CN105112969A - Process for electroplating plastic on automobile mask - Google Patents
Process for electroplating plastic on automobile mask Download PDFInfo
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- CN105112969A CN105112969A CN201510607305.3A CN201510607305A CN105112969A CN 105112969 A CN105112969 A CN 105112969A CN 201510607305 A CN201510607305 A CN 201510607305A CN 105112969 A CN105112969 A CN 105112969A
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Abstract
The invention provides a process for electroplating plastic on an automobile mask. The process comprises the following steps: 1), oil removal; 2), expansion; 3), roughening; 4), reduction; 5), preimpregnation; 6), activation; 7), dispergation ; 8), copper replacement; 9), acid copper plating; 10), copper-tin alloy plating; 11), chrome plating ; 12), drying. The brand-new plastic electroplating process is provided through complete improvement on a whole conventional plastic electroplating process, the whole process is environment-friendly, non-toxic and harmless, chemical plating is not required to be used, the operation is easier, the process stability is improved, the wastewater treatment is simple, the production time is greatly shortened, a hanging tool is not required to be replaced in the production process, and the production efficiency is greatly improved.
Description
Technical field
The present invention relates to a kind of automobile face shield plastic electroplating technique.
Background technology
Plating (Electroplating) is exactly the process utilizing electrolysis principle to plate other metal or alloy of skim on substrate material surface, be utilize electrolytic action to make the technique of the surface attachment layer of metal film of metal or other material thus play to prevent burning (as corrosion), improve the effects such as wear resistance, electroconductibility, reflective, erosion resistance (copper sulfate etc.) and having improved aesthetic appearance.
Wherein, the body material of plating, except the cast iron of iron-based, steel and stainless steel, also has non-ferrous metal, or ABS plastic, polypropylene, polysulfones and phenoplast, electroplates, be namely referred to as plastic electroplating on plastic basis material surface.Plastic electroplating product has the advantages such as lightweight, easily processing, surface luster property and Surface flat are good, applies widely in automobile, motorcycle, five metals and daily houseware.
Plastic electroplating conventional process comprises two kinds: water power plating and vacuum plating.
Wherein, water power plates because technique is comparatively simple, and slave unit must be asked to environment does not all have vacuum ion plating harsh, thus is widely used.
At present, the plastic electroplating technique that Electroplate Factory is conventional comprises the steps:
Plastics plating piece → oil removing → alligatoring → reduction → preimpregnation → sensitization → activation → dispergation → electroless plating → acid copper-plating → plate half light nickel → bright nickel plating → nickel envelope → chromium plating → drying.
As China Patent Publication No. CN104499019A, disclose a kind of trolley part plastic electroplating method, its innovative point is: comprise and carry out electrochemical deoiling, alligatoring, reduction, preimpregnation, palladium activation, dispergation, chemical nickel plating, copper pre-plating, acid coppering, plating half light nickel, bright nickel plating, nickel envelope, chromium plating step successively.
Wherein, " plastics plating piece → oil removing → alligatoring → reduction → preimpregnation → sensitization → activation → dispergation → electroless plating " is called as the pre-treating technology of plastic electroplating, because plastics are a kind of nonconducting isolators, therefore directly can not carry out coating at frosting by one electroplating technology specification to be coated to, so before surface treatment, necessary pre-treatment should be carried out, to improve bonding force that coating is coated to and to be coated to the conductive substrate providing and there is good combination power for coating.
Wherein, electroless plating is mainly chemical nickel plating and/or electroless copper, electroless copper is a kind of high and cheap plastics Direct Electroplating method of efficiency, but, usually containing the reluctant complexing agent such as EDTA or trolamine in chemical bronze plating liquid, containing carcinogens formaldehyde, technology stability is poor, and coating easily produces pit.
In addition, electroless plating is on the impact of sensitization before, activation procedure operative technique.The object of sensitization, activation, is that one deck is uniform in order to make product surface be formed, continuous print, the catalysis " " center ", but the precious metal of this jelly particulate, has " induction " and act on when electroless copper or chemical nickel plating that has precious metal to form.But in existing conventional production practices, be difficult to the homogeneity and the continuity that ensure this layer of catalytic center, thus very easily form the defect of chemical plating.
And for the technical process of " acid copper-plating → plate half light nickel → bright nickel plating → nickel envelope → chromium plating " this part, be then called as electroplating technology.Wherein, in acid copper-plating process, because acid copper sulfate baths direct copper plating when electroplating replacement(metathesis)reaction can occur, cause the bonding force of plastic basis material and copper coating very poor.In order to obtain high-bond, present industrial widely used be alkaline cyanide electroplate liquid.But because prussiate has very large bio-toxicity, great environmental and social safety accident potential can be produced.And in " plating half light nickel → bright nickel plating → nickel envelope " process, can use a large amount of solution containing nickels, nickel has toxic to human body, carries out electroplating operations for a long time, can bring harm to workman's health.And in chrome-plating process, usually adopting hexavalent chromium solution as electroplate liquid, sexavalent chrome has high toxicity and carinogenicity, has serious harm to human body and environment; Sexavalent chrome is easy to be absorbed by the body, and it invades human body by digestion, respiratory tract, skin and mucous membrane.By in breathe air containing hoarse, the Atrophic nasal mucosas that have during the chromic trioxide of different concns in various degree, also can make perforation of nasal septum and bronchiectasis etc. time serious.Can cause vomiting when digestive tube invades, abdomen pain.Dermatitis and eczema can be produced when skin invades.Endanger maximum be long-term short term contact or suck time have carcinogenic danger.
For solving above-mentioned existing problems, the following patent documentation of current domestic existence:
China Patent Publication No.: CN104674314A, discloses a kind of gunmetal cyanide-free and nickel-free electroplating method, and the method comprises carries out electroless copper, non-cyanide copper electroplating, vitriol electro-coppering, cyanideless electro-plating gunmetal, Pb-free wave soldering chromium successively by body material; The electroplate liquid of non-cyanide copper electroplating is cupric pyrophosphate 10 ~ 20g/l, trisodium phosphate 230 ~ 280g/l; The electroplate liquid of cyanideless electro-plating gunmetal is potassium pyrophosphate 240 ~ 280g/l, cupric pyrophosphate 12 ~ 17g/l, sodium stannate 10 ~ 20g/l; The electroplate liquid of Pb-free wave soldering chromium is trivalent chromium 20 ~ 24g/l, boric acid 65 ~ 85g/l.Based on plated item carries out without phosphorus oil removing, chemical copper, non-cyanide pre-plating copper, acidiccopper plating, without cyanogen gunmetal, unleaded chromium plating, meet country to the requirement of setting up environment-protecting industrial and Intensive economy, and not containing carcinogenic substance in producing, reduce environmental pollution further.But this patent document simply show the correlation step technique in electroplating process, and to the pre-treatment before plating and electroless plating, all do not provide corresponding terms of settlement, and the plastic electroplating technique of Electroplate Factory comprises a whole set of flow process, only to the improvement of plating workshop section, the problem that existing plastic electroplating technique is brought fundamentally cannot be solved.
Summary of the invention
For solving above-mentioned Problems existing, the object of the present invention is to provide a kind of automobile face shield plastic electroplating technique, described technique, by the complete improvement to plastic electroplating whole set process, provides a set of brand-new plastic electroplating technique, whole technological process environmental protection, toxicological harmless, without the need to using electroless plating, operation is more prone to, and technology stability improves, wastewater treatment is simple, substantially reduce the production time, produce midway without the need to changing hanger, productivity improves greatly.
For achieving the above object, technical scheme of the present invention is:
A kind of automobile face shield plastic electroplating technique, comprises the steps:
1) oil removing
Carry out oil removal treatment to the automobile face shield plastic basis material surface of injection moulding, then carry out ultrasonic cleaning, then put into rinse bath clear water and rinse and clean, the degreaser that described oil removing adopts is that composition comprises the NaOH of 20 ~ 30g/L, the Na of 10 ~ 20g/L
2cO
3, 10 ~ 15g/L Na
3pO
412H
2the anionic polyacrylamide of O and 2 ~ 5g/L; Except oil temperature is 30 ~ 40 DEG C, oil removing time 5 ~ 10min;
2) expand
Plastic basis material after oil removing is sent in expansion slot and carries out expansion process, the amides plastic expansion agent containing 200 ~ 400g/L in expansion slot, temperature 40 ~ 50 DEG C, time 60 ~ 100s;
3) alligatoring
Plastic basis material is sent into alligatoring liquid bath and carry out roughening treatment, then put into rinse bath clear water water and rinse clean, Coarsening Temperature 70 ~ 75 DEG C, coarsening time 3 ~ 7min, in described alligatoring liquid bath, coarsening solution is high chromic acid content type coarsening solution, by 600 ~ 800g/LH
2sO
4, 50 ~ 100g/L CrO
3and the Pd of 10 ~ 20mg/L
2+add water to 1L to be mixed to form;
4) reduce
Plastic basis material after alligatoring is sent in reducing bath and carries out reduction treatment, put into rinse bath clear water after process to rinse, comprise the agent of 40 ~ 50g/L hydrazine hydrate reduction in reducing bath, the hydrochloric acid of 40 ~ 60g/L and the adjustment agent of 1g/L, reduction temperature is room temperature, recovery time 1 ~ 3min;
5) preimpregnation
Sent in pre-immersion trough by plastic basis material after reduction treatment and carry out preimpregnation, put into rinse bath clear water after preimpregnation and rinse, the presoak in pre-immersion trough is the hydrochloric acid of 200 ~ 250g/L, and temperature is room temperature, preimpregnation time 0.5 ~ 1min;
6) activate
Plastic basis material after preimpregnation is sent into activated bath and carries out activation treatment, put into rinse bath clear water after process and rinse, the activation solution in activated bath is Pd-Sn activation solution, and temperature is room temperature, soak time 10 ~ 15min;
7) dispergation
Plastic basis material after activation treatment is sent into dispergation groove and carries out dispergation process, put into rinse bath clear water after process and rinse, the solution glue in dispergation groove is the hydrochloric acid of 80 ~ 100g/L, temperature 30 ~ 40 DEG C, time 5 ~ 10min;
8) copper displacement
Plastic basis material after dispergation process is sent into copper displacement slot and carries out copper displacement, then put into rinse bath clear water to rinse, copper substitutional solution comprises: cupric chloride 5 ~ 10g/L, S-WAT 20 ~ 30g/L, rose vitriol 5 ~ 10g/L, novalgin 10 ~ 15g/L, sodium hydroxide 20 ~ 30g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium 5 ~ 15g/L; PH value 10 ~ 12, temperature 55 ~ 65 DEG C, time 15 ~ 30min;
9) acid copper-plating
Electroplate liquid comprises: content is the ethylene thiourea of the copper sulfate of 150 ~ 180g/L, 0.0020 ~ 0.0045g/L, the 2-mercaptobenzoimidazole of 0.0065 ~ 0.04g/L, the H of the NaOH of the HEDP of 50 ~ 80g/L, 30 ~ 40g/L, 40 ~ 50g/L
2sO
4, the Na of 10 ~ 15g/L
2sO
3, the deionized water of the HCl of 20 ~ 30g/L, 40 ~ 50g/L; Temperature of electroplating solution 20 ~ 40 DEG C, current density 1 ~ 2A/dm
2, pH value 6 ~ 8, electroplating time 10 ~ 15min;
10) bronze (copper-tin alloy) electroplating
Electroplate liquid comprises: potassium pyrophosphate 300 ~ 350g/L, cupric pyrophosphate 25 ~ 30g/L, phosphatase 11 ~ 5g/L, sodium stannate 10 ~ 20g/L, trolamine 1 ~ 5g/L, citric acid 0.5 ~ 2g/L; Bath pH values 8.5 ~ 9.5, electroplating voltage 1.5 ~ 2.5V, current density 4 ~ 5A/dm
2, electroplating temperature 20 ~ 30 DEG C, electroplating time 5 ~ 10min
11) chromium plating
Electroplate liquid comprises: concentration is the boric acid of the chromium sulphate of 20 ~ 30g/L, the potassium sulfate of 40 ~ 50g/L, the ammonium formiate of 10 ~ 15g/L, the ethynyl phenyl ketone of 0.5 ~ 1g/L, the alkylphenol polyoxyethylene of 0.5 ~ 1g/L, the acetic acid of 5 ~ 10g/L and 1 ~ 5g/L, and all the other are water; Temperature of electroplating solution 30 ~ 40 DEG C, pH value 3 ~ 4, current density 5 ~ 10A/dm
2, electroplating time 5 ~ 10min;
12) dry.
Further, described plastic basis material is Plating grade ABS plastic, and in this Plating grade ABS plastic, the mass percentage content of divinyl is 18 ~ 24wt%.
Separately, described adjustment agent is the NoviganthPA adjustment agent that Atotech Chemical Co., Ltd. produces.
Preferably, step 8) described in copper substitutional solution comprise: cupric chloride 6g/L, S-WAT 27g/L, rose vitriol 5g/L, novalgin 13g/L, sodium hydroxide 25g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium 15g/L.
Preferably, step 9) described in electroplate liquid comprise: content is the ethylene thiourea of the copper sulfate of 170g/L, 0.0025g/L, the 2-mercaptobenzoimidazole of 0.02g/L, the H of the NaOH of the HEDP of 50g/L, 40g/L, 50g/L
2sO
4, the Na of 13g/L
2sO
3, the deionized water of the HCl of 25g/L, 46g/L.
Preferably, step 10) described in electroplate liquid comprise: potassium pyrophosphate 340g/L, cupric pyrophosphate 26g/L, phosphatase 24 g/L, sodium stannate 16g/L, trolamine 3g/L, citric acid 1.5g/L.
Preferably, step 11) described electroplate liquid comprises: concentration is the boric acid of the chromium sulphate of 28g/L, the potassium sulfate of 46g/L, the ammonium formiate of 13g/L, the ethynyl phenyl ketone of 1g/L, the alkylphenol polyoxyethylene of 0.5g/L, the acetic acid of 10g/L and 3g/L, and all the other are water.
Separately having, step 6) described Pd-Sn activation solution comprises:
Component A:
PdCl
2: 1 ~ 5g/L, SnCl
22H
2o:2 ~ 3g/L, distilled water 200 ~ 300g/L, hydrochloric acid 50 ~ 100g/L;
B component:
SnCl
22H
2o:60 ~ 80g/L, Na
2snO
33H
2o:5 ~ 10g/L, hydrochloric acid: 150 ~ 200g/L.
Again, the preparation of described Pd-Sn activation solution comprises the steps:
A) component A preparation
By solid PdCl
2be dissolved in the mixed solution of hydrochloric acid and distilled water, under the condition of 25 ~ 35 DEG C, add SnCl
22H
2o, stirring reaction 10 ~ 15min;
B) B component preparation
By SnCl
22H
2o is added in hydrochloric acid, is stirred to and dissolves completely, then adds Na
2snO
33H
2o, makes white emulsion;
C) mix
By the B component prepared under continuous stirring, slowly pour in component A, rare to 1L, just obtain auburn sensitization activation solution, at 40 ~ 45 DEG C, be incubated 3h, obtain described Pd-Sn activation solution.
Beneficial effect of the present invention is:
After oil removing, before alligatoring, increase the expansion process to plastic basis material, with amides swelling agent, pre-roughening treatment is carried out to plastic basis material, increase plastic basis material surface-area, improve alligatoring effect, to improve integrity and the outward appearance of coating;
Design special coarsening solution, coarsening solution is long for duration of service, the roughening treatment time is short, do not need frequent adjustment, there is stronger alligatoring ability to Plating grade ABS plastic, the divinyl that chromic acid Main Function is oxidation ABS or contains in the ABS of PC, form anchor chalaza, frosting is made to generate more hydrophilic polar group, as=C=O ,-OH ,-SO
3h and-COOH etc., the existence of these groups, drastically increases the wetting ability of frosting, is conducive to Chemical bond, thus improves the bonding force of coating.And sulfuric acid can react with vinylbenzene, increase the bonding force of palladium;
Reduction operation mainly reduces the sexavalent chrome of frosting, prevent the plating solution of subsequent handling by hexavalent chromium polluted and cause degradation, particularly activate plating solution, add special adjustment agent, microetch is carried out to plastic basis material surface, make frosting charged, increase palladium adsorptive power, be conducive to the heavy palladium effect of subsequent activation operation palladium, make to be difficult to ABS or the PC plastics electroplated containing PC and be easy to plating, and after described NoviganthPA adjustment agent rinse water sodium hydroxide or calcium hydroxide neutralization precipitation, directly can be disposed to waste water treatment plant's process;
Adopt special Pd-Sn activation solution, make sensitization, activate and carry out in a step, use colloidal pd activation solution gained plating piece, in smooth finish, bonding force etc., not second to the situation of sensitization activation proceed step by step.Good stability, safeguard, use all more convenient, required operation simplifies greatly;
Abandon existing chemical plating technology, after dispergation process completes, directly carry out copper displacement, flow time shortens greatly, successfully avoid the drawback that electroless plating is brought, make that described technique conductivity is better, stability is stronger and cost is lower, design special copper substitutional solution, form one deck copper displacement conducting film on plastic basis material surface, plastic basis material can be conducted electricity, facilitate follow-up plating to carry out, improve the bonding force of electrolytic coating and plastic basis material;
In electroplating process, adopt gunmetal layer to replace existing plating half light nickel → bright nickel plating → nickel envelope operation, avoid the use of nickel, ensure that workman is healthy;
In the operation of decorative chromium plating, adopt trivalent chromium to replace traditional hexavalent chromium plating liquid, ensure that workman is healthy further.
Embodiment
Following examples for illustration of the present invention, but can not be used for limiting the scope of the invention.The implementation condition adopted in embodiment can be for further adjustments according to the condition of producer, and unaccounted implementation condition is generally conventional laboratory conditions.
A kind of automobile face shield plastic electroplating technique of the present invention, comprises the steps:
1) oil removing
Carry out oil removal treatment to the automobile face shield plastic basis material surface of injection moulding, then carry out ultrasonic cleaning, then put into rinse bath clear water and rinse and clean, the degreaser that described oil removing adopts is that composition comprises the NaOH of 20 ~ 30g/L, the Na of 10 ~ 20g/L
2cO
3, 10 ~ 15g/L Na
3pO
412H
2the anionic polyacrylamide of O and 2 ~ 5g/L; Except oil temperature is 30 ~ 40 DEG C, oil removing time 5 ~ 10min;
2) expand
Plastic basis material after oil removing is sent in expansion slot and carries out expansion process, the amides plastic expansion agent containing 200 ~ 400g/L in expansion slot, temperature 40 ~ 50 DEG C, time 60 ~ 100s;
3) alligatoring
Plastic basis material is sent into alligatoring liquid bath and carry out roughening treatment, then put into rinse bath clear water water and rinse clean, Coarsening Temperature 70 ~ 75 DEG C, coarsening time 3 ~ 7min, in described alligatoring liquid bath, coarsening solution is high chromic acid content type coarsening solution, by 600 ~ 800g/LH
2sO
4, 50 ~ 100g/L CrO
3and the Pd of 10 ~ 20mg/L
2+add water to 1L to be mixed to form;
4) reduce
Plastic basis material after alligatoring is sent in reducing bath and carries out reduction treatment, put into rinse bath clear water after process to rinse, comprise the agent of 40 ~ 50g/L hydrazine hydrate reduction in reducing bath, the hydrochloric acid of 40 ~ 60g/L and the adjustment agent of 1g/L, reduction temperature is room temperature, recovery time 1 ~ 3min;
5) preimpregnation
Sent in pre-immersion trough by plastic basis material after reduction treatment and carry out preimpregnation, put into rinse bath clear water after preimpregnation and rinse, the presoak in pre-immersion trough is the hydrochloric acid of 200 ~ 250g/L, and temperature is room temperature, preimpregnation time 0.5 ~ 1min;
6) activate
Plastic basis material after preimpregnation is sent into activated bath and carries out activation treatment, put into rinse bath clear water after process and rinse, the activation solution in activated bath is Pd-Sn activation solution, and temperature is room temperature, soak time 10 ~ 15min;
7) dispergation
Plastic basis material after activation treatment is sent into dispergation groove and carries out dispergation process, put into rinse bath clear water after process and rinse, the solution glue in dispergation groove is the hydrochloric acid of 80 ~ 100g/L, temperature 30 ~ 40 DEG C, time 5 ~ 10min;
8) copper displacement
Plastic basis material after dispergation process is sent into copper displacement slot and carries out copper displacement, then put into rinse bath clear water to rinse, copper substitutional solution comprises: cupric chloride 5 ~ 10g/L, S-WAT 20 ~ 30g/L, rose vitriol 5 ~ 10g/L, novalgin 10 ~ 15g/L, sodium hydroxide 20 ~ 30g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium 5 ~ 15g/L; PH value 10 ~ 12, temperature 55 ~ 65 DEG C, time 15 ~ 30min;
9) acid copper-plating
Electroplate liquid comprises: content is the ethylene thiourea of the copper sulfate of 150 ~ 180g/L, 0.0020 ~ 0.0045g/L, the 2-mercaptobenzoimidazole of 0.0065 ~ 0.04g/L, the H of the NaOH of the HEDP of 50 ~ 80g/L, 30 ~ 40g/L, 40 ~ 50g/L
2sO
4, the Na of 10 ~ 15g/L
2sO
3, the deionized water of the HCl of 20 ~ 30g/L, 40 ~ 50g/L; Temperature of electroplating solution 20 ~ 40 DEG C, current density 1 ~ 2A/dm
2, pH value 6 ~ 8, electroplating time 10 ~ 15min;
10) bronze (copper-tin alloy) electroplating
Electroplate liquid comprises: potassium pyrophosphate 300 ~ 350g/L, cupric pyrophosphate 25 ~ 30g/L, phosphatase 11 ~ 5g/L, sodium stannate 10 ~ 20g/L, trolamine 1 ~ 5g/L, citric acid 0.5 ~ 2g/L; Bath pH values 8.5 ~ 9.5, electroplating voltage 1.5 ~ 2.5V, current density 4 ~ 5A/dm
2, electroplating temperature 20 ~ 30 DEG C, electroplating time 5 ~ 10min
11) chromium plating
Electroplate liquid comprises: concentration is the boric acid of the chromium sulphate of 20 ~ 30g/L, the potassium sulfate of 40 ~ 50g/L, the ammonium formiate of 10 ~ 15g/L, the ethynyl phenyl ketone of 0.5 ~ 1g/L, the alkylphenol polyoxyethylene of 0.5 ~ 1g/L, the acetic acid of 5 ~ 10g/L and 1 ~ 5g/L, and all the other are water; Temperature of electroplating solution 30 ~ 40 DEG C, pH value 3 ~ 4, current density 5 ~ 10A/dm
2, electroplating time 5 ~ 10min;
12) dry.
Further, described plastic basis material is Plating grade ABS plastic, and in this Plating grade ABS plastic, the mass percentage content of divinyl is 18 ~ 24wt%.
Separately, described adjustment agent is the NoviganthPA adjustment agent that Atotech Chemical Co., Ltd. produces.
Separately having, step 6) described Pd-Sn activation solution comprises:
Component A:
PdCl
2: 1 ~ 5g/L, SnCl
22H
2o:2 ~ 3g/L, distilled water 200 ~ 300g/L, hydrochloric acid 50 ~ 100g/L;
B component:
SnCl
22H
2o:60 ~ 80g/L, Na
2snO
33H
2o:5 ~ 10g/L, hydrochloric acid: 150 ~ 200g/L.
Again, the preparation of described Pd-Sn activation solution comprises the steps:
A) component A preparation
By solid PdCl
2be dissolved in the mixed solution of hydrochloric acid and distilled water, under the condition of 25 ~ 35 DEG C, add SnCl
22H
2o, stirring reaction 10 ~ 15min;
B) B component preparation
By SnCl
22H
2o is added in hydrochloric acid, is stirred to and dissolves completely, then adds Na
2snO
33H
2o, makes white emulsion;
C) mix
By the B component prepared under continuous stirring, slowly pour in component A, rare to 1L, just obtain auburn sensitization activation solution, at 40 ~ 45 DEG C, be incubated 3h, obtain described Pd-Sn activation solution.
Wherein, in each embodiment of a kind of automobile face shield plastic electroplating technique of the present invention, the list of copper substitutional solution each component is as shown in table 1.In each embodiment of a kind of automobile face shield plastic electroplating technique of the present invention, in acid copper-plating electroplate liquid, each component list is as shown in table 2.In each embodiment of a kind of automobile face shield plastic electroplating technique of the present invention, the list of bronze (copper-tin alloy) electroplating electroplate liquid each component is as shown in table 3.In each embodiment of a kind of automobile face shield plastic electroplating technique of the present invention, in chromium plating electroplate liquid, each component list is as shown in table 4.
Table 1. (unit: ml/L)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Cupric chloride | 6 | 5 | 10 | 8 | 7 |
| S-WAT | 27 | 30 | 25 | 28 | 20 |
| Rose vitriol | 5 | 8 | 7 | 10 | 6 |
| Novalgin | 13 | 15 | 10 | 12 | 11 |
| Sodium hydroxide | 25 | 30 | 20 | 28 | 23 |
| 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium | 15 | 10 | 5 | 8 | 12 |
Table 2. (unit: g/L)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 |
| Copper sulfate | 170 | 180 | 160 | 150 | 175 |
| Ethylene thiourea | 0.0025 | 0.002 | 0.0030 | 0.0045 | 0.0035 |
| 2-mercaptobenzoimidazole | 0.02 | 0.01 | 0.0065 | 0.0087 | 0.04 |
| HEDP | 50 | 70 | 60 | 80 | 75 |
| NaOH | 40 | 35 | 38 | 33 | 30 |
| H 2SO 4 | 50 | 45 | 43 | 40 | 48 |
| Na 2SO 3 | 13 | 15 | 14 | 10 | 11 |
| HCl | 25 | 28 | 30 | 27 | 23 |
| Deionized water | 46 | 45 | 48 | 40 | 50 |
Table 3. (unit: g/L)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Potassium pyrophosphate | 340 | 300 | 330 | 350 | 310 |
| Cupric pyrophosphate | 26 | 28 | 25 | 30 | 27 |
| Phosphoric acid | 4 | 3 | 5 | 1 | 2 |
| Sodium stannate | 16 | 15 | 10 | 20 | 13 |
| Trolamine | 3 | 1 | 5 | 4 | 2 |
| Citric acid | 1.5 | 1 | 0.5 | 2 | 0.8 |
Table 4. (unit: part)
| Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | |
| Chromium sulphate | 28 | 25 | 20 | 23 | 30 |
| Potassium sulfate | 46 | 43 | 40 | 48 | 50 |
| Ammonium formiate | 13 | 15 | 11 | 10 | 12 |
| Ethynyl phenyl ketone | 1 | 0.8 | 0.5 | 0.6 | 0.9 |
| Alkylphenol polyoxyethylene | 0.5 | 0.7 | 0.8 | 1 | 0.6 |
| Acetic acid | 10 | 8 | 6 | 7 | 5 |
| Boric acid | 3 | 5 | 4 | 1 | 2 |
Adopt the plastic electroplating technique gained automobile face shield that various embodiments of the present invention provide, Deposit appearance is bright, smooth, fine and closely woven in vain, adopt cross-hatching and the bonding force of thermal shock method to trivalent chromium coating to test, test result shows that peeling, foaming phenomena do not appear in trivalent chromium coating, and bonding force is good.By subsides filter paper method test coating porosity, trivalent chromium layer thickness is 1 μm, and porosity is 0.05/cm
2.By electro-chemical test and CASS experiment, plastic electroplating technique provided by the present invention and comparative example and traditional sexavalent chrome technique are contrasted, the corrosion potential of chromium coating and corrosion electric current density contrast as shown in table 5.
Table 5. chromium coating corrosion potential and corrosion electric current density contrast
| Corrosion potential (E corr)/V | Corrosion electric current density (J corr)/μA·cm -2 | |
| Embodiment 1 | -0.205 | 0.089 |
| Embodiment 2 | -0.289 | 0.097 |
| Embodiment 3 | -0.276 | 0.088 |
| Embodiment 4 | -0.206 | 0.085 |
| Embodiment 5 | -0.235 | 0.091 |
| Comparative example | -0.387 | 1.562 |
| Hexavalent chromium plating | -0.309 | 1.031 |
Wherein, corrosion potential is higher, and the corrosion-resistant tendency of coating is better.Corrosion electric current density is lower, and the corrosion resistance of coating is stronger.Therefore, as seen from Table 5, in the embodiment of the present invention corrosion resistance of trivalent chromium coating apparently higher than comparative example and hexavalent chromium plating technique.
And various embodiments of the present invention gained trivalent chromium coating CASS experimental grade is up to 9 grades, suitable with the solidity to corrosion of traditional sexavalent chrome coating, can substitute sexavalent chrome coating completely, and solidity to corrosion is good.
It should be noted that, above embodiment is only in order to illustrate technical scheme of the present invention and unrestricted.Although with reference to preferred embodiment to invention has been detailed description, those of ordinary skill in the art is to be understood that, can modify to the technical scheme of invention or equivalent replacement, and not depart from the scope of technical solution of the present invention, it all should be encompassed in right of the present invention.
Claims (9)
1. an automobile face shield plastic electroplating technique, is characterized in that, comprise the steps:
1) oil removing
Carry out oil removal treatment to the automobile face shield plastic basis material surface of injection moulding, then carry out ultrasonic cleaning, then put into rinse bath clear water and rinse and clean, the degreaser that described oil removing adopts is that composition comprises the NaOH of 20 ~ 30g/L, the Na of 10 ~ 20g/L
2cO
3, 10 ~ 15g/L Na
3pO
412H
2the anionic polyacrylamide of O and 2 ~ 5g/L; Except oil temperature is 30 ~ 40 DEG C, oil removing time 5 ~ 10min;
2) expand
Plastic basis material after oil removing is sent in expansion slot and carries out expansion process, the amides plastic expansion agent containing 200 ~ 400g/L in expansion slot, temperature 40 ~ 50 DEG C, time 60 ~ 100s;
3) alligatoring
Plastic basis material is sent into alligatoring liquid bath and carry out roughening treatment, then put into rinse bath clear water water and rinse clean, Coarsening Temperature 70 ~ 75 DEG C, coarsening time 3 ~ 7min, in described alligatoring liquid bath, coarsening solution is high chromic acid content type coarsening solution, by 600 ~ 800g/LH
2sO
4, 50 ~ 100g/L CrO
3and the Pd of 10 ~ 20mg/L
2+add water to 1L to be mixed to form;
4) reduce
Plastic basis material after alligatoring is sent in reducing bath and carries out reduction treatment, put into rinse bath clear water after process to rinse, comprise the agent of 40 ~ 50g/L hydrazine hydrate reduction in reducing bath, the hydrochloric acid of 40 ~ 60g/L and the adjustment agent of 1g/L, reduction temperature is room temperature, recovery time 1 ~ 3min;
5) preimpregnation
Sent in pre-immersion trough by plastic basis material after reduction treatment and carry out preimpregnation, put into rinse bath clear water after preimpregnation and rinse, the presoak in pre-immersion trough is the hydrochloric acid of 200 ~ 250g/L, and temperature is room temperature, preimpregnation time 0.5 ~ 1min;
6) activate
Plastic basis material after preimpregnation is sent into activated bath and carries out activation treatment, put into rinse bath clear water after process and rinse, the activation solution in activated bath is Pd-Sn activation solution, and temperature is room temperature, soak time 10 ~ 15min;
7) dispergation
Plastic basis material after activation treatment is sent into dispergation groove and carries out dispergation process, put into rinse bath clear water after process and rinse, the solution glue in dispergation groove is the hydrochloric acid of 80 ~ 100g/L, temperature 30 ~ 40 DEG C, time 5 ~ 10min;
8) copper displacement
Plastic basis material after dispergation process is sent into copper displacement slot and carries out copper displacement, then put into rinse bath clear water to rinse, copper substitutional solution comprises: cupric chloride 5 ~ 10g/L, S-WAT 20 ~ 30g/L, rose vitriol 5 ~ 10g/L, novalgin 10 ~ 15g/L, sodium hydroxide 20 ~ 30g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium 5 ~ 15g/L; PH value 10 ~ 12, temperature 55 ~ 65 DEG C, time 15 ~ 30min;
9) acid copper-plating
Electroplate liquid comprises: content is the ethylene thiourea of the copper sulfate of 150 ~ 180g/L, 0.0020 ~ 0.0045g/L, the 2-mercaptobenzoimidazole of 0.0065 ~ 0.04g/L, the H of the NaOH of the HEDP of 50 ~ 80g/L, 30 ~ 40g/L, 40 ~ 50g/L
2sO
4, the Na of 10 ~ 15g/L
2sO
3, the deionized water of the HCl of 20 ~ 30g/L, 40 ~ 50g/L; Temperature of electroplating solution 20 ~ 40 DEG C, current density 1 ~ 2A/dm
2, pH value 6 ~ 8, electroplating time 10 ~ 15min;
10) bronze (copper-tin alloy) electroplating
Electroplate liquid comprises: potassium pyrophosphate 300 ~ 350g/L, cupric pyrophosphate 25 ~ 30g/L, phosphatase 11 ~ 5g/L, sodium stannate 10 ~ 20g/L, trolamine 1 ~ 5g/L, citric acid 0.5 ~ 2g/L; Bath pH values 8.5 ~ 9.5, electroplating voltage 1.5 ~ 2.5V, current density 4 ~ 5A/dm
2, electroplating temperature 20 ~ 30 DEG C, electroplating time 5 ~ 10min
11) chromium plating
Electroplate liquid comprises: concentration is the boric acid of the chromium sulphate of 20 ~ 30g/L, the potassium sulfate of 40 ~ 50g/L, the ammonium formiate of 10 ~ 15g/L, the ethynyl phenyl ketone of 0.5 ~ 1g/L, the alkylphenol polyoxyethylene of 0.5 ~ 1g/L, the acetic acid of 5 ~ 10g/L and 1 ~ 5g/L, and all the other are water; Temperature of electroplating solution 30 ~ 40 DEG C, pH value 3 ~ 4, current density 5 ~ 10A/dm
2, electroplating time 5 ~ 10min;
12) dry.
2. a kind of automobile face shield plastic electroplating technique according to claim 1, it is characterized in that, described plastic basis material is Plating grade ABS plastic, and in this Plating grade ABS plastic, the mass percentage content of divinyl is 18 ~ 24wt%.
3. a kind of automobile face shield plastic electroplating technique according to claim 1, is characterized in that, described adjustment agent is the NoviganthPA adjustment agent that Atotech Chemical Co., Ltd. produces.
4. a kind of automobile face shield plastic electroplating technique according to claim 1, is characterized in that, step 8) described in copper substitutional solution comprise: cupric chloride 6g/L, S-WAT 27g/L, rose vitriol 5g/L, novalgin 13g/L, sodium hydroxide 25g/L, 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid sodium 15g/L.
5. a kind of automobile face shield plastic electroplating technique according to claim 1, it is characterized in that, step 9) described in electroplate liquid comprise: content is the copper sulfate of 170g/L, the ethylene thiourea of 0.0025g/L, the 2-mercaptobenzoimidazole of 0.02g/L, the H of the NaOH of the HEDP of 50g/L, 40g/L, 50g/L
2sO
4, the Na of 13g/L
2sO
3, the deionized water of the HCl of 25g/L, 46g/L.
6. a kind of automobile face shield plastic electroplating technique according to claim 1, is characterized in that, step 10) described in electroplate liquid comprise: potassium pyrophosphate 340g/L, cupric pyrophosphate 26g/L, phosphatase 24 g/L, sodium stannate 16g/L, trolamine 3g/L, citric acid 1.5g/L.
7. a kind of automobile face shield plastic electroplating technique according to claim 1, it is characterized in that, step 11) described electroplate liquid comprises: concentration is the boric acid of the chromium sulphate of 28g/L, the potassium sulfate of 46g/L, the ammonium formiate of 13g/L, the ethynyl phenyl ketone of 1g/L, the alkylphenol polyoxyethylene of 0.5g/L, the acetic acid of 10g/L and 3g/L, and all the other are water.
8. a kind of automobile face shield plastic electroplating technique according to claim 1, is characterized in that, step 6) described Pd-Sn activation solution comprises:
Component A:
PdCl
2: 1 ~ 5g/L, SnCl
22H
2o:2 ~ 3g/L, distilled water 200 ~ 300g/L, hydrochloric acid 50 ~ 100g/L;
B component:
SnCl
22H
2o:60 ~ 80g/L, Na
2snO
33H
2o:5 ~ 10g/L, hydrochloric acid: 150 ~ 200g/L.
9. a kind of automobile face shield plastic electroplating technique according to claim 8, it is characterized in that, the preparation of described Pd-Sn activation solution comprises the steps:
Component A prepares
By solid PdCl
2be dissolved in the mixed solution of hydrochloric acid and distilled water, under the condition of 25 ~ 35 DEG C, add SnCl
22H
2o, stirring reaction 10 ~ 15min;
B component is prepared
By SnCl
22H
2o is added in hydrochloric acid, is stirred to and dissolves completely, then adds Na
2snO
33H
2o, makes white emulsion;
Mixing
By the B component prepared under continuous stirring, slowly pour in component A, rare to 1L, just obtain auburn sensitization activation solution, at 40 ~ 45 DEG C, be incubated 3h, obtain described Pd-Sn activation solution.
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| CN105603478A (en) * | 2016-03-23 | 2016-05-25 | 武汉诚盛电子有限公司 | Two-color electroplating technology of automobile ornament |
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| CN111962111A (en) * | 2020-08-04 | 2020-11-20 | 深圳市生利科技有限公司 | Mobile phone material containing cobalt alloy coating and preparation method thereof |
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| CN111501075A (en) * | 2020-05-06 | 2020-08-07 | 清远敏惠汽车零部件有限公司 | Plastic electroplating pretreatment process |
| CN111962111A (en) * | 2020-08-04 | 2020-11-20 | 深圳市生利科技有限公司 | Mobile phone material containing cobalt alloy coating and preparation method thereof |
| CN115261938A (en) * | 2022-05-07 | 2022-11-01 | 深圳市生利科技有限公司 | Butadiene-based plastic surface metallization process and application thereof |
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Application publication date: 20151202 |