FLEXIBLE FILMS TREATMENT

Transcription

1 FLEXIBLE FILMS TREATMENT ROLL TO ROLL ATMOSPHERIC PRESSURE COLD PLASMA - SURFACE CHEMICAL ACTIVATION & FUNCTIONNALIZATION - DEPOSITION of NANO COATINGS At INDUSTRIALSCALE Eric GAT & TRAN Minh Duc

2 PRODUCTS AND SERVICES OF CPI TREATED MATERIALS Polypropylene (BOPP, CPP, COPO) Polyethylene (HDPE, BDPE, ) Polyester (PET, OPET), Polyamide (OPA) Fluorinated polymers (PVF, PVDF, PTFE ) Functional Poly olefins (EVOH, EVA, PVDC ) Siloxanes (PDMS) Printed polymer Papers, textiles & fabrics Metal foils & metallised films SERVICES R&D Industrial subcontracts Trials Manufactured products

3 APP TREATMENT UNIT APP TREATMENT Filamentary DBD CORONA like discharge Flexible film Slitting Treated film

4 P unit at CPI APP Reactor Slitter & winder Un winder Web

5 P600 Unit at CPI

6 SPECIFICATIONS Conveying specifications Film width & thickness:500 to 2000 mm wide & 5 to 600 µm thick Reel max external diameter (Unwinding/winding) 1200 to 800 mm Reel max external diameter (Unwinding/Winding) 900/400 kg Core diameter 76 or 152 m Slitting ability just before winding (two winding axes) APP reactor specifications Gaseous mixtures; pure N 2 (< 10 ppm O 2 ) or with 500 ppm dopants ( N 2 O / CO 2 / H 2 / C 2 H 2( 4) / SiH 4, TEOS, HMDSO Frequency 45 khz, Power 35 kw Film speed 40 to 300 m/min APP Dosage 5 to 300 W.min/m 2 Pre CORONA Dosage 5 to 1000 W.min/m 2 Electrodes nature Metal, ceramics

7 MAIN SURFACE PROPERTIES APPLICATIONS Grafting and coating by chemical covalent bond High level and stable surface energy Permanent modification of the wettability Improvement of adhesive & printing properties Adjustable coefficient of friction Anti-blocking effect ADVANTAGES Suppression of adhesion primer & varnishing High quality printing with all type of inks (water based, solvents, UV curable) Film adhesion for lamination, metallization,,...

8 APP TREATMENT REACTOR APP design O 2 analyser Injection of Working gases : - pure N 2, (< 10 ppm O 2 ) - N 2 + dopants ( ppm) (N 2 O, CO 2, H 2, SiH 4, C X H Y, TEOS, HMDSO) Pressure Control Exhaustion Nitrogen knife Nitrogen knife Electrodes Film

9 APP Filamentary DBD DISCHARGE N 2 (C 3 Π u ) ν=3 (13 ms) 11.1 ev 4.9 ev N 2 (A 3 Σ u ) ν=2 (1 3s) 6.2 ev C( 3 P) + N( 4 S) 11.1 ev N 2 (X 1 Σ g ) Ground state B 1 Σ 3.2 ev A 2 Π X 2 Σ Molecular N 2 2 nd positive system CN violet system

10 APP Dielectric Barrier Discharge (DBD) at Atmospheric Pressure : 10 ns 100 µm 20 kv 50 khz N 2 - High dielectric solid between electrodes - Discharges in pure N 2 atmosphere (<10 ppm O 2 ) - Avoid electric arcing, thermal & chemical degradation - Filamentary - streamers (10 ns duration, 100 µm diameter ) - Distributed statistically over the treated surface

11 APP Chemical reactive species hν Electrons Ions Atoms Radicals Metastables 10 nm Atmospheric Pressure Plasma only long life time neutral metastables (no ion ) surface activation by chemical grafting, gradient in depth, different analytical data according to used techniques and inspection depth

12 SURFACE ENERGY BY CALIBRATED INKS APP treated BOPP Untreated E surface <32 mn/m (*) APP H2 - treated E surface =60 mn/m (*) ( * ) ASTM D a test method / SOFTAL GmbH calibrated inks

13 PROCESS OPTIMIZATION 62 Surface energy vs dosage for APP-H treated PET and PP Surface energy (mn/m) PET Pure PP t = 0 j APP dosage (W.min/m 2 )

14 PROCESS OPTIMIZATION 62 Surface energy vsdosage for APP -H treated PP Surface energy (mn/m) Pure PP PP with additives t = 0 j APP dosage (W.min/m 2 )

15 SURFACE AGEING 62 Surface energy ageing of APP -H treated PP Surface energy (mn/m) Pure PP - 50 W.min/m 2 PP with additives W.min/m Shelf life (days)

16 PROCESS OPTIMIZATION Surface energy vs dosage for APP treated Pure PP APP -H APP PN2O Surface energ gy (mn/m) t = 0 j APP dosage (W.min/m 2 )

17 SURFACE AGEING Surface energy ageing of APP treated Pure PP APP-H 2 Surface energy (mn/m) APP -N2O AIR CORONA Shelf life (days)

18 MORPHOLOGY BY AFM (*) TREATMENTS ON BOPP FILM Untreated R a = 0.52 nm Air Corona Ra= 0.36 nm N 2 Ra= 0.41 nm N 2 +N 2 O (500ppm) Ra= 0.46 nm (*) AFM Tapping mode by BIOPHY RESEACH

19 N & O Grafting on BOPP surface by APP C1s Untreated BOPP C1s APP treated BOPP O1s N1s XPS analysis by BIOPHY RESEACH

20 N & O Grafting on BOPP surface by APP Treatment parameters: Gas : N2 Specific power: W.min/m2 Speed: 50 m/min Exposure time : 0.5 s YIELD of GRAFTING % Grafted N : In depth grafting reaction ATOM PERCENTAGE 4 2 % Grafted O : Surface adsorption by return to air (partially) PLASMA SPECIFIC DOSE (W.min/m2)

21 CHEMICAL COMPOSITION (XPS) APP Treated BOPP : Grafting controlled by reactant gas mixture composition GAS MIXTURES % C % O % N AIR CORONA PURE N N 2 O (500 ppm) CO 2 (500ppm) H 2 (500ppm)

22 CHEMICAL FUNCTIONNALITIES GRAFTED ON PP BY APP C1s C-C N1s N-(CO) 2 C-N N-C=O N-C=O N-(CO) 2 N-C Treatment parameters: Gas : pure N2 Specific power: 70 W.min/m2 Speed: 50 m/min NR 4 +

23 CHEMICAL FUNCTIONNALITIES (XPS) APP treated PP : Chemical functionalities controlled by reactant gas mixture composition Gas mixtures % Amine % Amide % Imide Pure N N 2 + N 2 O N 2 + CO N 2 + H Percentages of total grafted N

24 SURFACE FUNCTIONNALIZATION: CHEMICAL GRAFTING Amine Amide Imide H H O H H N O O NH 2 O N C C C O O O O C C C C C C C C C C C H SPECIFIC CHEMISTRY Standard oxygen based surface chemistry New Amino, Amido and Imido based surface chemistry

25 AMINO and and AMIDO/IMIDO chemistry chemistry features features Amine H H N C 50% 0% Amide+Imide O NH 2 C C 50% 100% Amino and amido groups covalently linked to the surface providing: PERMANENT SURFACE MODIFICATION HIGH & STABLE SURFACE ENERGY STRONG CHEMICAL REACTIVITY with: Alkyds Epoxydes Isocyanates Acids and Esters (e.g. acrylates) CHARACTERISTICS Improved adhesion via hydrogen bonding or covalent bonding with binders Fast reaction kinetics leading to reduced curing time

26 ADHESION PEELING TESTS ON TREATED BOPP Air Corona Adhesion: 1/5 (*) APP H2 treated Adhesion: 5/5 (*) (*) ASTM D test method / AKZO blue water ink 0/5 : Total peeling of ink from the film to the tape (TESA 4104) 5/5 : No peeling

27 Surface Energy and Adhesion APP treated BOPP RECIPE UNTREATED AIR CORONA ALDYNE TM -P ALDYNE TM -C ALDYNE TM -H SURFACE ENERGY (*) mn/m (after 100 days) < ADHESION (**) 0/5 1/5 1/5 3/5 4/5 (*) ASTM D a test method / SOFTAL GmbH calibrated inks (**) ASTM D test method / AKZO blue water ink 0/5 : Total peeling of ink from the film to the tape (TESA 4104) 5/5 : No peeling

28 Nanocoating Silica nanocoating on BOPP Untreated θ = 106 Silica nanocoating θ 20 MODIFICATION OF SURFACE PROPERTIES HYDROPHOBIC HYDROPHILIC

29 ANTI-FOG PROPERTIES Silica nanocoating on BOPP Untreated Silica nanocoating

30 Nanocoating Silica nanocoating on BOPP (AFM surface imaging) Untreated BOPP Silane treated BOPP Ra = 3.35 ±0.1 nm Ra = ±4 nm 1 µm x 1 µm AFM images (Tapping)

31 Nanocoating Silica nanocoating on BOPP (TEM section Imaging) Low density layer (few tens nm thick) BOPP Thin dense layer (few nm thick) Dissolved agglomerate Resin Silane treated BOPP

32 Nanocoating Silica nanocoating on BOPP (AFM surface imaging) Untreated BOPP TEOS treated BOPP Ra = 2.84 ±0.2 nm Ra = 1.42 ±0.2 nm 1 µm x 1 µm AFM images (Tapping)

33 Nanocoating Silica nanocoating on BOPP (TEM section Imaging) Resin Thin dense continuous layer (10 nm thick) BOPP Irregularities In the section TEOS treated BOPP

34 ACTIPOLE SAINT CHARLES FUVEAU FRANCE Tel: 33 (0) Fax: 33 (0) cpi@cpi-plasma.com