CN102936742B - Method for electroplating black trivalent chromium on surface of plastic for vehicle decorating strip - Google Patents

Method for electroplating black trivalent chromium on surface of plastic for vehicle decorating strip Download PDF

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CN102936742B
CN102936742B CN201210440818.6A CN201210440818A CN102936742B CN 102936742 B CN102936742 B CN 102936742B CN 201210440818 A CN201210440818 A CN 201210440818A CN 102936742 B CN102936742 B CN 102936742B
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CN102936742A (en
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江民初
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Jiaxing Minhui Automotive Parts Co Ltd
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Jiaxing Minhui Automotive Parts Co Ltd
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Abstract

The invention provides a method for electroplating black trivalent chromium on the surface of plastic for a vehicle decorating strip. The method includes the steps of surface roughening processing, surface neutralizing processing, surface activating treatment, surface accelerated processing, chemical nickel precipitating, plating bottom nickel, plating acid copper, sequentially plating semi-bright nickel, full-bright nickel and microporous nickel and plating the black trivalent chromium. According to the method, the surface of a plastic workpiece is subjected to processes of ultrasonic grease removing, roughening, neutralizing, colloid palladium activating, accelerating and the like, the foundation is established for subsequently plating copper, nickel and finally the black trivalent chromium, the process is stable, and the formula is reasonable. Besides, when the formula is selected, a plating solution which has small influence on the environment is used as far as possible, and the electroplating process is environment-friendly.

Description

The method of the black chromium of a kind of automotive trim strip plastic surface plating trivalent
Technical field
The present invention relates to electroplating technology field, particularly relate to the method for the black chromium of a kind of automotive trim strip plastic surface plating trivalent.
Background technology
Electroplating black chromium is a kind of special plating in chromium plating system, and black chromium, in the chromic acid with strong oxidizing property, obtains the chromium metal of disperse in chromium sesquioxide hydrate through strong electron exchange.Chromium metal forms the coating of built-in type, and this coating is dendritic structure, and crystallization is loosened, and all absorbs, cause coating to be black to incident light wave.Because the stability of black chromium coating is high, be widely used in the Application Areass such as automobile component, opticinstrument, photographic apparatus, weaponry.
Have plating decorations sexavalent chrome and plating decorations trivalent chromium at plastic surface in prior art, but plating sexavalent chrome coating skewness, bonding force is looked into, to environmental protection and human health damage larger.Automotive trim strip plastic surface of the prior art adopts the chromic technique of plating, as Chinese patent application (publication number is: CN102242384A): relate to a kind of process for plating trivalent chromium on surfaces of plastic, this technique comprises the surperficial grease of removing, surface microscopic roughening treatment, reduction treatment, colloidal palladium activation, dispergation process, plating chemical nickel, plating watt nickel, plates the steps such as bright copper, bright nickel plating, plating trivalent chromium.Although this technique by repeatedly processing plastic surface thus reaching stable, the uniform effect of coating before plating trivalent chromium.But before plating trivalent chromium, plastic surface process is not in place, causes that coating covering power is poor, the easy embrittlement of coating, work-ing life are short.
Summary of the invention
Technical problem to be solved by this invention is, for the above-mentioned deficiency of prior art, proposes a kind of method that plating performance is better, coating is stablized, the automotive trim strip plastic surface of environmental protection electroplates the black chromium of trivalent.
The technical scheme that the present invention solves the employing of its technical problem is, propose the method for the black chromium of a kind of automotive trim strip plastic surface plating trivalent, the method comprising the steps of:
A, by automotive trim strip plastic cement at sodium hydroxide NaOH, sodium carbonate Na 2cO 3with water glass Na 2siO 3in mixing solutions, grease is removed in cleaning, immerses chromic trioxide CrO after removing grease 3with sulfuric acid H 2sO 4carry out surface coarsening process in mixed solution, then put into hydrochloric acid soln and carry out surface neutralization, after neutralization, adopt colloidal palladium solution to carry out surface activation process, then at sulfuric acid H 2sO 4carry out surface in solution and accelerate process;
B, by the plastic cement after above-mentioned surface treatment containing sulfuric acid nickel 2sO 4, inferior sodium phosphate Na 2pO 3with Trisodium Citrate C 6h 5na 3o 7mixing solutions in carry out chemical sinking nickel, then containing aqueous sulfuric acid nickel 2sO 4-7H 2o, moisture nickelous chloride NiCl 2-6H 2o, boric acid H 3bO 3plating bottoming nickel is carried out in mixing solutions;
C, the plastic cement after above-mentioned process is put into copper sulfate CuSO 4with sulfuric acid H 2sO 4in mixing solutions, carry out acid coppering process, then carry out plating half light nickel, full light nickel and microporous nickel successively, plate half light nickel, full light nickel is the same with the main component of microporous nickel plating solution, be aqueous sulfuric acid nickel 2sO 4-7H 2o, moisture nickelous chloride NiCl 2-6H 2o and boric acid H 3bO 3mixing solutions;
D, last at trivalent chromium base chromium sulphate Cr 2(SO 4) 3, stablizer H 2siF 4, wetting agent CH 3(CH 2) 11sO 3na, boric acid H 3bO 3the black chromium of trivalent is plated in mixing solutions.
As preferably, each constituent concentration in the degrease mixing solutions described in steps A: the concentration of sodium hydroxide NaOH is 20 ~ 35g/L, sodium carbonate Na 2cO 3concentration be 20 ~ 38g/L, water glass Na 2siO 3concentration be 55 ~ 93g/L.
Surface degrease step can know greasy dirt and other impurity of automotive trim strip plastic surface, impels surface coarsening even, improves binding force of cladding material.
As preferably, the concentration of each component in the surface coarsening process mixed solution described in steps A: chromic trioxide CrO 3concentration be 120 ~ 280g/L, sulfuric acid H 2sO 4concentration be 210 ~ 340g/L; Further preferably, chromic trioxide CrO 3concentration be 150 ~ 230g/L, sulfuric acid H 2sO 4concentration be 210 ~ 270g/L.
Chromic trioxide CrO 3be the main salt in plating solution, deposit chromium metal and production chromium sesquioxide hydrate etc. by the mechanism of oxidation-reduction reaction and electron exchange at automotive trim strip plastic surface, coating is turned black.Chromic trioxide CrO 3considerable influence is had, if chromic trioxide CrO to the covering power of plating solution 3content is high, then covering power is strong, and crystallization is careful, but if chromic trioxide CrO 3too high levels, then can make the hardness of coating decline.
In addition, chromic trioxide CrO 3with sulfuric acid H 2sO 4can at corrosion automotive trim strip plastic surface to form micro-roughened surface at automotive trim strip plastic surface as etching reagent, " snap close effect " required during to guarantee electroless plating, improves the bonding force of automotive trim strip plastic surface and coating with this.But sulfate radical can reduce the color characteristics of coating, coating is turned to be yellow, in order to can reach corrosion automotive trim strip plastic surface and reduce harmful effect simultaneously, need the content of accurately configuration sulfuric acid.
As preferably, the concentration of hydrochloric acid solution of the surperficial neutralizing treatment described in steps A is 18 ~ 68g/L.
Surface neutralizing treatment mainly removes the sexavalent chrome produced in surface coarsening treating processes, prevents hexavalent chromium polluted subsequent technique.
As preferably, the concentration of each component in the colloidal palladium solution of the surface activation process described in steps A: Palladous chloride PdCl 2concentration be 1.1 ~ 1.9g/L, tin protochloride SnCl 2concentration be 1.2 ~ 4.5g/L; Further preferably, Palladous chloride PdCl 2concentration be 1.4 ~ 1.7g/L, tin protochloride SnCl 2concentration be 3.1 ~ 4.5g/L.
In colloidal palladium solution, Palladous chloride is covered in automotive trim strip plastic surface, for follow-up chemical nickel provides catalytic center, the tin ion of tin protochloride then can be deposited on around palladium ion with the group of chemical combination state, avoid palladium ion be oxidized in water or in air and come off, the life cycle of colloidal palladium solution can be increased.
As preferably, the sulfuric acid H of process is accelerated on the surface described in steps A 2sO 4strength of solution is 25 ~ 82g/L.
Surface is accelerated process and is referred to and utilize sulfuric acid to remove in colloidal palladium solution the tin protochloride be coated on around palladium, is come out by palladium metal particle, makes subsequent chemistry sink nickel technique more smooth and easy.
As preferably, each concentration of component in the chemical sinking nickel mixing solutions described in step B: sulfuric acid nickel 2sO 4concentration be 15 ~ 28g/L, inferior sodium phosphate Na 2pO 3concentration be 23 ~ 32g/L, Trisodium Citrate C 6h 5na 3o 7concentration be 11 ~ 24g/L; Further preferably, sulfuric acid nickel 2sO 4concentration be 22 ~ 28g/L, inferior sodium phosphate Na 2pO 3concentration be 23 ~ 27g/L, Trisodium Citrate C 6h 5na 3o 7concentration be 11 ~ 24g/L.
Chemical sinking nickel refers to and deposit the thin conductive layer of one deck in the palladium metal that automotive trim strip plastic surface has catalytic activity, is convenient to the various metal of follow-up plating.
In chemical sinking nickel process, single nickel salt provides nickel element; Inferior sodium phosphate is strong reductant, and it is by the nickel ion (Ni in single nickel salt 2+) be reduced into metallic nickel; Trisodium Citrate is buffer reagent, and it makes the reaction of inferior sodium phosphate reduced nickel ion more mild.In the present invention, adopt Trisodium Citrate as buffer reagent, instead of existing boric acid, Trisodium Citrate is more friendly and cost is lower to environment, and by test of the present invention, the buffering energy of Trisodium Citrate is also better than boric acid, and this mainly because there is citric acid freely in Trisodium Citrate, can provide hydrogen ion and hydroxide ion.
As preferably, each concentration of component in the mixing solutions of the plating bottoming nickel described in step B: aqueous sulfuric acid nickel 2sO 4-7H 2the concentration of O is 87 ~ 120g/L, moisture nickelous chloride NiCl 2-6H 2the concentration of O is 5 ~ 84g/L, boric acid H 3bO 3concentration be 64 ~ 79g/L; Further preferably, aqueous sulfuric acid nickel 2sO 4-7H 2the concentration of O is 94 ~ 110g/L, moisture nickelous chloride NiCl 2-6H 2the concentration of O is 51 ~ 84g/L, boric acid H 3bO 3concentration be 68 ~ 72g/L.
In chemical sinking nickel, automotive trim strip plastic surface is made to cover the nickel dam of the conduction of layer by redox reaction; And in plating bottoming nickel, then adopt electrochemical method in chemical nickel, plate one deck nickel, strengthen the electroconductibility of coating further.In this step, aqueous sulfuric acid nickel 2sO 4-7H 2o, moisture nickelous chloride NiCl 2-6H 2o provides nickel ion needed for electrochemical reaction.
As preferably, each concentration of component in the mixing solutions of the acid coppering described in step C: copper sulfate CuSO 4concentration be 85 ~ 116g/L, sulfuric acid H 2sO 4concentration be 65 ~ 85g/L.Further preferably, copper sulfate CuSO 4concentration be 110 ~ 116g/L, sulfuric acid H 2sO 4concentration be 65 ~ 80g/L.
The object of acid coppering utilizes the characteristic of copper sulfate to improve luminance brightness and the planarization of automotive trim strip plastic surface, and can also improve the toughness of coating entirety.This is because copper coating compares nickel coating and other metal plating, its ductility is better, and after therefore plating sour layers of copper, toughness and the Surface flat of overall coating are improved.
Plating successively half light nickel described in step C, full light nickel and microporous nickel: plate in the processing step of half light nickel, full light nickel and microporous nickel, the main component of plating solution is the same, and the concentration of each component is: aqueous sulfuric acid nickel 2sO 4-7H 2the concentration of O is 150 ~ 240g/L, moisture nickelous chloride Nicl 2-6H 2the concentration of O is 55 ~ 85g/L, boric acid H 3bO 3concentration be 1 ~ 3g/L; Wherein plate plating solution in half light nickel step and be also added with butynediol additive, plate plating solution in full light nickel and be also added with saccharin sodium additives, in plating microporous nickel, plating solution is also added with 2-sulfonic group sodium phenyl aldehyde additive.
Plate half light nickel, full light nickel is the same with solution composition in microporous nickel, additive is different, thus makes the coating structure of formation different, makes each step all play different effects.Particularly, plate half light nickel and refer to the nickel dam plating one deck half light at automotive trim strip plastic surface, half light nickel coating is columnar structure, can improve the corrosion stability of coating; And this layer of electronickelling has good Surface flat and low porosity.Plate full light nickel and refer to the nickel dam plating one deck entire bright at automotive trim strip plastic surface, full light nickel coating is laminate structure, can improve the luminance brightness of coating.Plating microporous nickel refers to and plates one deck uniformly containing the coating of numerous non-conductive particulate at automotive trim strip plastic surface, can disperse corrosion current, reduce corrosion electric current density, improve coating erosion resistance further.
In addition, in plating half light nickel, full light nickel and microporous nickel step, stablizer all have employed boric acid but not Trisodium Citrate in chemical sinking nickel and plating bottoming nickel step.This is because more pay close attention to the covering power of coating and the compactness of coating when plating half light nickel, full light nickel and microporous nickel step, in chemical sinking nickel and plating bottoming nickel step, nickel coating mainly helps out.In the plating solution, boric acid can not only play the effect of stablizer plating solution, and can improve covering power and the covering power of plating solution, improves compactness of electroplating.Therefore choosing of boric acid needs comprehensive consideration environmental factors and it is to the reclamation element of coating.
As preferably, each concentration of component in the plating trivalent black chromium mixing solutions described in step D: trivalent chromium base chromium sulphate Cr 2(SO 4) 3concentration be 85 ~ 165g/L, stablizer H 2siF 4concentration be 25 ~ 55ml/L, wetting agent CH 3(CH 2) 11sO 3the concentration of Na is 5 ~ 65ml/L, boric acid H 3bO 3concentration be 15 ~ 35g/L.Further preferably, trivalent chromium base chromium sulphate Cr 2(SO 4) 3concentration be 120 ~ 150g/L, stablizer H 2siF 4concentration be 25 ~ 50ml/L, wetting agent CH 3(CH 2) 11sO 3the concentration of Na is 27 ~ 65ml/L, boric acid H 3bO 3concentration be 15 ~ 35g/L.
In the black chromium step of plating trivalent, stablizer H 2siF 4for forming stable compound with trivalent chromium, if too high can the impact of its concentration walks, if too low, easily there is blackstreak at coating surface or causing color and luster uneven; Wetting agent CH 3(CH 2) 11sO 3na can reduce liquid phase and solid phase surface tension, improve and walk; Boric acid uses as buffer reagent, can also take into account stabilizer function.Trivalent chromium base chromium sulphate Cr 2(SO 4) 3there is provided trivalent chromic ion, be different from existing hexavalent chromium, trivalent chromic ion has characteristic that is nontoxic, environmental protection.
The present invention is by art breading such as automotive trim strip plastic workpiece surface ultrasonic wave grease removal, alligatoring, neutralization, colloidal palladium activation and acceleration, and for follow-up electro-coppering, nickel and the black chromium of final trivalent lay the first stone process stabilizing, formula rationally.In addition, the present invention selects the plating solution little to environmental influence when filling a prescription and choosing as far as possible, makes electroplating technology more environmental protection.Further, the present invention also had the step of plating half light nickel, full light nickel and microporous nickel before the black chromium of final plating trivalent, and make the final coating formed more stable, color and luster is smooth, even, longer service life.
Embodiment
Be below that specific embodiments of the invention are further described technical scheme of the present invention, but the present invention is not limited to these embodiments.
Automotive trim strip plastic cement of the present invention comprises the automotive trim strip plastic workpiece that the materials such as all kinds of ABS, PC, PP, PVC, PET are made.
The method that above-mentioned automotive trim strip plastic workpiece is electroplated the black chromium of trivalent comprises the steps:
(1) surperficial degrease: at sodium hydroxide NaOH, sodium carbonate Na 2cO 3and Na 2siO 3clean in mixing solutions.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table one:
Table one
(2) surface coarsening process: at chromic trioxide CrO 3with sulfuric acid H 2sO 4carry out in mixed solution.In this step, chromic trioxide CrO 3with sulfuric acid H 2sO 4concentration proportioning is in different embodiments in table two:
Table two
(3) surperficial neutralizing treatment: the automotive trim strip plastic cement after surface coarsening process is put into hydrochloric acid soln and carries out.In this step, hydrochloric acid soln at the concentration proportioning of different embodiment in table three:
Table three
(4) surface activation process: surface activation process adopts colloidal palladium solution, colloidal palladium Chlorine in Solution palladium PdCl 2with tin protochloride SnCl 2at the concentration proportioning of different embodiment in table four:
Table four
(5) process is accelerated on surface: at sulfuric acid H 2sO 4carry out in solution.In this step sulphuric acid soln at the concentration proportioning of different embodiment in table five:
Table five
(6) chemical sinking nickel: containing sulfuric acid nickel 2sO 4, inferior sodium phosphate Na 2pO 3with Trisodium Citrate C 6h 5na 3o 7carry out in mixing solutions.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table six:
Table six
(7) bottoming nickel is plated: containing aqueous sulfuric acid nickel 2sO 4-7H 2o, moisture nickelous chloride NiCl 2-6H 2o, boric acid H 3bO 3mixing solutions in carry out.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table seven:
Table seven
(8) acid coppering: at copper sulfate CuSO 4with sulfuric acid H 2sO 4carry out in mixing solutions.Copper sulfate CuSO 4with sulfuric acid H 2sO 4at the concentration proportioning of different embodiment in table eight:
Table eight
(9) half light nickel, full light nickel and microporous nickel is plated successively.Plate in the processing step of half light nickel, full light nickel and microporous nickel, the main component of plating solution is the same, is aqueous sulfuric acid nickel 2sO 4-7H 2o, moisture nickelous chloride NiCl 2-6H 2o and boric acid H 3bO 3mixing solutions, but in the processing step of plating half light nickel, full light nickel and microporous nickel, the additive of different step is different.Plate half light nickel, full light nickel and the microporous nickel concentration proportioning in different embodiment respectively in table nine, table ten and table ten one.
Table nine (plating half light nickel)
Table ten (plating full light nickel)
Table ten one (plating microporous nickel)
(10) the black chromium of trivalent is plated: at trivalent chromium base chromium sulphate Cr 2(SO 4) 3, stablizer H 2siF 4, wetting agent CH 3(CH 2) 11sO 3na, boric acid H 3bO 3carry out in mixing solutions.In this step, in mixing solutions, each component concentration proportioning is in different embodiments in table ten two:
Table ten two
Through all smooth exquisiteness of trivalent black chromium plating color of the automotive trim strip plastic surface that embodiment 1 to embodiment 5 obtains, there is not the phenomenon that variegated, colourity is uneven.And this coating is stable, firmly, work-ing life is longer.Further, the trade effluent environmental pollution that the inventive method produces is less, environmental protection and reduce the cost of factory's back segment process trade effluent.
Specific embodiment described herein is only to the explanation for example of the present invention's spirit.Those skilled in the art can make various amendment or supplement or adopt similar mode to substitute to described specific embodiment, but can't depart from spirit of the present invention or surmount the scope that appended claims defines.

Claims (6)

1. a method for the black chromium of automotive trim strip plastic surface plating trivalent, the method comprising the steps of:
A, by automotive trim strip plastic cement at sodium hydroxide NaOH, sodium carbonate Na 2cO 3with water glass Na 2siO 3in mixing solutions, grease is removed in cleaning, immerses chromic trioxide CrO after removing grease 3with sulfuric acid H 2sO 4carry out surface coarsening process in mixed solution, then put into hydrochloric acid soln and carry out surperficial pickling, adopt colloidal palladium solution to carry out surface activation process after pickling, then at sulfuric acid H 2sO 4carry out surface in solution and accelerate process;
B, by the plastic cement after above-mentioned surface treatment containing sulfuric acid nickel 2sO 4, inferior sodium phosphate and Trisodium Citrate C 6h 5na 3o 7mixing solutions in carry out chemical sinking nickel, then containing aqueous sulfuric acid nickel 2sO 47H 2o, moisture nickelous chloride NiCl 26H 2o, boric acid H 3bO 3plating bottoming nickel is carried out in mixing solutions; In described chemical sinking nickel mixing solutions, each component and concentration thereof are: sulfuric acid nickel 2sO 4concentration be 15 ~ 28g/L, the concentration of inferior sodium phosphate is 23 ~ 32g/L, Trisodium Citrate C 6h 5na 3o 7concentration be 11 ~ 24g/L;
C, the plastic cement after above-mentioned process is put into copper sulfate CuSO 4with sulfuric acid H 2sO 4in mixing solutions, carry out acid coppering process, then carry out plating half light nickel, full light nickel and microporous nickel successively, plate half light nickel, full light nickel is the same with the main component of microporous nickel plating solution, be aqueous sulfuric acid nickel 2sO 47H 2o, moisture nickelous chloride NiCl 26H 2o and boric acid H 3bO 3mixing solutions; In the processing step of described plating half light nickel, full light nickel and microporous nickel, each component of plating solution and concentration thereof are: aqueous sulfuric acid nickel 2sO 47H 2the concentration of O is 150 ~ 240g/L, moisture nickelous chloride Nicl 26H 2the concentration of O is 55 ~ 85g/L, boric acid H 3bO 3concentration be 1 ~ 3g/L; Wherein plate plating solution in half light nickel step and be also added with butynediol additive, plate plating solution in full light nickel and be also added with saccharin sodium additives, in plating microporous nickel, plating solution is also added with 2-sulfonic group sodium phenyl aldehyde additive;
D, last at trivalent chromium base chromium sulphate Cr 2(SO 4) 3, stablizer H 2siF 4, wetting agent CH 3(CH 2) 11sO 3na, boric acid H 3bO 3the black chromium of trivalent is plated in mixing solutions; Each component in described plating trivalent black chromium mixing solutions and concentration thereof are: trivalent chromium base chromium sulphate Cr 2(SO 4) 3concentration be 85 ~ 165g/L, stablizer H 2siF 4concentration be 25 ~ 55ml/L, wetting agent CH 3(CH 2) 11sO 3the concentration of Na is 5 ~ 65ml/L, boric acid H 3bO 3concentration be 15 ~ 35g/L.
2. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1, is characterized in that: in the degrease mixing solutions described in steps A, each component and concentration thereof are: the concentration of sodium hydroxide NaOH is 20 ~ 35g/L, sodium carbonate Na 2cO 3concentration be 20 ~ 38g/L, water glass Na 2siO 3concentration be 55 ~ 93g/L.
3. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1 and 2, is characterized in that: in the surface coarsening process mixed solution described in steps A, each component and concentration thereof are: chromic trioxide CrO 3concentration be 120 ~ 280g/L, sulfuric acid H 2sO 4concentration be 210 ~ 340g/L.
4. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1 and 2, is characterized in that: in the colloidal palladium solution of the surface activation process described in steps A, each component and concentration thereof are: Palladous chloride PdCl 2concentration be 1.1 ~ 1.9g/L, tin protochloride SnCl 2concentration be 1.2 ~ 4.5g/L.
5. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1, is characterized in that: in the mixing solutions of the plating bottoming nickel described in step B, each component and concentration thereof are: aqueous sulfuric acid nickel 2sO 47H 2the concentration of O is 87 ~ 120g/L, moisture nickelous chloride NiCl 26H 2the concentration of O is 5 ~ 84g/L, boric acid H 3bO 3concentration be 64 ~ 79g/L.
6. the method for the black chromium of automotive trim strip plastic surface plating trivalent according to claim 1, is characterized in that: in the mixing solutions of the acid coppering described in step C, each component and concentration thereof are: copper sulfate CuSO 4concentration be 85 ~ 116g/L, sulfuric acid H 2sO 4concentration be 65 ~ 85g/L.
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