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Review and evaluation

of AlOx clear barrier
production processes

Technical content, problem solving solutions and the latest news from the packaging films industry
Technic al Articles

Review and evaluation of

thermore, polymer resins such as
PVA or EVOH have high tempera-
ture and humidity dependency that

AlOx clear barrier production

lower gas barrier property. Boiling
or retort treatment during convert-
ing affects the barrier properties of

processes
such laminated film.
The alternative to thick polymer-
ic clear coatings such as PVDC or
PVC can be a vacuum clear coat-
Professor Nadir A. G. Ahmed ing process with a coating thick-
ness several orders of magnitude
thinner and in the range of only ~
Aluminium oxide (AlOx) clear barrier coating has become one of the 10 nanometers achieving the same
favoured choices for flexible packaging. Different processes and tech- or better barrier properties than pol-
niques are used for the production of AlOx on flexible films. The selection ymeric coatings. Another advan-
of AlOx production process is mainly based on achieved barrier level, low tage of vacuum based processes; the
cost, fast production speed and the availability of vacuum web metal- coating material for the barrier lay-
lisers for industrial production. This paper will review the main AlOx ers is usually oxide like AlOx, which
clear barrier production processes available in the market and outline is non-toxic to the environment.
the mechanism of each process. Although environmental aspects,
barrier and optical properties are
all important, equally important

T he advantages of using the

Plasma Assisted Deposition
technique for the production of
AlOx with high barrier will be dis-
cussed in details. In this technique
plasma is used during deposition to
enhance the structure of AlOx par-
ticularly at the coating/ film inter-
face to increase adhesion, barrier
and optical transparency.
Introduction
Most of the transparent flexible
Figure 1: barrier coated films available at
Reactive Evaporation of present are produced by polymeric
aluminium with oxygen. barrier layers including EVOH and
PVDC. The thickness of such layers
is in the range of several microm-
eters to several 10’s of micrometers.
“Plasma is used during
deposition to enhance
the structure of AlOx
particularly at the coating/
film interface to increase
adhesion, barrier and
optical transparency.”
However, some of these coatings
may contain chemicals like chlo-
rine, which are not considered to
be environmentally friendly. Fur-
are cost aspects, process flexibility
regarding different base films and
coating robustness to survive the
converting processes.
AlOx offers other advantag-
es over conventional aluminium
metallised film including transpar-
ency for easier product identifica-
tion, microwave transparency, and
potential recyclability.
At present, there are vacuum web
metallisers available in the market
that can be used for conventional
aluminium metallisation as well as
the production of AlOx.
This paper will outline the phys-
ical vacuum deposition processes
used in the production of oxygen
rich and metal rich AlOx coating
onto flexible films such as PET or
OPP and will discuss the mecha-
nism of each process particularly
the plasma assisted deposition of
AlOx.

Vacuum deposition
processes used for the
production of AlOx

At present, there are two main vac-

uum deposition processes used for
the production of AlOx clear barrier
coating. These are:
a. Reactive thermal evaporation of
aluminium with oxygen.
b. Plasma assisted deposition.
The selection of a particular pro-
cess depends on many factors in-
cluding barrier level required and
the financial budget available to

2 www.packagingfilms.com PackagingFilms

acquire a new generation of plasma
assisted metalliser or a retrofit onto
a standard aluminium metalliser.
a. Reactive thermal evaporation
of aluminium with oxygen.
This process is carried out inside
a standard vacuum web metalliser.
However, during the evaporation of
aluminium a controlled injection of
oxygen is required to oxidise alu-
minium and deposit AlOx coating
onto the moving web. Aluminium
oxide and metal/aluminium ox-
ide can be deposited by aluminium
reaction with oxygen. The overall
stoichiometry is dependent upon
oxygen-to-metal feed ratio during
deposition. It is well known that
aluminium oxidises very quickly
in the presence of oxygen gas or
water vapour. For example, in the
standard aluminium metallised film
there is a low percentage of ox-
ide formation at the interface be-
tween the aluminium and the film
as well as another oxide layer at
PackagingFilms
Technic al Articles
the top of the metallised surface.
This is due to outgassing of air and
moisture from various parts inside
the metalliser during metallising.
When the metallised film is left in
open air after metallisation is com-
plete, the top oxide layer increases
in thickness with time due to dif-
fusion of air or moisture. But the
growth will slow down and stop
eventually. Typically the oxide lay-
er thickness in standard metallised
film could be within 2 nm–2.5 nm
almost immediately and 3 nm–4.5 er, this amount of oxygen is not Figure 2:
nm after 1 month to 1 year depend- high enough to achieve almost a EDAX analysis of oxygen
ing upon exposure conditions. In complete oxidation and clear ox- rich AlOx clear coating.
standard aluminium metallisation ide coating. Therefore, for the pro-
process there is always plenty of ox- duction of clear oxygen rich AlOx
ygen in the chamber even at a good or metal rich AlOx coatings, a con-
base pressure due to outgassing and trolled injection of oxygen is direct-
moisture level in the chamber. For ed towards the aluminium vapour
example, at a base pressure of about stream during metallising causing a
1x10-4 mb the arrival rate of oxygen reaction between the two elements
at the film surface could be about to produce aluminium oxide (AlOx).
2x1016 atom/cm2.sec , while the ar- The reactive balance between the
rival rate of aluminium is about amounts of oxygen and alumini-
1x1021 atom/sec to deposit 2.5 OD um produces either oxygen rich or
aluminium onto the film. Howev- metal rich coating with good bar-
www.packagingfilms.com 3
Technic al Articles

rier. Metal rich coating consist of

metallic clusters embedded into an
amorphous aluminium oxide ma-
trix. An oxygen rich coating has
an amorphous structure. Both of
these coatings exhibit gas barrier
performance, comparable to that of
standard metallised film. Figure 1
shows the schematic of AlOx pro-
duction process inside a standard
aluminium vacuum web metalliser.
The reactive balance between the
amount of oxygen and aluminium
is very important. In the oxygen
rich AlOx coating process, the coat-
ing can be clear with an amorphous
structure, but if the amount of ox-
ygen is very high the structure can
become porous resulting in a poor
barrier. If the amount of oxygen is
“The reactive balance
between the amount of Energy Dispersive X-ray analysis bonyl groups in the polyester re- Figure 3:
oxygen and aluminium is system. sulting in a good barrier. Plasma assisted AlOx Depo-
Barrier properties of Polyester sition.
very important.”
film coated with an oxygen rich or b. Plasma Assisted Deposition
reduced the final AlOx coating will metal rich AlOx using thermal reac- of AlOx
be metal rich with a grey to dark tive evaporation of aluminium with
colour. A closed loop feedback con- oxygen usually shows OTR and In this process a plasma source with
trol system is usually used to con- WVTR levels <5. However, by us- a gas such as argon is employed to
trol the optical density of the AlOx ing a pre and post plasma treatment ionise the oxygen atoms, thus en-
coating as a function of the alumin- during the process the barrier level hancing the chemical reaction with
ium evaporation rate and oxygen can be reduced to <3. For polypro- aluminium. Figure 3 shows a sche-
flow rate or pressure. pylene, the barrier property of the matic diagram of the plasma assist-
Figure 2 shows EDX analy- AlOx coating depends strongly on ed deposition of AlOx.
sis of PET film coated with clear many factors including the initial In this process ion gun or a
AlOx, which has been deposited at surface condition and the growth magnetron plasma source is used
high oxygen pressure. This coating mechanism of the AlOx coating. It to bombard oxygen and alumini-
shows a very low amount of alu- is possible that the low interaction um molecules with argon ions to
minium compared to oxygen peak. between hydrocarbon groups in the increase ionisation and, thus en-
Such a coating is characterised by polypropylene and the aluminium hance the chemical reaction. This
a porous structure and poor barrier. atoms plays an important role in process produces a dense AlOx coat-
EDX analysis results were obtained the final barrier level. On the other ing structure with high barrier and
using the FEI Quanta 250 ESEM hand, there is a strong bonding be- optical transparency. In this pro-
microscope interfaced to the EDAX tween alumina layer and the car- cess the plasma source produces an
argon ion density of about 1x1012
adphos Digital Printing GmbH ion/cm3. Upon collision with oxy-
Bruckmuehler Str. 27 · D-83052 Bruckmuehl gen atoms and aluminium mole-
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cules, argon ions cause further ion-
High speed drying solutions for thermal processes isation of both species leading to
with the fastest processing technology world wide! enhanced chemical reaction. Plas-
adphosNIR®-technology provides a ultrafast and controlled ma assisted reactive coating of AlOx
drying of ink and/or curing of other coated surfaces can produce OTR and WVTR level
• less than half a second or even of 0.5–0.1 in PET. The barrier lev-
within milliseconds
• defined controlled and reproducible
• on temperature sensitive materials
• energy efficiently
adphosNIR® –
The ultimate drying technology Figure 4:
for different drying applications! SEM picture of AlOx pro-
duced by plasma assisted
deposition process.

4 www.packagingfilms.com PackagingFilms

el of OPP can be improved by us-
ing this process but the final level
depends strongly on the initial film
surface condition and the AlOx/Film
interface formation.
Figure 4 shows the surface to-
pography of a PET film coated with
AlOx using Plasma assisted pro-
cess. High resolution surface mi-
crographs were obtained using the
Philips XL30 SFEG Scanning Elec-
tron Microscope.
Final product
Clear barrier vacuum coated films,
particularly those produced by re-
active thermal evaporation of alu-
minium with oxygen, are usually
laminated or coated with a top coat
for retort or non retort application.
The laminated substrate or top coat
enhances the moisture and oxygen
barrier of the structure. Lamination
also protects the coating from me-
“With a plasma assisted
deposition of AlOx on
PET film the WVTR and
OTR values are <0.5
without lamination.”
chanical damages during convert-
ing processing.
Heat sealable resin top layer
is formed by the dry lamination
method. A thermoplastic polymer
forming a heat sealable resin layer
may be used as long as the sealant
adhesive level can be sufficiently
achieved. Polyethylene resins such
as PE, LDPE, LLDPE, PP resin, eth-
PackagingFilms
ylene-vinyl acetate copolymer and
ionomere resin can be used to pro-
tect the AlOx coating .
Figure 5 shows the barrier level
improvement in the AlOx and Sili-
con Oxide (SiOx) clear barrier coat-
ing prepared by thermal evapora-
tion after lamination. With a plas-
ma assisted deposition of AlOx on
PET film the WVTR and OTR values
are <0.5 without lamination.
Conclusion
In comparison with wet polymeric
atmospheric coating, AlOx vacuum
coating requires only a small frac-
tion of the thickness of the equiv-
alent atmospheric coated layer to
produce similar functionality. Typ-
ically, atmospheric coatings are
measured in micrometres (10–6 m)
while, vacuum coated AlOx layer is
measured in nanometres (10–9 m).
This reflects a huge environmental
and economic advantage for vacu-
um coating technology.
AlOx is a natural oxide and non-
dangerous to the environment or
individuals. Recycling and waste
www.packagingfilms.com
Technic al Articles
Figure 5:
Barrier properties of AlOx
and SiOx on PET after
lamination.
management is relatively cheap
and simple. In combination with a
compostable substrate, it can even
be fully bio-degradable.
Metallising of transparent AlOx
barrier coating can be accom-
plished by a standard or specialised
vacuum web metallisers. Selecting
the most convenient clear barrier
AlOx process depends on the ap-
plication. For a medium barrier, re-
active thermal evaporation of alu-
minium with oxygen is used. For a
high barrier requirement plasma as-
sisted deposition process is recom-
mended. n
Nadir A G Ahmed
He is a Professor of Advanced Materi-
als and Nanotechnology, and founder
and managing director of Idvac ltd.
His main research interests are in ad-
vanced materials using vacuum thin
films and nanotechnology to develop
new processes for packaging, securi-
ty holograms, solar window films and
smart devices. He worked at Salford and Huddersfield Univer-
sities as well as the industrial sector of advanced metallisation
and optical coatings.
5
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Datum, Uhrzeit: 26.06.2016, 09:01:00
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