Sustainable functional coatings

for future packaging: barrier

and antimicrobial coatings
Sabine Amberg-Schwab, Daniela Collin (ISC)
Ilija Nasov, Anka Trajkovska Petkoska
(PLASMA)
Zaragoza, 24 February 2016
 Outline

• Present situation
• New approaches for packaging
• Material base for sustainable functional coatings
Pied de page ‹#›
• Results
• Summary

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Present situation
Pied de page ‹#›

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 Plastic containers for convenience

Food is mostly packaged

in plastic

Convenience Food:
 long shelf life
 availability at all times Pied de page ‹#›
 in all situations

Quelle: http://www.eufh.de/daten/bilder/news-events/presse/000097-2.jpg

Part of our life quality

Quelle: „Cup-Noodles-2“ von Rainer Zenz - Eigenes Werk (Own photo). Lizenziert unter CC BY-SA 3.0 über
Wikimedia Commons - https://commons .wikimedia.org/wiki/File:Cup-Noodles-2.jpg#/media/ File:
Cup-Noodles-2.jpg

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 Poisoning of nature and people
 Accumulation of plastics in the
environment
 Degradation to micro and nano
particles
 Accumulation of toxic and
carcinogenic chemicals
(DDT, PCB) to the particles
Pied de page ‹#›

 Accumulation of the
particles in the food chain

particles and adhering

toxins are ingested by
humans
Quelle:
Quelle:
http://de.wikipedia.org/wiki/Plastikm%C3%BCll_in_den_Ozeanen
http://de.wikipedia.org/wiki/Plastikm%C3%BCll_in_den_Ozeanen

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New approaches
for packaging ‹#›
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 Biodegradable packaging

State-of-the-art: Films based on cellulose, polylactic

biodegradable films acid and starch have long been known

 no sufficient barrier properties against oxygen, water

vapor and flavors
 these materials cannot guarantee the required minimum
Pied de page ‹#›
shelf life of many food products

Solution: Optimizing the substrate properties

through biodegradable functional coatings

Biodegradable packaging

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Barrier requirements for films

Pied de page ‹#›

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ORMOCER® chemistry: specialty of Fraunhofer ISC

ORMOCER®
adjustable material properties
generate new functions

R1
R2

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R2

Inorganic Hybrid material Organic

material ORMOCER® polymer

ORMOCER®s: developed at Fraunhofer ISC, Trademark of Fraunhofer-

Gesellschaft zur Förderung der angewandten Forschung e.V. in Germany

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 Barrier coatings

Oxygen transmission rates

Hybrid polymer (5 µm)

on BOPP- (30 µm) and
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SiOx- coated film
(DIN 53 380; 23 C, 50 % r. F.)

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Taking advantage of synergy effects between layers

Inorganic vacuum deposited barrier layer + barrier

lacquers on the basis of hybrid polymers (ORMOCER®s)

Chemical bondings at
the interface:
compensation of Pied de page ‹#›
defects

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Barrier requirements for films

Pied de page ‹#›

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Material base for sustainable
functional coatings ‹#›
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New concept: biodegradable ORMOCER®s
ORMOCER®

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bioORMOCER®
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Material base: biodegradable ORMOCER®s

Polycaprolactone-triol
Chitosan Cellulose
(PCL-T)

PCL-T-
Epoxy-cellulose triethoxysilane
OEt
EtO
Si
OEt
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HO

NH
O
O
HO
Carboxy-methyl- Cellulose-
chitosan triethoxysilan

Covalent bonding to an organic and inorganic network through

reactive groups
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Results
Pied de page ‹#›

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 Biodegradable ORMOCER®-coatings
Experiments for
biodegradability
Pretest: compost storage

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 Considerable
biodegradation for
bioORMOCER®s 6 weeks compost

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 Biodegradable ORMOCER®-coatings
Biodegradation of (bio)ORMOCER® coatings
(measured@ARCHA; DIN ISO 14885-1:2005)

1st campaign: moderate amount of biopolymer within hybrid polymer

sample Biodegradation (%)

pure hybrid polymer
ORMOCER® 64,0
Pied de
bioORMOCER page
®-1a ‹#› +10 %
bioORMOCER®-2a +12%
Cellophane coated with
bioORMOCER®-1a 97.9
bioORMOCER®-1b 97.3
bioORMOCER®-2a 98.2

 Biodegradation rate is INCREASED by the bioORMOCER® concept

 Next step was: INCREASE in biopolymer content within bioORMOCER®

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Functional properties of bioORMOCER® coatings

 humidity-triggered
antimicrobial action
 barrier properties
against gases and
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vapors

© Fraunhofer ISC

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Antimicrobial properties of functionalized bioORMOCER®s

Humidity triggered release of antimicrobial additives

Coated substrates stored in

varying climates

 Humid: 25 ºC; 80 % r. h.
 Dry: 20 - 25 ºC; 20 % r. h. Pied de page ‹#›

Humidity triggered

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Antimicrobial properties of functionalized bioORMOCER®s

Humidity triggered release of antimicrobial additives

Dependancy on the
network density

 Lacquer systems
with variable Pied de page ‹#›
network density
 Release rate
depends on network
density

Release controllable

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Biodegradable packaging material – barrier coatings

ORMOCER® bioORMOCER®

Pied de page ‹#›

ORMOCER® bioORMOCER®
Biodegradable lacquer

SiOx SiOx / sputtered SiOx/SiN (PLASMA)

PET Commercially available

Biodegradable film substrate
Option: (bio)ORMOCER® planarization layer directly onto substrate
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 Barrier properties of bioORMOCER®s

Oxygen transmission rate on PET/SiOx

(23 °C, 50 % r. h.)

PET/SiOx
bioORMOCER®-1a
bioORMOCER ®-1b
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bioORMOCER®-2a
bioORMOCER®-2b
ORMOCER®

 First results very promising

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 Barrier properties of bioORMOCER®s

Water vapor transmission rate on PET/SiOx

(23 °C, 85 % r. h.)

PET/SiOx
bioORMOCER®-1a
bioORMOCER®-1b
Pied de page ‹#› bioORMOCER®-2a
bioORMOCER®-2b
ORMOCER®

 First results very promising

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 Barrier properties of bioORMOCER®s

Transfer of barrier concept to:

 biodegradable films: Cellophane NK45 (INNOVIA)
 Inorganic sputtered layers: SiOx/SiN (PLASMA)

Barrier
Piedconcept for
de page ‹#› PLASMA
Bio- DIBBIOPACK film Technology
ORMOCER® substrates for barrier
coatings (Cellophane, PLA) enhancement

 Optimiziation of processes and layer set-up

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Plasma Technology: Activation and deposition of
inorganic coating on polymer based substrates

Plasma deposition process

Processes are performed in PVD chamber:

- by magnetron sputtering ‹#›

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- Si target in atmosphere of
O2. N2 and Ar gasses

• deposition of
Si / SiO2 / SiNx
multilayered coating

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 Plasma Technology: background in barrier coating
technology

• For the aim of FP7 project Composol, Plasma performed

successfully barrier coating over a multilayered reflective
coating.
Barrier coating
Ag/Al
coatingcoatingprotec
Pied de page ‹#› Metal
tiveprotective
layer
layer layer
Protective
Adhesive
Polymer composite holder

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 Plasma Technology: background in barrier coating
technology

• For the aim of the FP7 project Polysol, Plasma

performed successfully barrier coating over multilayered
solar selective coating.

Antireflection layer / protective layer

Pied de page ‹#›

LMVF-Low metal volume fraction
thermal IR Transparent

Interface /IR reflective layer

POLYMER

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 Plasma Technology: background in barrier coating
technology

• For the aim of the FP7 project Soleglass, Plasma

performed successfully barrier coating over multilayered
solar selective coating.
Antireflection layer / protective layer

LMVF-Low metal volume fraction

thermal IR Transparent
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HMVF-high metal volume fraction
thermal IR Transparent
Interface Adhesive layer

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 WP2.3 – Plasma Technology: Activation of polymer
based substrates (D2.8)

 Plasma deposition of inorganic Dibbiopack barrier layers -

process steps:

1. Activation of foils - plasma activation in atmosphere of Ar and O2

2. Time of deposition - from 10’ toPied

30’ per layer (within
de page ‹#› the multilayered coating)

3. In gas atmosphere in PVD chamber - O2 and N2 for forming SiOx or SiNx layers

4. Layer thickness - from 10 nm to 100 nm per layer within the coating

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 Barrier properties of DIBBIOPACK films

Biodegradable substrate: cellophane 45NK (INNOVIA)

Pied de page ‹#›

!
6 5 4 3 2 1 0
WVTR (23°C/100% r.h.) [g/m2d]

Results very promising

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 Barrier properties of DIBBIOPACK films

Biodegradable Substrate: PLA (INNOVIA)

Pied de page ‹#›

Results very promising

* also bioORMOCER®
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 Barrier properties of DIBBIOPACK films

First Tests: bioORMOCER® coating by roll-to-roll application for

continuous coating processes (ISC) and semi-continuous
process for inorganic sputtering layers (PLASMA)

Pied de page ‹#›

© Fraunhofer ISC © Fraunhofer ISC

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WP2.3 – Plasma Technology: Activation of polymer
based substrates (D2.8)

 Key results:

Plasma improved barrier performance of biodegradable polymer foils

intended for packaging during DIBBIOPACK project :
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1. Initially, PVD deposition of inorganic multilayered coatings on cellulose
films as well as on PLA films (initial dimension of A4 size),
2. Continue on: discontinuous PVD inorganic coating on 2 m roll of PLA film,
3. Finally, PVD deposition process of inorganic coating on 80 m roll-to -roll
PLA foil in semi-continual organization of the work.

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WP2.3 – Plasma Technology: Activation of polymer
based substrates (D2.8)

Know-how technology of deposition of DIBBIOPACK

inorganic layers within barrier coating was initially
established for smaller lab pieces
Pied de pageof ‹#›
biodegradable polymer
sheets and successfully transferred to deposition method on
discontinuous 2 m PLA roll and later on semi-continual 80 m
roll-to-roll process.

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 WP2.3 – Plasma Technology: Activation of polymer
based substrates (D2.8)

 Semi-continual roll-to-roll process of PLASMA

deposition of barrier inorganic coating in pictures

Pied de page ‹#›

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Summary
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 Summary (ISC)

Hybrid functional coatings for bio-based

packaging materials

Aim: Biologically degradable packaging materials

based on renewable resources
Property Combination
© Fraunhofer ISC

 Antimicrobial Pied de page ‹#›

 Barrier (water vapor, oxygen)

Approach
 bioORMOCER®sSi-based Plasma coating © Fraunhofer ISC

© Fraunhofer ISC

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