exploring the use of dlc diffusion barrier & corrosion...
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Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Packed. The 6th Global Summit, 19-20 June Amsterdam
Prof. Dr Eva Maria MOSER
Exploring the Use of DLC Diffusion Barrier & Corrosion
Protection Coating (Nano Contacts) in Packaging
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Content
Exploring the Use of DLC Diffusion Barrier & Corrosion Protection Coating (Nano Contacts) in Packaging
v Production of PE-CVD thin filmsv Sustainable DLC diffusion barrier layersv Adjustable wettability of DLC diffusion barrier layers:
Developments in nano-polar coating for anti-fogging, easy to clean, and adhesion promoter onto polyolephins
v Corrosion protection by embedding “active” nano contacts in sustainable DLC diffusion barrier layer
v Impact of nano-crystalline domains of titania (TiO2*) and imbedding of nano-clusters onto antimicrobial effects
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Motivation: Functionalization of sustainable packaging
TiO2*anti-germ
TiO2* barrier (UV & gas)
Replacement of varnish in metallic containers and on lids
Advanced DLC diffusion barrier
Titania*
*TiO2 with photocatalytic activity
Surfaces of everyday life products often miss
- long life durability- specifically desired functionality
Actual EU project FLEXIFUEL:900 Al-plates coated for heat exchange prototype
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Production of plasma coatings: Advanced DLC and Titania*
PVD &PE-CVD processes at reduced pressure
Pilot R&D plasma coaterwith a web width of 630 mm
PE-CVD and PVD processes at ambient temperature
PVD: Physical Vapour DepositionPE-CVD: Plasma Enhanced Chemical Vapour Deposition
Production of TiO2* coatings onto flat substrates at atmospheric pressure
Upscaledplasmaprocess:30 cm
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Why plasma coatings ?
Adaptation of established processes in manufacturing: Ø Nano structuring of the coatings
Ø Encapsulation of the nano particles
+/- Criteria Sol-Gel PECVD incoat/IPIMethods in general in particular
Investment coating equipment ++ - -
Chemicals (price, amount, toxicity) - + +Sustainability (process & coating) - + ++Dry process, cycle interruption - + +Ambient process temperature - - ++
Adhesion (ev. plasma pretreatment) - + +Specific coating structures + + ++Resistant, durable thin films - + +
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Basic properties of DLC: Diamond Like Carbon
DLC diffusion barrier layer:
Highly cross-linked and inherently
flexible hydrocarbon thin film
I: diamond-likesp3 > sp2; C > H
II: graphite-likesp3 < sp2; C > H
III: polymer chainssp3 > sp2; C < H
HH
HH
HHH
HH
H
HH
HH H
HH
HH
HHH
H
H
H
HHH
HHHH H
H H
H
H H
HH
Amorphous DLC layer of 70 nm
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Functional testing of coated PET and CPP
Coated PET/CPP
O2-Perm. 0% r.h. [ml/m2dbar]
O2-Perm. 85% r.h. [ml/m2dbar]
H2O-Permeability90% r.h. [g/m2d]
Stretch failure[%]
PET: DC/RF/GHzPET: Web coater
1.0 - 1.2 ± .20.8 - 2.1 ± .2
0.8 - 0.9 ± .20.8 - 2.1 ± .2
0.2 - 0.3 ± .20.1 - 0.8 ± .2
2.6 – 3.7 ± .23.1 – 5.1 ± .2
Hydrophobe/PETphob/phil/PET
< 1.0 ± .2 < 1.9 ± .2
< 0.8 ± .2 < 0.7 ± .2
< 0.2 ± .2< 0.2 ± .2
> 2.5 ± .2 > 4.7 ± .2
Hydrophobe/CPPphob/phil/CPP
40 ± .2 27 ± .2
--
0.4 ± .20.8 ± .2
--
Ref.: PET 12 µm < 123.9 ± .3 < 93.0 ± .3 < 20.4 ± .3 -
Ref.: CPP 75 µm 1000 - 4000 - 4 -
Barrier effect is enhanced in humid conditions due to the hydrophobic feature of DLC – contrary to SiO2 coatings
Manufacturing of SiO2/DLC barrier coatings forPET bottles > 20’000 bottles/hour à tubes
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Direct contact of DLC with content
CPP/PET filmplasma treated
3 wt% acetic acid (2h@90°C, 10d@40°C)
95 vol% ethanol (4h@60°C, 10d@40°C)
isooctane (2h@60°C, 2d@20°C)
Ref: CPP/PET < 1 mg/dm2 < 1 mg/dm2 < 4 mg/dm2
wincoat CPP < 1 mg/dm2 < 1 mg/dm2 < 1 mg/dm2
Phil /CPP < 1 mg/dm2 < 1 mg/dm2 < 1 mg/dm2
Phil /CPP < 1 mg/dm2 < 1 mg/dm2 < 1 mg/dm2
Phob /CPP < 1 mg/dm2 < 1 mg/dm2 < 1 mg/dm2
Global migration according to EU guidelines 2002/72/EG (detection limit: <1 mg/dm2, tolerance limit: <10 mg/dm2)
ESR and fluorescence spectroscopy; DLC coating: food for germs(1020 Spins/cm3, g-value: 2.0023 (11 Gauss):
à no free radicals in DLCà no interaction, no migration
Hydrophobic DLC
HydrophilicDLC
Welding-peeling properties:
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Stable polyolefin surface due to nano structuring
AFM images of plasma treated cast polypropylene
The surface of the plasma treated cast-polypropylene is stable:à no «hydrophobic recovery phenomenon»à no additives / no VOC’s at surfacesà CPP is printable and can be coated
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Additional functionality: Structuring of polymers
Hydrophilic polyolefin• sustainable (no interaction)• super-polar, anti-fogging• stretchable• chemically resistant• printable, good adhesion• weldable
Hydrophobic polyolefin• sustainable (no fluorine)• super-hydrophobic • stretchable• water repellent, easy-to-clean• chemically resistant• weldable
AFM-image of plasma nano structured CPP à stable, non-restructuring surface
SEM-image of CPP with micro structures produced by hot embossing
à Functionalization of packaging surfaces
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Functionalization: Tailoring the wettability
with nano
without nano
WCA = 6°
WCA = 146°
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Additional functionality: Wettability of CPP
Structured/coated CPP: 6°
Untreated CPP: 97°
Structured/coated CPP: 146°
Anti-fogging effect Water repellence
v Anti-fogging effectv Easy-to-clean surfacesv Complete emptying of content
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Additional functionality of polypropylene
wettable - anti-fogging – weldable - sealable
storage @ RT storage @ 4°C storage @ 80°C
ref. ref. ref.
incoat incoat incoat printed, incoat© plasma-treated CPP film (75 µm)
removed tape
printable, ready to be coated
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
DLC with metallic contacts : Corrosion protection
Sustainable Nano Texturing of DLC Layers:Ø Durable encapsulation of metallic nano contactsØ Tailoring of wettabilityØ Substitution of varnish in metallic cans & containersØ Replacement of varnish on metallic lids
DLC matrix of 70 nm:Diamond Like Carbon layer
10 of 11 Alu cans: Bisphenol A
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
DLC thin film and active corrosion protection
Anodic corrosion protectionReaction: 2 Me + O2 à 2 MeO
Plasma layer: 50 nm
Metallic nano contacts(< 10 mg/m2)
Micro defectAdjustable wettability
Metallic substrate:Aluminium, steel,….
Metallic nano contacts: Æ 5 nm in DLC permanently immobilised
DLC: Diamond Like Carbon layer (50 nm): Highly cross-linked plasma polymer as durable matrix
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Excellent corrosion protection by nano contacts
Corrosion tests performed at EMPA:- Pore test according to Verpackungsrundschau 11/1976- Determination of electrochemical parameters (impedance-spectroscopy)- Salt spray test (DIN EN ISO 9227 NSS): Storage for 3 days at 35 °C- Condensed water test climate (DIN EN ISO 6270-2 AHT: 7 days with 2 cycles at 100% rel. humidity (8 h at 40°C and 16 h at 23°C)
Pure DLC layer deposited onto Al-foil with poor protection; pores
Metal-doped DLC layer onto Al-foil with good protection; without pores
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Excellent corrosion protection by nano contacts
Al-foils after 27 days condensed water test: left: Hydrophobic, metal-doped DLCright: Chemically cleaned Al-foil, without coating
Corrosion tests performed at EMPA:- Pore test according to Verpackungsrundschau 11/1976- Determination of electrochemical parameters (impedance-spectroscopy)- Salt spray test (DIN EN ISO 9227 NSS): Storage for 3 days at 35 °C- Condensed water test climate (DIN EN ISO 6270-2 AHT: 7 days with 2 cycles at 100% rel. humidity (8 h at 40°C and 16 h at 23°C)
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Protection against corrosion, chemical attacks, and abrasion for metallic packaging
Ø Optimised coatings could not be attacked by aggressive acid solutions such as acetic acid Ø Excellent adhesion at dry and wet conditions : 5B (Cross hatch/scotch test,
ASTM D 3359-97 Test B and bending tests)
Poor DLC on Al, partly peeled off after 27 days in 50 % HAc
Good DLC on Al, without delamination after 27 days in 50 % acetic acid
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Benefits of photo-induced titania layers (TiO2*)
disinfectionUV-protection
selective diffusion barrier
biocompatibility
bioactivity
detoxification
active self-cleaning
anti-fogging
decontamination
HRTEM image of a titania* thin film PVD ref. with a thickness of 192 nm: Crystalline domains of anatase [110] in a amorphous matrix
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Photocatalytically active titania layers (TiO2*)
Activation of titania layers at 365 nm*
Bleaching of a 0.05 mmolmethylene blue solution
Activation of titania layers at 428 nm
Activation of titania under visible light at 625 nm
*CIF = 1.0 corresponds to bleaching of 1.7 mmol/m2×d of methylene blue by a PVD-TiO2 ref. layer (50 nm, on a glass slide) according to ISO 10678:2010
Titania coated surfaces:Fingerprints disappear……
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Photocatalytic reactions at titania* surfaces
H2O
CO2
O2- Ti4+
CHx
O2
TiO2* (anatase) hn ³ Eg Titania TiO2*
O2-
OH*
H2O
h+
Photocatalyst reaction TiO2 à electron + hole
e- ReactionsRedox potential
3.2 eV
CB
VB
Organic compound + Mineral acid
O2
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Improvement of Photocatalytic Activity by Doping
AFM-image of an atomic layer of Ag-clusters with Ø of 10-20 nm
500
nm
0
0
nm 500
Monolayers of noble metal clustersà Increase of activity > 30%
Doping of TiO2* with nitrogen, etc. à Variation of Eg and increase of activity
Doping with metal cations or non-metallic elements Large surface area, open surface morphologyParticle size: nanometer-size range (optimum size around 10 nm)
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Functional properties of titania* layers
*Catalytic Improvement Factor CIF: Comparison to the internal reference layer PVD TiO2 ref.(50 nm, on a glass slide) for bleaching of 1.7 mmol/m2×d aqueous solution of methylene blue
1LED white light (LEDON 10 W, 2700 K, 600 lumen, 625 nm, distance 5 cm): CIF = 6.8
TiO2Layer/glass
Sample no.
Thick-ness[nm]
Rough-ness[nm]
n @ 633[nm]
Egap
[eV]
Wetta-bilityin dark
ActivityISO 10678[µmol/m2h]
CIF*@ 365
nm
CIF*@ 428
nm
Stearic acide
[mmol/h]@365 nm
Stearic acide
[mmol/h]@428 nm
PVD TiO2 ref. 09.11.18 130 3.4 2.18 3.29 27 2.4 2.3 1.3 4.8 0.08
TiO2 a 11.04.20-IC 223 12.9 2.15 3.04 38 4.4 4.1 1.5 4.2 -
TiO2 b 11.04.19-IB 186 11.2 2.17 3.15 28 5.6 5.3 1.7 2.6 0.03
TiO2 c 11.04.21-IB 225 14.7 2.11 2.85 55 5.1 4.8 1.7 4.8 -
TiO2 black1 12.10.08-IB 1000 14.9 2.17 3.15 24 10.1 10.1 1.3 19.6 -
PE-MOCVD TiO2 09.08.21 MA 230 1.1 1.79 3.48 75 4.8 4.5 1.3 0.1 0.02
TiO2 a 11.04.27 MA 339 0.5 1.71 3.27 67 3.6 3.4 1.7 0.1 -
TiO2 b 11.05.23 MA 276 0.9 1.76 3.33 68 7.5 7 2.2 0.1 -
TiO2 c 11.05.19 MA 237 1.0 1.79 3.39 86 7.8 7.3 3.1 0.4 0.02
TiO2 ATMO 200 5.6 1.99 3.44 3.1 2.6 1.7 - -
Pilkington ~ 30 - - - - 1.3 1.5 0.3 - -
Improvement of photocatalytic activity by doping and co-doping the titania layers*
PVD TiO2 layers are more efficient in destroying stearic acid than PE-MOCVD TiO2 layers
*Eva Maria Moser et al., Surface & Coatings Technology 227 (2013) 2-9
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Destruction of stearic acid: Fingerprints & germs
Roughness [nm]: 14.9 7.2 4.7 5.4 3.5
AFM-Images: ~ 200 nm thick PVD-TiO2
0
5
10
15
20
25
0 1 2 3 4 5 6 7 24 32 48
Concen
trationofstearic
acid[m
ol×10-
3 ]
Timeofirradiation[h,@365nm]
PVD-b 1000 nm PVD-b 200 nm PVD 1000 nm PVD 200 nm PECVD-c 130 nm
1 h 1 h 1 h
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Germ-inhibiting features of titania*
*Tests were performed according to ISO 22196: Sterilisation if <1 of 1 mio germs after 24 hours
Antibacterial activity under visible light
Tests according to ISO 22196:Growth reduction efficacy [log cfu]
PVD TiO2-b 13.8.3.0047-1 (300 nm, CIF = 7.0/1.7RMS = 5.2 nm, hydrophilic)
E. coli: 0.75 (slight)S. aureus: 0.62 (slight)
PE-MOCVD TiO2-c 13.8.3.0047-2(200 nm, CIF = 7.3/3.1RMS = 1.0 nm, hydrophobic)
E.coli: 2.35 (significant)S. aureus: 2.46 (significant)E. coli do not stick well to the titania surface and can be removed easily
PVD TiO2 black 13.8.3.0047-3(1.4 µm, CIF = 10.1/1.3RMS = 5.0 nm, hydrophilic)
E. coli: > 5.52 (strong) à 20 of 1 mio germsS. aureus: > 3.68 (strong)
no illumination illumination for 1 day illumination for 6 days
AFM images of E. coli on the TiO2 surface: Kayano Sunada et al., Journal of Photochemistry and Photobiology A: Chemistry 156 (2003) 227–233
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Combination of structuring and plasma layers
The surfaces “easy-to-clean” are distinguished by their surface energies and the micro-nano structures of the surfaces. (Θ = water contact angle)
DLC phob flat orwith micro structure
super-hydrophobicΘ >120°
surface with very weak polarity
hydrophobic120 °
80°< Θ <120°surface with weak polarity
hydrophilic20°
10°< Θ <80° surface with high polarity
super-hydrophilic Θ < 10° surface with very high polarity
DLC and polymers (-C-H, Si-C-, F-Si-,)
TiO2* and
micro structure
Passive, not interacting surfaces
Active*, interacting surfaces
TiO2* flat or with
micro structure
TiO2* smooth
or nano structure
TiO2* smooth
or nano structure
DLC phil, SiOx, TiOx(-C-OH, -CO, -NOx)
DLC phil, SiOx, TiOx(-C-OH, -CO, -NOx)
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Summary
multi functio-nality
advancedbarriers
structuring
wettabilityDLC phob and TiO2
*
clusters
Dr Eva Maria MoserPacked. The 6th Global Summit, 19-20 June Amsterdam
Thank you !
The human tendencyto regard little things as importanthas produced very many great things.
Georg Christoph Lichtenberg (1742-1799)
R&D projects No. 7960.2, 10778.1, 10747.2 PFNM-NM have been funded by CTI
Several patents are hold for all presented thin films and deposition processes.
Prof. Dr Eva Maria Mosereva.moser@incoat.chincoat GmbHCH-8212 Neuhausen am Rheinfall+41 76 321 21 59
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