CN111893463A - Surface adjustment process for improving palladium adsorption performance of surface of electroplating-grade plastic part - Google Patents
Surface adjustment process for improving palladium adsorption performance of surface of electroplating-grade plastic part Download PDFInfo
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- CN111893463A CN111893463A CN202010766750.5A CN202010766750A CN111893463A CN 111893463 A CN111893463 A CN 111893463A CN 202010766750 A CN202010766750 A CN 202010766750A CN 111893463 A CN111893463 A CN 111893463A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 118
- 239000004033 plastic Substances 0.000 title claims abstract description 78
- 229920003023 plastic Polymers 0.000 title claims abstract description 78
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 59
- 238000000034 method Methods 0.000 title claims abstract description 41
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 38
- 230000008569 process Effects 0.000 title claims abstract description 37
- 238000009713 electroplating Methods 0.000 claims abstract description 15
- 230000004913 activation Effects 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 10
- 239000000084 colloidal system Substances 0.000 claims abstract description 9
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- 230000007547 defect Effects 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000003814 drug Substances 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000000465 moulding Methods 0.000 claims abstract description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 58
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 229910052759 nickel Inorganic materials 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000006386 neutralization reaction Methods 0.000 claims description 11
- 238000007747 plating Methods 0.000 claims description 10
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004327 boric acid Substances 0.000 claims description 9
- 238000007788 roughening Methods 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 6
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 6
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 6
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 239000011651 chromium Substances 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 238000005282 brightening Methods 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 claims description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical group [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 3
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 3
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 3
- 239000000945 filler Substances 0.000 claims description 3
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 claims description 3
- 150000002500 ions Chemical group 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004094 surface-active agent Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005238 degreasing Methods 0.000 claims description 2
- 230000003750 conditioning effect Effects 0.000 claims 3
- 238000004458 analytical method Methods 0.000 abstract description 3
- 230000009466 transformation Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 7
- 239000004417 polycarbonate Substances 0.000 description 7
- 230000009467 reduction Effects 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 230000003213 activating effect Effects 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000003562 lightweight material Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910000861 Mg alloy Inorganic materials 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910000797 Ultra-high-strength steel Inorganic materials 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000012938 design process Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229920006351 engineering plastic Polymers 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
- C23C18/30—Activating or accelerating or sensitising with palladium or other noble metal
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
- C25D5/14—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium two or more layers being of nickel or chromium, e.g. duplex or triplex layers
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/54—Electroplating of non-metallic surfaces
- C25D5/56—Electroplating of non-metallic surfaces of plastics
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Chemically Coating (AREA)
Abstract
The invention belongs to the field of plastic electroplating, and particularly relates to a surface adjustment process for improving palladium adsorption performance on the surface of an electroplating-grade plastic part. The surface adjusting process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part specifically comprises the following steps: the method has the advantages that the ethylenediamine with a certain concentration is added in the plastic electroplating pretreatment process through water washing to adjust the surface of the plastic part after coarsening, so that the adsorption efficiency of active palladium on the surface of the plastic part is improved, particularly the adsorption efficiency of the PC plastic surface on an active palladium colloid is improved, and the defect of poor leakage molding of a product is effectively overcome. The surface adjusting process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part is simple to realize and high in operability. Need not hardware transformation, the teaching agent liquid medicine only need add in any one washing before palladium activation the inside add can, the tank liquor need not heat, need not filter etc. extra operation, only need once only add fluting concentration before the open line can continuously use need not daily analysis and extra not add, regular replacement can.
Description
Technical Field
The invention belongs to the field of plastic electroplating, relates to an electroplating pretreatment process of a plastic electroplated part, and particularly relates to a surface adjustment process for improving the palladium adsorption performance of the surface of an electroplating-grade plastic part.
Background
In the automobile industry, automobile decorative part products need to meet the market requirements of light weight, environmental protection, energy conservation and low cost while meeting the luxurious and beautiful effect of automobile decoration. To achieve market goals, modern automotive products have the following main features: (1) the proportion of the various materials used in automobiles is changing and, although steel materials are now dominating, the main trend is that the amount of plastics and composites used will increase considerably. The proportion of cast iron to medium and low strength steel will be gradually reduced, the combination of lightweight material technology and the design and manufacturing process of automobile products will be closer, and the automobile body structure will tend to the direction of multi-component materials. (2) The development and utilization of special materials for environment-friendly energy automobiles and functional materials are continuously strengthened. The reduction of the self weight of the automobile is one of effective measures for reducing the emission of the automobile and improving the fuel efficiency. The fuel consumption can be reduced by about 6% to 8% for every 10% reduction in the own weight of the automobile. The data show that the self weight of foreign cars is reduced by 20-26% compared to the early stage, and as a long-term strategic goal, the self weight of cars will continue to decrease. The development and application of light-weight materials such as aluminum, magnesium alloy, engineering plastics, composite materials, high-strength steel, ultrahigh-strength steel and the like can play an important role in the light-weight problem of automobiles, and the reduction of the weight of automobile bodies can reach 20% in the next 10 years. (3) The plastic and the composite material thereof are important light materials, which not only can reduce the mass of parts by about 40 percent, but also can correspondingly reduce the purchasing cost by about 40 percent. In recent years, the usage amount of plastic materials in automobiles is rapidly increased, and according to statistics, the usage amount of plastic materials in each automobile reaches 105kg in 2000 in the world on average, and accounts for about 8-12% of the total weight of the automobile. For decades, in view of energy conservation and consumption reduction, developed countries have been accelerating the steps of light weight and plastification of automobiles, and the amount of plastics for each automobile is taken as a mark of automobile modernization and technological progress. The plastic electroplating is applied to the front grille, the handle, the decorative strip, the interior trim, the dial plate decoration, the gearbox, the wave stick, the wheel shell cover, the hub cover and other parts, and plays a great role in the aspects of vehicle body light weight and cost reduction. Foreign automotive interior parts have been mainly plated with plastics, and the application range is spreading from interior parts to exterior parts. The traditional plastic electroplating-main process comprises: chemical degreasing, hydrophilization, coarsening, neutralization, presoaking, sensitization, dispergation, chemical nickel, acid activation, nickel preplating, copper, chromium and nickel electroplating. The prior art has poor applicability to plastic parts with high PC content, and causes high scrapping ratio of product plastic leakage defects. Particularly, for structural special workpieces, the quality of products with high PC content is unstable. Therefore, the research focus is on the problem of improving the palladium adsorption performance on the surface of the electroplating-grade plastic part. In conclusion, it is very important to research a surface tuning process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part.
Disclosure of Invention
The invention provides a surface adjustment process for improving the palladium adsorption performance of the surface of an electroplating-grade plastic part, aiming at solving the problems that the poor defect is prominent and the product quality is restricted caused by the plastic leakage of a product due to the pretreatment failure of the electroplating-grade plastic part with high PC content (higher than 50%) in the traditional roughening process. According to the process, ethylenediamine with a certain concentration is added in the plastic electroplating pretreatment procedure through water washing to adjust the surface of the plastic part after roughening, so that the adsorption efficiency of active palladium on the surface of the plastic part is improved, especially the adsorption efficiency of the active palladium colloid on the surface of PC plastic is improved, and the defect of poor plastic leakage of the product is effectively overcome.
In order to achieve the above object, the present invention adopts the following technical solutions.
A surface adjustment process for improving palladium adsorption performance on the surface of an electroplating-grade plastic part specifically comprises the following steps: the method has the advantages that the ethylenediamine with a certain concentration is added in the plastic electroplating pretreatment process through water washing to adjust the surface of the plastic part after coarsening, so that the adsorption efficiency of active palladium on the surface of the plastic part is improved, particularly the adsorption efficiency of the PC plastic surface on an active palladium colloid is improved, and the defect of poor leakage molding of a product is effectively overcome.
Further, the surface adjusting process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part is carried out at room temperature.
Further, the surface adjusting process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part lasts for 60 s.
Further, according to the surface adjusting process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part, the concentration of the ethylenediamine is 3-10 mL/L.
A plastic electroplating process specifically comprises the following steps.
1. Chemical oil removal:
the upper-hanging finished whole flying bar workpiece product is immersed into a chemical oil removing groove station, and the operating conditions are oil removing groove parameter control: (1) ultrasonic treatment at 50 ℃; (2) the time is 1 minute; (3) the components are chemical oil removal powder with the concentration of 10 g/L.
2. And (3) hydrophilic:
after the hanger which is completely filled with the plastic part and is cleaned by water, the hanger is immersed into the hydrophilic tank, and the hydrophilic tank controls parameters: temperature: room temperature, treatment time: 10s-30s, and the liquid medicine comprises the following components: 50-100mL of sulfuric acid, surfactant: 1mL/L, and the surface of the product is adjusted to be beneficial to the smooth and new-in of the coarsening of the surface of the product.
3. Coarsening:
directly immersing the product subjected to hydrophilic treatment into a roughening tank solution, wherein specific roughening tank control parameters are as follows: (1) the temperature is 63-70 ℃; (2) the coarsening treatment time is 6-16 min; (3) the main components are as follows: chromic anhydride: 350-440g/L, and 320-430 g/L.
4. Neutralizing:
and fully cleaning the surface of the coarsened product by multi-connection washing, and transferring the product to a neutralization station through a traveling crane, wherein the neutralization station meets the treatment requirement, and hexavalent chromium residues which are not thoroughly cleaned are treated. The neutralization station control parameters are as follows: (1) the time is 30s-90s, (2) the temperature is room temperature, and (3) the component reducing agent: 40 mL/L.
5. Adjusting:
after the product is immersed in the adjusting process, the surface of the plastic part is adjusted, so that the best adsorption performance is achieved and preparation is made for subsequent palladium precipitation. The parameter requirements are as follows: (1) the temperature is room temperature, (2) the running is carried out for 5-60s, and (3) the main component of the regulator is ethylenediamine with the concentration of 3-10 mL/L.
6. Pre-dipping:
before the product enters palladium activation, the product needs to be soaked in a hydrochloric acid solution, so that the surface acidity of the product is ensured, and the concentration of diluted palladium activation is avoided. The presoaking control parameters (1) temperature is room temperature, (2) time is 60s, and (3) HCL concentration is 30-200 mL/L.
7. Activating palladium:
the palladium is present in colloidal form. A layer of palladium colloid is uniformly adsorbed on the surface of the plastic part, so that the subsequent chemical nickel can react on the surface of the product. Specific control parameters are as follows: (1) concentration: 10-35ppm of palladium, 320mL/L of hydrochloric acid 240-.
8. And (3) gel releasing:
transferring the activated product to a dispergation station to enable the colloidal palladium on the surface of the product to exist in an ion form, wherein the specific operation conditions are as follows: (1) the temperature is 50 ℃, the time is 2-5min, (2) the sulfuric acid is 5-10 mL/L.
9. Chemical nickel:
chemical nickel control parameters: (1) concentration: controlling the ratio of metal nickel to metal sodium to metal nickel, wherein the ratio of metal nickel to metal nickel: 12-18g/L, pH 7.8-9; (2) the time is 6-18 min; (3) the temperature is 25-40 ℃.
10. Acid activation:
(1) the bath solution is 0.05% sulfuric acid solution, (2) temperature: room temperature, (3) time: 5-20 s.
11. Pre-nickel plating:
(1) concentration control of nickel sulfate: 180-250g/L, nickel chloride: 40-50g/L of boric acid and 40-45g/L of boric acid; (2) the temperature is controlled at 50 ℃, and (3) the pH value is 3.6-4.8.
12. Acid copper:
(1) the main components are as follows: copper sulfate: 160-220g/L, 60-70g/L sulfuric acid, 0.2-0.8mL/L filling agent and 0.5-2.0mL/L brightening agent; (2) the temperature is 20-30 ℃; (3) stirring with air.
13. Nickel plating:
(1) the main components are as follows: nickel sulfate: 230-280g/L, 40-50g/L of nickel chloride, 40-50g/L of boric acid, and the amount of a cylinder opening agent: 5-10mL/L of brightener 0.2-0.5m L/L; (2) the temperature is 50-58 ℃; (3) the pH value is 3.8-4.4.
14. And (3) chromium plating:
(1) concentration control chromic acid: 180-320g/L, 0.8-3g/L sulfuric acid; (2) the temperature is 38-45 ℃; (3) the time is 5-8 min.
The beneficial effects of the invention are as follows.
According to the surface adjusting process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part, provided by the invention, ethylenediamine with a certain concentration is added in the plastic electroplating pretreatment process by washing, so that the roughened surface of the plastic part is adjusted, the adsorption efficiency of active palladium on the surface of the plastic part is improved, especially the adsorption efficiency of the active palladium colloid on the surface of PC (polycarbonate) plastic is improved, and the defect of poor plastic leakage of the product is effectively overcome. Taking the NCS door handle as an example, the plastic leakage ratio is about 60% after the treatment of the prior art, and by applying the surface adjustment process provided by the invention, the plastic leakage ratio is controlled within 5%, and the plastic leakage ratio is obviously reduced.
The surface adjusting process for improving the palladium adsorption performance of the surface of the electroplating-grade plastic part is simple to realize and high in operability. Need not hardware transformation, the teaching agent liquid medicine only need add in any one washing before palladium activation the inside add can, the tank liquor need not heat, need not filter etc. extra operation, only need once only add fluting concentration before the line is opened and can continuously use and do not need daily analysis and extra not add. The replacement is carried out regularly.
Detailed Description
The present invention will be further described with reference to the following specific examples.
Example 1 modulator concentration screening experiment.
The modifier concentration screening experiments are shown in tables 1 and 2.
Table 1 concentration of the teaching agent-plating-missing ratio of the product.
Table 2 ethylenediamine concentration screening-adsorption performance.
The adsorption efficiency is estimated according to experience, and the process principle is that the aim of solving the plastic leakage is achieved by improving the adsorption quantity of palladium on the surface of the product. At present, no analysis means is carried out on the adsorption performance index, but the palladium is not adsorbed or the palladium adsorption is extremely low due to the skip plating.
Example 2 a new plastic electroplating process.
The novel plastic electroplating process for improving the surface palladium adsorption performance of the electroplating-grade plastic part comprises the following steps:
a plastic electroplating process specifically comprises the following steps.
1. Chemical oil removal:
the upper-hanging finished whole flying bar workpiece product is immersed into a chemical oil removing groove station, and the operating conditions are oil removing groove parameter control: (1) ultrasonic treatment at 50 ℃; (2) the time is 1 minute; (3) the components are chemical oil removal powder with the concentration of 10 g/L.
2. And (3) hydrophilic:
after the hanger which is completely filled with the plastic part and is cleaned by water, the hanger is immersed into the hydrophilic tank, and the hydrophilic tank controls parameters: temperature: room temperature, treatment time: 10s-30s, and the liquid medicine comprises the following components: 50-100mL of sulfuric acid, surfactant: 1mL/L, and the surface of the product is adjusted to be beneficial to the smooth and new-in of the coarsening of the surface of the product.
3. Coarsening:
directly immersing the product subjected to hydrophilic treatment into a roughening tank solution, wherein specific roughening tank control parameters are as follows: (1) the temperature is 63-70 ℃; (2) the coarsening treatment time is 6-16 min; (3) the main components are as follows: chromic anhydride: 350-440g/L, and 320-430 g/L.
4. Neutralizing:
and fully cleaning the surface of the coarsened product by multi-connection washing, and transferring the product to a neutralization station through a traveling crane, wherein the neutralization station meets the treatment requirement, and hexavalent chromium residues which are not thoroughly cleaned are treated. The neutralization station control parameters are as follows: (1) the time is 30s-90s, (2) the temperature is room temperature, and (3) the component reducing agent: 40 mL/L.
5. Adjusting:
after the product is immersed in the adjusting process, the surface of the plastic part is adjusted, so that the best adsorption performance is achieved and preparation is made for subsequent palladium precipitation. The parameter requirements are as follows: (1) the temperature is room temperature, (2) the running is carried out for 5-60s, and (3) the main component of the regulator is ethylenediamine with the concentration of 3-10 mL/L.
6. Pre-dipping:
before the product enters palladium activation, the product needs to be soaked in a hydrochloric acid solution, so that the surface acidity of the product is ensured, and the concentration of diluted palladium activation is avoided. The presoaking control parameters (1) temperature is room temperature, (2) time is 60s, and (3) HCL concentration is 30-200 mL/L.
7. Activating palladium:
the palladium is present in colloidal form. A layer of palladium colloid is uniformly adsorbed on the surface of the plastic part, so that the subsequent chemical nickel can react on the surface of the product. Specific control parameters are as follows: (1) concentration: 10-35ppm of palladium, 320mL/L of hydrochloric acid 240-.
8. And (3) gel releasing:
transferring the activated product to a dispergation station to enable the colloidal palladium on the surface of the product to exist in an ion form, wherein the specific operation conditions are as follows: (1) the temperature is 50 ℃, the time is 2-5min, (2) the sulfuric acid is 5-10 mL/L.
9. Chemical nickel:
chemical nickel control parameters: (1) concentration: controlling the ratio of metal nickel to metal sodium to metal nickel, wherein the ratio of metal nickel to metal nickel: 12-18g/L, pH 7.8-9; (2) the time is 6-18 min; (3) the temperature is 25-40 ℃.
10. Acid activation:
(1) the bath solution is 0.05% sulfuric acid solution, (2) temperature: room temperature, (3) time: 5-20 s.
11. Pre-nickel plating:
(1) concentration control of nickel sulfate: 180-250g/L, nickel chloride: 40-50g/L of boric acid and 40-45g/L of boric acid; (2) the temperature is controlled at 50 ℃, and (3) the pH value is 3.6-4.8.
12. Acid copper:
(1) the main components are as follows: copper sulfate: 160-220g/L, 60-70g/L sulfuric acid, 0.2-0.8mL/L filling agent and 0.5-2.0mL/L brightening agent; (2) the temperature is 20-30 ℃; (3) stirring with air.
13. Nickel plating:
(1) the main components are as follows: nickel sulfate: 230-280g/L, 40-50g/L of nickel chloride, 40-50g/L of boric acid, and the amount of a cylinder opening agent: 5-10mL/L of brightener 0.2-0.5m L/L; (2) the temperature is 50-58 deg.C (3), and pH is 3.8-4.4.
14. And (3) chromium plating:
(1) concentration control chromic acid: 180-320g/L, 0.8-3g/L sulfuric acid; (2) the temperature is 38-45 ℃; (3) the time is 5-8 min.
Taking the NCS door handle as an example, the plastic leakage ratio is about 60% after the treatment of the prior art, and by applying the surface adjustment process provided by the invention, the plastic leakage ratio is controlled within 5%, and the plastic leakage ratio is obviously reduced. The plating missing defects of the product are mainly identified by 100% detection of the product after the product is electroplated and off-line.
Claims (5)
1. A surface adjustment process for improving palladium adsorption performance on the surface of an electroplating-grade plastic part is characterized by comprising the following steps: the method has the advantages that the ethylenediamine with a certain concentration is added in the plastic electroplating pretreatment process through water washing to adjust the surface of the plastic part after coarsening, so that the adsorption efficiency of active palladium on the surface of the plastic part is improved, particularly the adsorption efficiency of the PC plastic surface on an active palladium colloid is improved, and the defect of poor leakage molding of a product is effectively overcome.
2. The surface conditioning process for improving the palladium adsorption performance on the surface of the electroplating-grade plastic part as claimed in claim 1, wherein the temperature is room temperature.
3. The surface conditioning process for improving the palladium adsorption performance on the surface of the electroplating-grade plastic part as claimed in claim 1, wherein the time is 60 s.
4. The surface conditioning process for improving the palladium adsorption performance on the surface of the electroplating-grade plastic part as claimed in claim 1, wherein the concentration of the ethylenediamine is 3-10 mL/L.
5. A plastic electroplating process specifically comprises the following steps:
step 1, chemical degreasing:
the upper-hanging finished whole flying bar workpiece product is immersed into a chemical oil removing groove station, and the operating conditions are oil removing groove parameter control: (1) ultrasonic treatment at 50 ℃; (2) the time is 1 minute; (3) chemical oil removal powder with the concentration of 10g/L is used as the component;
step 2, hydrophilization:
after the hanger which is completely filled with the plastic part and is cleaned by water, the hanger is immersed into the hydrophilic tank, and the hydrophilic tank controls parameters: temperature: room temperature, treatment time: 10s-30s, and the liquid medicine comprises the following components: 50-100mL of sulfuric acid, surfactant: 1mL/L, and adjusting the surface of the product to facilitate smooth new progress of surface roughening of the product;
step 3, coarsening:
directly immersing the product subjected to hydrophilic treatment into a roughening tank solution, wherein specific roughening tank control parameters are as follows: (1) the temperature is 63-70 ℃; (2) the coarsening treatment time is 6-16 min; (3) the main components are as follows: chromic anhydride: 350-440g/L, and 320-430g/L sulfuric acid;
step 4, neutralization:
fully cleaning the surface of the coarsened product through multi-connection washing, transferring the product to a neutralization station through a traveling crane, and treating the treatment requirement of the neutralization station to remove hexavalent chromium residues which are not thoroughly cleaned; the neutralization station control parameters are as follows: (1) the time is 30s-90s, (2) the temperature is room temperature, and (3) the component reducing agent: 40 mL/L;
step 5, adjustment:
after the product is immersed in the adjusting process, the surface of the plastic part is adjusted, so that the best adsorption performance is achieved to prepare for subsequent palladium precipitation; the parameter requirements are as follows: (1) the temperature is room temperature, (2) the vehicle is driven for 5-60s, (3) the main component of the regulator is ethylenediamine 3-10 mL/L;
step 6, presoaking:
before the product enters palladium activation, the product needs to be soaked in a hydrochloric acid solution again, so that the surface acidity of the product is ensured, and the concentration of diluted palladium activation is avoided; the presoaking control parameter (1) is room temperature, (2) time is 60s, and (3) HCl concentration is 30-200 mL/L;
step 7, palladium activation:
the palladium exists in a colloid form, and a layer of palladium colloid is uniformly adsorbed on the surface of the plastic part, so that the subsequent chemical nickel can react on the surface of the product; specific control parameters are as follows: (1) concentration: 10-35ppm of palladium, 320mL/L of hydrochloric acid 240-;
step 8, dispergation:
transferring the activated product to a dispergation station to enable the colloidal palladium on the surface of the product to exist in an ion form, wherein the specific operation conditions are as follows: (1) the temperature is 50 ℃, the time is 2-5min, (2) the sulfuric acid is 5-10 mL/L;
step 9, chemical nickel:
chemical nickel control parameters: (1) concentration: controlling the ratio of metal nickel to metal sodium to metal nickel, wherein the ratio of metal nickel to metal nickel: 12-18g/L, pH: 7.8-9; (2) the time is 6-18 min; (3) the temperature is 25-40 ℃;
step 10, acid activation:
(1) the bath solution is 0.05% sulfuric acid solution, (2) temperature: room temperature, (3) time: 5-20 s;
step 11, nickel preplating:
(1) concentration control of nickel sulfate: 180-250g/L, nickel chloride: 40-50g/L of boric acid and 40-45g/L of boric acid; (2) controlling the temperature at 50 ℃, and (3) controlling the pH value to be 3.6-4.8;
step 12, acid copper:
(1) the main components are as follows: copper sulfate: 160-220g/L, 60-70g/L sulfuric acid, 0.2-0.8mL/L filling agent and 0.5-2.0mL/L brightening agent; (2) the temperature is 20-30 ℃; (3) stirring with air;
step 13, nickel plating:
(1) the main components are as follows: nickel sulfate: 230-280g/L, 40-50g/L of nickel chloride, 40-50g/L of boric acid, and the amount of a cylinder opening agent: 5-10mL/L of brightener 0.2-0.5m L/L; (2) the temperature is 50-58 ℃; (3) pH 3.8-4.4;
step 14, chromium plating:
(1) concentration control chromic acid: 180-320g/L, 0.8-3g/L sulfuric acid; (2) the temperature is 38-45 ℃; (3) the time is 5-8 min.
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