminance brightness is three grades, and by metallography microscope observation, coating is smooth, and in conjunction with fine and close, bonding force is good.
Claims (2)
1. method that generates the palladium-free plastic chemical plating of reductant film is characterized in that may further comprise the steps:
(1) will be through the oven dry of the plastic basis material of electrochemical deoiling and roughening treatment, put into and be reduced in the film, to leave standstill 15～30 seconds, the plastic basis material surface forms liquid membrane;
(2) base material is air-dry: above-mentioned film forming plastic basis material is air-dry, form solid film until surface of plastic matrix;
(3) generate active center: the plastic basis material after air-dry is put in the plating wastewater, reacted 5～10 seconds;
(4) electroless plating: reacted plastic basis material is taken out cleaning, put into plating in the plating bath again;
The described film that is reduced into is to prepare according to the following steps:
(1) be to be mixed into solvent in 1: 1～7: 3 by volume with methyl alcohol and ethanol;
(2) add sodium hydroxide, stir and make its dissolving;
(3) biphenyl, silane coupling agent and the sodium borohydride that adds again slowly stirs and makes its dissolving,
The add-on of above-mentioned substance is sodium hydroxide: 10g/L～20g/L with the ratio of solvent volume, biphenyl: 2g/L～5g/L, silane coupling agent: 5mL/L～8mL/L, sodium borohydride: 15～25g/L.
2. method according to claim 1 is characterized in that described silane coupling agent comprises silane coupling agent KH-560.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2010100192323A CN101736327B (en) | 2010-01-07 | 2010-01-07 | Palladium-free plastic chemical plating method for generating reductant film |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010100192323A CN101736327B (en) | 2010-01-07 | 2010-01-07 | Palladium-free plastic chemical plating method for generating reductant film |
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| CN101736327A CN101736327A (en) | 2010-06-16 |
| CN101736327B true CN101736327B (en) | 2011-08-17 |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102409320B (en) * | 2011-11-29 | 2015-02-25 | 沈阳工业大学 | Electroplating pretreatment method for acrylonitrile butadiene styrene (ABS) plastic surface |
| CN105586581B (en) * | 2016-03-04 | 2017-12-12 | 济南大学 | A kind of method in cement base piezoelectric composite material chemical nickel plating on surface |
| CN111763931A (en) * | 2020-07-15 | 2020-10-13 | 上海大学 | Preparation method of nickel-plated glass microspheres and product |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772950A (en) * | 2005-11-01 | 2006-05-17 | 桂林工学院 | No-palladium activating recipe for chemical nickel plating on plastic surface and its technological process |
| CN101067206A (en) * | 2007-06-06 | 2007-11-07 | 南开大学 | ABS plastic surface non-palladium activating treatment new technology |
| CN101126156A (en) * | 2007-06-06 | 2008-02-20 | 南开大学 | Technique used for ABS plastic substrate chemical plating pre-processing |
| CN101381865A (en) * | 2008-10-23 | 2009-03-11 | 中国人民解放军第二炮兵工程学院 | Palladium-free activation process for plastic substrate surface of nickel adsorbed sodium carboxymethylcellulose by chelating function |
-
2010
- 2010-01-07 CN CN2010100192323A patent/CN101736327B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1772950A (en) * | 2005-11-01 | 2006-05-17 | 桂林工学院 | No-palladium activating recipe for chemical nickel plating on plastic surface and its technological process |
| CN101067206A (en) * | 2007-06-06 | 2007-11-07 | 南开大学 | ABS plastic surface non-palladium activating treatment new technology |
| CN101126156A (en) * | 2007-06-06 | 2008-02-20 | 南开大学 | Technique used for ABS plastic substrate chemical plating pre-processing |
| CN101381865A (en) * | 2008-10-23 | 2009-03-11 | 中国人民解放军第二炮兵工程学院 | Palladium-free activation process for plastic substrate surface of nickel adsorbed sodium carboxymethylcellulose by chelating function |
Non-Patent Citations (2)
| Title |
|---|
| JP平1-222064A 1989.09.05 |
| JP昭63-195281A 1988.08.12 |
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