PLATING ON PLASTICS POP

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1

2

3

4 POP

5 A WIDE RANGE OF APPLICATIONS

6 PLASTICS FOR METALLIZATION PP 3% PA 3% others 2% ABS/PC 42% ABS 50%

7 STAGES FOR METALLIZATION OF PLASTIC

8 PRETREATMENT : CLEANING This stage improves the wettability of the parts and decreases the surface energy Before : contact angle > 90 deg After cleaning : contact angle < 90 deg

9 FIRST IMPORTANT STEP : ETCHING Strong oxidizing solution At high temperature C CONVENTIONNAL 40%CrO 3 40%H 2 SO COVENTYA Patent : Silken process 6% CrO 3 + Catalyst 65% H 2 SO COVENTYA KMnO 4 H 3 PO 4 solution

10 SEM device : QUANTA FEG FEI XFlash Brüker GSED ESEM Up to 2600 Pa ETD HIGH VACUUM < Pa STEM II TE SE BSE GAD 400 Pa LOW VACUUM 10 Pa 130 Pa LFD CBS

11 SEM PICTURES OF ABS ABS is a dispersion of nodules of butadiene in a styrene /acrylonitrile copolymer matrix Ra= 25 nm During oxidation stage : First nodules of butadiene are oxidized then more or less the matrix

12 SEM PICTURES AFTER ETCHING ON ABS Ra= 240 nm CONVENTIONNAL 40%CrO3 40%H2SO4

13 SEM PICTURES AFTER ETCHING ON ABS Ra= 48 nm 2003 COVENTYA patent: SILKEN Process 6% CrO3 65% H2SO4

14 SEM PICTURES AFTER ETCHING ON ABS Ra= 78 nm 2014 COVENTYA KMnO4 H3PO4 solution

15 Cr VI reducing : NEUTRAL Reducing solution Hydrate hydrazine, Ascorbic acid, Chromic acid : CrO 3

16 Cr VI reducing : NEUTRAL Reducing solution CrVI is reduced into CrIII Easier to rinse and avoid contamination for next steps

17 FIRST THIN LAYER : CATALYST PdSn colloid ( <10 nm diameter) stabilized in hydrochloride acid The colloidal particles diffuse into the microscopic porosity present on the plastic surface and are chemically adsorbed. Nanosizer ZS- Malvern

18 TIN OXIDATION : ACCELERATOR Oxidizing solution Sn2+ is oxidized into Sn4+ and «liberates» Palladium as metal Sn IV precipitates in the solution Sn IV Pd (0) remains in the porosities There is about 0.08 mg/dm² of Palladium on the surface

19 FIRST METAL LAYER : Nickel or Copper Electroless Processes The plastic part becomes CONDUCTIVE For Ni, sodium hypophosphite is used as the reducing agent. For Cu, formaldehyde is used as the reducing agent. Copper Nickel ABS ABS

20 LEVELING LAYER : Copper Electrolytic process Cu deposit levels the surface to ensure the brightest finish CuSO4 Sulfuric acid Organic additives : Base Brightener Leveler Current density : 2-3 A/dm² Cathode Cu e- Cu Thickness : up to 25 µm Hull cell

21 CROSS SECTION EDX phases analysis Electrolytic Copper Electroless Nickel ABS

22 Example : Layers for automotive industry High corrosion resistance and wear resistance

23 Example : Cross section

24 Under layer Ni effect FINAL CHROME DEPOSIT Mate Satin Bright White Cr Dark Fume Cr Good resistance to shock, wear and decorative aspect

25 Aspect of under layer : SATIN Nickel Ni + - Part The bathes contain an emulsion of micelles of surfactant. Based on the cloud point of the surfactant.

26 QUALITY CONTROL Sratch test (ASTM-B571) 90 Peel test (ASTM B )

27 QUALITY CONTROL Pits Salt spray test ( NaCl spray) or Cass Test ( NaCl +Cuproacetic spray)

28 POP video INDUSTRIAL APPLICATIONS

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