PACKAGING TECHNOLOGY AND SCIENCE

Packag. Technol. Sci. 2003; 16: 149–158

DOI:10.1002/pts.621

Recent Innovations in Barrier Technologies for

Plastic Packaging – a Review
By J. Lange# and Yves Wyser*
Packaging Laboratory, Nestlé Research Centre,Vers-chez-les-Blanc, CH-1000 Lausanne 26, Switzerland

The barrier solutions presently available on the market all have their drawbacks,
e.g. cost, water-sensitivity, opacity or perceived environmental bad-will. At the
same time there is a trend to use more plastic-based packaging materials for
different applications, e.g. as replacements for metal and glass containers. This
situation has stimulated the industry to provide new, more efficient barrier
solutions. The innovations go along five major lines: (a) thin, transparent vacuum-
deposited coatings; (b) new barrier polymers as discrete layers; (c) blends of barrier
polymers and standard polymers; (d) organic barrier coatings; and (e)
nanocomposite materials. This paper provides a comprehensive review of the
different approaches, outlining the principle behind each barrier technology, its
performance, its potential and the companies developing and producing the
materials. Copyright © 2003 John Wiley & Sons, Ltd.
Received 21 March 2002; Revised 26 June 2003; Accepted 11 July 2003
KEY WORDS: barrier; oxygen; gas; innovation; shelf-life; barrier polymer; vacuum-deposited
coating; blending; nanocomposite

INTRODUCTION the use of plastic barrier packaging, and finally

Although a large number of barrier solutions
are available on the market, they all have their
drawbacks, e.g. cost, water-sensitivity, opacity or
limited mechanical resistance. At the same time
there is a trend to use more plastic-based packag-
ing materials for different applications, e.g. as
replacements for metal and glass containers, which
stimulates the industry to provide new, more effi-
cient barrier solutions. Currently, a number of dif-
ferent barrier technologies are being developed
and are making their way into the marketplace. It
is the aim of the present article to provide a back-
ground to, and an overview of, these develop-
ments. The paper starts with an outline of barrier
technologies and solutions that are in use today,
then presents some current trends influencing
reviews recent innovations in materials for high-
barrier flexible and rigid plastic packaging.
BACKGROUND
Barrier approaches and
current solutions
In principle, a barrier function can be incorporated
into a plastic-based packaging material in two
different ways, either by adding a layer of barrier
material or by mixing the barrier material into the
base polymer.
For flexible materials, the traditional barrier
layer has been aluminium, at first in the form of a

* Correspondence to: Y. Wyser, Packaging Laboratory, Nestlé Research Centre, Vers-chez-les-Blanc, CH-1000 Lausanne 26,
Switzerland.
Email: yves.wyser@rdls.nestle.com
#
Present address: Amersham Biosciences, S-751 84 Uppsala, Sweden.

Copyright © 2003 John Wiley & Sons, Ltd.

Packaging Technology

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J. LANGE AND Y. WYSER

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Table 1. Permeability of polymers commonly used in packaging1

Oxygen permeability at Water vapour permeability at

23°C 50% or 0% RH 23°C 85% RH
Polymer [cm3 mm/(m2 day atm)] [g mm/(m2 day)]

Poly(ethylene terephthalate) (PET) 1–5 0.5–2

Polypropylene (PP) 50–100 0.2–0.4
Polyethylene (PE) 50–200 0.5–2
Polystyrene (PS) 100–150 1–4
Poly(vinyl chloride) (PVC) 2–8 1–2
Poly(ethylene naphthalate) (PEN) 0.5 0.7
Polyamide (PA) 0.1–1 (dry) 0.5–10
Poly(vinyl alcohol) (PVAL) 0.02 (dry) 30
Ethylene vinyl alcohol (EVOH) 0.001–0.01 (dry) 1–3
Poly(vinylidene chloride) (PVDC) 0.01–0.3 0.1

Table 2. Barrier properties of common flexible packaging films.The polymer abbreviations are
defined in Table 1.The number after each polymer is the layer thickness (mm)
Oxygen transmission rate Water vapour transmission rate
at 23°C 50% RH at 23°C 85% RH
Film [cm3/(m2 day atm)] [g/(m2 day)]

PET 12/Alu* 9/PE 50 0 0

PET 12/met.**/PE 50 1–2 0.1–0.5
PET 12/EVOH 5/PE 50 1 2–4
PET 12/PVDC 4/PE 50 5 2
PET 12/PVAL 3/PE 50 2 4–6
PET 12/PE 50 15–20 4–6
* Aluminium. ** Vacuum-deposited aluminium layer.

sheet a few micrometers thick and more recently
as a vacuum-deposited coating (metallization)
with a thickness in the nanometer range. An alu-
minium sheet provides a virtually total barrier,
whereas metallized layers may give almost as
high barriers at a lower cost. Another widely-used
method of creating a barrier layer is by lamination
or co-extrusion with a high-barrier polymer,
such as poly(vinylidene chloride) (PVDC), ethyl-
ene vinyl alcohol (EVOH), poly(vinyl alcohol)
(PVAL) or polyamide (PA). Many of these poly-
mers (e.g. PVAL, EVOH and most PAs) are good
oxygen barriers only in the dry state, which means
that they have to be sandwiched between water
vapour barrier films in order to maintain their
oxygen barrier function. Tables 1 and 2 present the
permeability of some commonly used polymers
and currently available flexible films with barrier
layers.1
For rigid packaging, a layer approach, realized
through co-injection and employing similar poly-
mers, as in the case of flexible laminates, is also in
use. The water sensitivity of some of the polymers
utilized is again a limitation, requiring sand-
wiching of the barrier layer between water barrier
materials in certain cases. Table 3 shows the per-
meability of common rigid packaging solutions.
†
In-house measurements performed using an Oxtran 2/20
from Mocon Inc, US (oxygen transmission rate) and a MAS
1000 from Mas Technologies, US (water vapour transmission
rate). All measurements were carried out on a minimum of
four samples.

Copyright © 2003 John Wiley & Sons, Ltd. 150 Packag. Technol. Sci. 2003; 16, 149–158

RECENT INNOVATIONS IN BARRIER TECHNOLOGIES
Table 3. Barrier properties of rigid containers
Oxygen transmission
Container composition rate at 23°C 50% RH
and size [cm3/(pack day atm)]
PP, 900 ml 6 through packaging waste disposal. Consumers
PP/PA, 530 ml 0.4
PP/EVOH/PP, 300 ml 0.2
HDPE, 500 ml 4
HDPE/PA, 500 ml 0.3–0.4
HDPE/EVOH/HDPE, 650 ml 0.1–0.2
PET, 500 ml 0.2–0.4
PET/PA, 500 ml 0.1–0.2
PET/EVOH/PET, 500 ml 0.1
Blending is an alternative route to improved
barrier properties. The mixing of a high-barrier
material into the matrix of a common film or bottle
polymer leads to an increase in effective path
length for the diffusing compound (increase in tor-
tuosity) and thereby to an improvement in barrier
performance. The high-barrier material can be a
polymer or inorganic filler. The improvement is
strongly dependent on the morphology of the
obtained blend or composite. This will be further
discussed below.
Consumer trends
A number of trends, expressed through consumer
demands, can be identified. One issue is the
increasing demand for transparency, where a
package combining good barrier properties with
product visibility is required. Obviously, alu-
minium and metallized coatings are unable to
provide this combination of properties, whereas
polymer-based barriers are well suited. The degree
of transparency of a polymer layer will depend on
its structure (amorphous, i.e. transparent, or crys-
talline, i.e. translucent) and its thickness. In some
cases, e.g. for replacing canning by retorting in
flexible pouches for shelf-stable products, the
barrier should ideally be both heat-resistant and
transparent. For many applications, there are con-
flicting interests between product visibility and
light protection. To some extent, the problems can
be alleviated by using small see-through windows
rather than fully transparent packages, and by
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using polymer additives that filter part of the light
spectrum.
There is a desire to avoid aluminium and chlo-
rine, mainly for environmental reasons. Chlorine,
present in PVDC and poly(vinyl chloride) (PVC),
may lead to toxic dioxins on combustion, e.g.
perceive aluminium and, to a lesser degree, metal-
lized layers, to be environmentally unfriendly. The
reason is the high amount of energy required to
produce aluminium. This trend started in the
German and Scandinavian markets, and is spread-
ing throughout the world.
Another trend is the move toward fresher prod-
ucts with shorter shelf-life. Instead of formulating
products for deep freezing or a canning or retort-
ing process, they are developed for chilled and
possibly modified atmosphere packaging. This
requires flexible packaging materials with good
and sometimes selective barrier properties in
combination with high transparency, good print
quality, etc.
There is a demand for more convenient packag-
ing, with good opening and re-closing functions,
and with the ability of sustaining preparation of
the packed product through, for example, boiling
or microwave heating. This places particular
demands on package design, but also requires spe-
cific material characteristics, such as heat resis-
tance and appropriate mechanical properties.
Technological trends
The sensitivity of many barrier polymers to water
vapour has already been mentioned. Since the
procedure of always placing the oxygen barrier
between two water vapour barrier layers is costly,
there is a demand for oxygen barriers that retain
their properties in the presence of water.
There are also the sometimes contradictory
demands for higher processing (line) speeds and
reduction in packaging material consumption
(down-gauging). The cost of the packaging mater-
ial represents 17% of the total cost of goods pro-
duced (Nestlé average), which means that there is
a potential for savings through source reduction.
At the same time there is a desire to increase pro-
ductivity. With increasing line speeds, the stress
and strain on the packaging material also increase,
which means that in the end the material has to be
151 Packag. Technol. Sci. 2003; 16, 149–158
Packaging Technology
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simultaneously thinner and stronger. The barrier
layers are often particularly sensitive to deforma-
tion, and it has to be ensured that the barrier per-
formance is not lost during processing.2
There is a general trend to move from glass to
plastic bottles, and a growing tendency to replace
glass also for sensitive beverages such as beer and
fruit juice. The reasons are several – potential cost
savings, weight reduction and reduced breakage.
The demands placed on the plastic bottles in these
applications are, among other things, a high bar-
rier against oxygen, chemical resistance (against
cleaning chemicals in re-use schemes), heat resis-
tance (for hot filling) and recycleability. Since the
technique of co-injection is costly, there is also a
demand for other ways of improving the barrier
properties.
Being innovative and making continuing efforts
for source reduction is obviously a key to cost
reduction. However, the packaging material devel-
opment should consider the total costs (including
e.g. line efficiency, investment, labour and quality
control), which means that there may be room for
a more expensive material if it allows saving else-
where, e.g. through a more efficient line operation.
EMERGING BARRIER
TECHNOLOGIES
Over the last few years, there has been a lot of
development in the area of new barrier technolo-
gies.3,4 The innovations go along five major lines:
(a) thin, transparent vacuum-deposited coatings;
(b) new barrier polymers; (c) blends of barrier
polymers and standard polymers; (d) organic
barrier coatings or adhesives; and (e) nanocom-
posite materials. One major driver for barrier
development has been the desire to find a plastic
beer bottle, i.e. capable of protecting beer against
oxidation for at least 6 months. Several of the tech-
nologies primarily developed for this application
have then been transferred to other areas of
packaging.
Thin coatings
Thin glass-like SiOx films can be produced by
physical vapour deposition (PVD) of SiO, or
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J. LANGE AND Y. WYSER
plasma-enhanced chemical vapour deposition
(PECVD) of gaseous organosilane and oxygen, on
poly(ethylene terephthalate) (PET), polypropylene
(PP) or PA.5–7 The development of these technolo-
gies started in the mid-1980s for PVD and early
1990s for PECVD and, although materials are
commercially available, their use increases rather
slowly. SiOx films are transparent, water-resistant,
retortable, microwaveable and provide barriers
comparable to the ones obtained by metallization.
Data for SiOx barrier films on different substrates
are presented in Table 4. The main drawbacks with
these materials are the limited flex and crack resis-
tance of the SiOx layer and the relatively high
production costs. The mechanical resistance can
be improved by covering the SiOx layer with a
varnish, or by lamination of the SiOx-coated sub-
strate. SiOx-coated, materials are produced by,
among others, Alcan Packaging, 4P Ronsberg and
Mitsubishi.5 For PET bottles, TetraPak has devel-
oped a technology called Glaskin, where a thin
layer of SiOx is deposited through microwave
PECVD on the inside of the bottle after stretch
blow-moulding. Barrier data for Glaskin bottles
can be found in Table 5. A number of Japanese sup-
pliers have also developed similar technologies.
Krones and Leybold have developed a technique
in which the silica is deposited on the outside of
the bottle.8 Data for these bottles are given in Table
5. Recent publications indicate that the future
trend in the development of this coating lies
in deposition at atmospheric pressure, either by
using flame treaters9 or atmospheric plasma
generators.10
Another technology, developed by the Fraun-
hofer Institute in Wurzburg, is inorganic–organic
hybrid polymers known as ormocers. These mate-
rials are produced through sol–gel chemistry and
deposited as coatings or adhesive layers with a
thickness in the micrometer range. They can
be used independently to obtain a moderate bar-
rier improvement or in combination with SiOx,
in which case very high-barrier materials are
obtained.11 Table 4 gives barrier data for some
ormocer materials. To our knowledge, this tech-
nology remains at a laboratory level.
With PECVD it is also possible to deposit hydro-
carbon (HC) films on different substrates.12 Such
films present properties and barrier performance
similar to SiOx but with a higher mechanical resis-
tance. The development of this technology has pro-
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RECENT INNOVATIONS IN BARRIER TECHNOLOGIES

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Table 4. Barrier properties of newly developed barriers for films.The number after each polymer
is the layer thickness (mm).The values for untreated PET and PP are shown for comparison
Oxygen Water vapour
transmission rate transmission
at 23°C 50% RH rate at 23°C 50% Resistance to
Film/treatment [cm3/(m2 day atm)] RH [g/(m2 day)] deformation Reference

PET 12/SiOx 0.5–5 0.2–5 OK to 4% 5

PP 20/SiOx 1–20 0.1–1 5
PA 20/SiOx 1 0.5 5
PET 12/Ormocer 20–27 14 9
PET 12/SiOx/Ormocer 0.05 0.1 9
PP 20/Ormocer 13–16 0.8 9
PP 20/SiOx/Ormocer 0.05 0.1 OK to 5% 9
PET 12/HC plasma 1–2 OK to >5% 10
PP 20/HC plasma 50 10
PET 12/melamine 1 14
PP 20/melamine 30 14
PET 12/LCP 4 2–7 0.9–2 Calculated from 15
PP 20/LCP 4 3–8 0.6–0.8 Calculated from 15


PET 12/epoxy coating 10 15–20 15
PET 12/hyperbranched 10 50–60 15
PP 30/hyperbranched 10 130–160 1 See footnote† on p. 
PET 12 110 15
PP 20 1500–1800 1–1.5

Table 5. Relative barrier performance of newly developed rigid packaging

Relative oxygen transmission

Container composition (supplier) rate at 23°C 50% RH Reference


PET 1
PET/SiOx (Tetrapak) 0.04–0.08
PET/SiOx (Krones) 0.4
PET/SiOx (Toppan) 0.1
PET/hydrocarb. plasma (Sidel) 0.1–0.2
PET/hydrocarb. plasma (Kirin) 0.3 See footnote† on p. 
PET/epoxy coating (PPG) 0.6
PET/thermoplastic epoxy (Tetrapak) 0.5
PET/PEN blend 0.2–0.8
PET/PA blend 0.8
PET/PA nanocomposite (Eastman) 0.4–0.7
PET/LCP 0.1 21
PET nanocomposite (Tetrapak) <0.3 41

gressed since the mid-1990s. However, cost is
an issue and to date no material has been made
commercially available, although Amcor (formerly
Akerlund and Rausing) are reported to have built
a production facility. A consortium of suppliers
around the EMPA in Switzerland have also devel-
oped materials based on this approach.12 Data for
hydrocarbon films on PET are given in Table 4. A
similar technique, the Actis process, has been
developed for coating PET bottles by the com-
pany Sidel and has been commercially available
since the late 1990s. Here a hydrocarbon film is

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J. LANGE AND Y. WYSER

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Table 6. Summary of suppliers and the barrier technologies they are developing or have
introduced in the market
Trade Development
Supplier Barrier technology name Application status

Lawson Mardon Coating/SiOx Ceramis Film Commercial

4P Ronsberg Coating/SiOx Film Commercial
Mitsubishi Coating/SiOx Film Commercial
TetraPak Coating/SiOx Glaskin Bottles (inside) Commercial
Toppan Coating/SiOx Bottles (inside) Commercial
Krones Coating/SiOx Bestpet Bottles (outside) Commercial
Fraunhofer Coating/organic–inorganic Ormocer Film Laboratory
Amcor (Akerlund and Rausing) Coating/Hydrocarbon Film Development
Swiss industry/EMPA Coating/Hydrocarbon Film Development
Sidel Coating/Hydrocarbon ACTIS Bottles (inside) Commercial
Kirin Coating/Hydrocarbon DLC Bottles (inside) Commercial
DSM/Fraunhofer Coating/melamine Film Laboratory
Ticona New polymer/LCP Vectran Film Commercial
Procter & Gamble New polymer/PHBH Nodax Commercial
Dow Chemical New polymer/epoxy BLOX Film and bottles Commercial
TetraPak/Dow New polymer/epoxy Sealica Bottles (outside) Commercial
DuPont Blend/EVOH and PE Development
BP Amoco Blend/Polyketone Development
Superex Inc Blend/LCP and PET or PA Films and bottles Commercial
Eastman Blend/PEN & PET Bottles Commercial
Nanocor/Amcol Int. Nanocomposites Nanomer Development
EMS Chemie Nanocomposites/PA Film Commercial
Ube Nanocomposites/PA Film Commercial
Allied Signal Nanocomposites/PA Development
Bayer Nanocomposites/PA Development
Honeywell Nanocomposites/PA Aegis Commercial
ICI/DuPont Nanocomposites/PET Film Development
Eastman Nanocomposites/PET Bottles Development
TetraPak Nanocomposites/PET Bottles Laboratory
ICI Nanocomposites/melamine Bottles (outside) Development
PPG Industries Nanocomposites/epoxy Bottles (outside) Development
PPG Industries Organic coating/epoxy Bairocade Bottles (outside) Commercial

deposited by PECVD on the inside of each bottle
after blow-moulding.13,14 The coating reduces the
oxygen permeability by a factor of up to 10 (see
Table 5).
In the late 1990s, DSM, in collaboration with the
Fraunhofer Institute in Munich, developed a PVD
method for deposition of melamine, which yields
thin, transparent layers with very low oxygen per-
meability.15,16 This technology, which still is in a
development stage, has the potential of being
low-cost, since melamine is a low-price commod-
ity chemical and the PVD process is technically
straightforward. However, as melamine is soluble
in water, the water sensitivity of the films can be
expected to be high, which limits the potential of
the approach. Data for melamine coatings on PET
and PP are given in Table 4.
An overview of the types of coatings developed
by different suppliers is provided in Table 6.
New barrier polymers
Several suppliers have brought or are bringing
new barrier polymers to the market. One example
is Ticona, who have developed a new version of
the classic aromatic polyester, liquid crystalline
polymer (LCP). The new polymer is translucent in
thin layers (other LCP materials are quite opaque,
even in very thin layers) and has an oxygen per-

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RECENT INNOVATIONS IN BARRIER TECHNOLOGIES
meability 50–100 times lower than PET. Ticona has
also developed tie layers for co-extruding the LCP
with most of the common packaging polymers.17
Indications of the barrier performance that can be
achieved with laminate structures are given in
Table 4. However, the material is expensive and to
date no packaging applications have been devel-
oped. Further recent development in the area of
new barrier polymers are the thermoplastic epoxy
resins [poly(amino ethers)] produced by Dow and
sold under the name Blox.4,18 These resins can be
employed for co-extrusion, over-injection (a first
application has been developed for PET bottle
preforms with TetraPak and has been commercial-
ized under the name Sealica19,20) or as barrier
adhesives.21 The resins typically have oxygen
permeability coefficients 50 times lower than PET.
Data for a bottle with Sealica is presented in Table
5. Procter and Gamble, together with Kaneda
Corp, are bringing a biodegradable polymer with
barrier properties resembling those of EVOH to
the market. In addition to low oxygen permeab-
ility, the polymer, poly(3-hydroxy butyrate co 3-
hydroxy hexanoate) (PHBH), is reputed to
have good resistance to grease and to be heat-
sealable.22,23
Blends
Blending is a way of producing barrier materials
using only limited amounts of the often expensive
barrier polymer in an inexpensive matrix ma-
terial.3,24 It is also a less complicated and therefore
a less costly technology than e.g. co-extrusion or
co-injection. However, it should be noted that
blends are as difficult to recycle as layered materi-
als. In general, the properties of the blend will fall
between those of the components, but in some
cases synergies arise and the blend obtains
improved properties. A common objective of
blending is to improve the deficient properties
while maintaining as much as possible of the desir-
able properties of the major components. For a
blend, the barrier properties will be strongly in-
fluenced by the morphology, and a lot of the
development is aimed at obtaining favourable
structures maximizing the tortuosity of the diffu-
sion path. The blend morphology arises as the
result of a complex interplay between the process-
ing conditions and the physical and chemical char-
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acteristics of the polymer components. Often com-
pounds capable of improving the adhesion and
interaction between the polymer phases (compati-
bilizers) are added. The structures that can be
obtained range from fully laminar systems, where
the barrier polymer is present as a continuous
layer, over interleaved sheets and lamellar or
fibrillar morphologies to particulate systems. In
Figure 1 the barrier properties of a blend as a func-
tion of the morphology is schematically illustrated.
Some of the blends that have been developed are
EVOH in PP,24, in PE25 or in PA,26,27 PA in PP28 or
PET,3 aliphatic polyketone in PE29 or in PVC,30 and
LCP in PET31 and in PE.32 Work is also under way
on blends of polyethylene naphthenate (PEN) in
PET and PA.3 Companies active in this area
are, among, others, DuPont with EVOH in PE,
Eastman with PEN in PET, and British Petroleum
with polyketone blends. Superex Polymer Inc has
developed processing equipment for making
blends of LCP in PET and PA. Data for PET/LCP
blend bottles is presented in Table 5. In the cases
where favourable morphologies are obtained,
barrier improvements of between 2 and 10 times
with respect to the base polymer are reached for
levels of 5–30% barrier polymer in the blend. In the
case of EVOH in PE, it has also been found that the
barrier properties of the blend are less sensitive to
humidity than in the case of a laminate.
Development work on blends has been ongoing
for several decades. The main challenge is obtain-
ing a favourable morphology at a reasonable cost.
Table 6 summarizes the different polymers and
blends developed by different suppliers.
Organic barrier coatings
In most cases packaging films are coated with
layers such as adhesives (e.g. for lamination),
printing inks and varnishes. Work has been per-
formed in trying to modify the formulations of the
coating resins so that they improve the barrier per-
formance of the film. Similar technologies are
already in use for plastic bottles, where an epoxy-
amine coating improves the oxygen barrier of PET
by a factor of 2 or more (Bairocade product from
PPG Industries, commercial since the mid-1990s:
data in Table 5).3,33,34 Such coatings could also
be applied to films and laminates.35 Candidate
polymers for use as binders in ink formulations
155 Packag. Technol. Sci. 2003; 16, 149–158
Packaging Technology
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Blend permeability
Permeability
B
A
0 C Particulate system
100
Volume percent
Figure 1. Schematic illustration of the permeability of a blend of a
high-barrier material in a low-barrier matrix as a function of the
morphology.29
are PAs, polyurethanes, polyacrylates and resins
derived from hyperbranched polymers.36,37 This
development is still at the laboratory stage. Values
for hyperbranched coatings on PET and PP sub-
strates are presented in Table 4. For adhesives,
polyurethanes and polyacrylates have been pro-
posed. With these technologies only a moderate
barrier improvement is to be expected, but the
added cost should also be small.
Table 6 lists the suppliers of barrier coatings.
Nanocomposites
The term ‘nanocomposites’ refers to polymers
filled with small inorganic particles with a high
aspect ratio. With the current interest in nanotech-
nologies, nanocomposite materials have become a
very hot topic, especially for academic research.38
As regards barrier properties, an improvement is
obtained by increasing the tortuosity of the diffu-
sion path and, as in the case of blends, the result is
strongly dependent on the morphology. The use of
small particles, typically 100–1000 ¥ 1 nm in size,
and moderate filler levels, means that the resulting
material in most cases remains transparent. Differ-
ent modelling approaches have shown that signifi-
cant barrier improvement factors of the order of 50
or higher, can be achieved with high aspect ratio
filler particles.39,40 This technology was first devel-
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J. LANGE AND Y. WYSER
A Laminar structure
B Lamellar blend
oped for automotive applications by Toyota in the
1980s, and has in the past years been extended to
packaging applications. As fillers, different types
of clays are employed, and the matrix can be vir-
tually any polymer. The difficulty lies in dispers-
ing the filler in the matrix (i.e. obtaining
intercalation and exfoliation). This is much easier
to achieve in low molecular weight substances
than in highly viscous polymers, which is why it
often is attempted to prepare composites by in situ
polymerization of a monomer – filler blend.
However, this approach has so far only been
achieved with a limited number of polymers, e.g.
PAs, thermosetting epoxies and, to some extent,
PET.3,41,42 For other polymers, the filler has to be
directly dispersed in the molten, highly viscous
material, something that is quite difficult to
achieve. At present, dispersion is generally only
obtained through the addition of compatibilizers
that significantly add to the cost of the material.
Companies developing and/or producing
nanocomposite materials are Nanocor (part of
Amcol International), TetraPak and Eastman with
PET materials,43–46 ICI with PET (business since
then sold to DuPont)47 and Ube, Allied Signal,
Bayer48 and EMS Chemie with PA-based systems.
At present, only the PA nanocomposite materials
are commercially available. Nanocomposite ther-
moset coatings have also been developed by ICI
and PPG Industries.42,49 Barrier improvements of a
156 Packag. Technol. Sci. 2003; 16, 149–158

RECENT INNOVATIONS IN BARRIER TECHNOLOGIES
factor between 2 and 20 compared to the pure
polymer for filler levels of 1–5% have been
reported.3,43 An example of the barrier improve-
ment that can be obtained with a PET nanocom-
posite bottle is given in Table 5. If the problems
with dispersion can be overcome at a reasonable
cost, it is believed that the technology will be
extended to polyolefin and polystyrene matrices in
the near future. In Table 6, a list of suppliers active
in the nanocomposite area can be found.
CONCLUSIONS
A number of trends can be seen in the marketplace.
Consumers demand transparency, avoidance of
aluminium and chlorine, fresher products and
increased packaging convenience. At the same
time there is a push towards increased line speeds
and reduced material consumption, as well as a
move from metal and glass to plastic packaging.
Over the last few years, there has been a lot of
development in the area of new barrier technolo-
gies. For both flexible materials and rigid contain-
ers, the innovations go along five major lines: (a)
thin, transparent vacuum-deposited coatings; (b)
new barrier polymers as discrete layers; (c) blends
of barrier polymers and standard polymers; (d)
organic barrier coatings; and (e) nanocomposite
materials.
For flexible materials, it can be seen that the thin
coatings perform well, are already available on the
market, but remain sensitive to mechanical defor-
mation. New polymers, such as LCPs, show
promising properties but remain costly. Blends and
nanocomposites are still largely under develop-
ment, whereas the organic barrier coatings and
adhesives have the potential of providing barrier
improvement at minimal added cost.
As regards bottles, both thin coatings and
organic coatings have proven their performance,
and have been introduced in the market, blends
are available but show limited performance,
whereas nanocomposites are promising but largely
still under development.
ACKNOWLEDGEMENT
C. Pelletier is thanked for having performed the oxygen
and water vapour permeability measurements.
Copyright © 2003 John Wiley & Sons, Ltd.
Packaging Technology
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and Science
REFERENCES
1. PDL Handbook Series, Plastics Design Library.
Permeability and Other Film Properties of Plastics and
Elastomers. William Andrew Inc. Norwich, NY, 1995.
2. Hertlein J. Investigation of the changes in barrier
properies of metallized films during processing.
PhD Thesis. Herbert Utz Verlag: Munich, 1998 (in
German).
3. Strupinsky G, Brody A. A twenty-year retrospective
on plastics: oxygen barrier packaging materials.
TAPPI Polymers, Laminations and Coatings Con-
ference Proceedings, San Francisco, CA, 1998; 119.
4. Silvis HC. Recent advances in polymers for barrier
applications. Trends Polymer Sci. 1997; 5: 75.
5. Lohwasser W, Frei O. Breakthrough in commercially
produced SiOx-films in Europe – It will happen. Pro-
ceedings of Flex-Pak Europe ’99, Amsterdam, The
Netherlands, 1999; 97.
6. Garbassi F, Occhiello E. Plasma deposition of
silicon-containing layers on polymer substrates.
Macromol. Symp. 1999; 139: 107.
7. Erlat AG, Spontak RJ, Clarke RP et al. SiOx gas barrier
coatings on polymer substrates: morphology and
gas transport considerations. J. Phys. Chem. 1999;
103: 6047.
8. Anon. Coca-cola’s barrier technology to double PET
shelf-life. Packag. World 1999; 11: 2.
9. Eckert W. Improvement of adhesion on polymer
film, foil and paperboard by flame treatment. Pro-
ceedings of TAPPI 9th European PLACE Confer-
ence, Rome, Italy, 2003.
10. Wolf R, Ellwanger RE. Inline functional coatings of
surfaces via plasma CVD at atmospheric pressure.
To be published at the PLACE Conference and the
Global Hot Melt Symposium, Orlando, FL, 2003.
11. Zehentner B. Transparent, flexible high-barrier films
prepared by vapour deposition of inorganic layers
in combination with inorganic-organic hybrid
polymers. Report from Coating Technologies AG,
Dieselstrasse 8, D-66763, Dillingen/Saar, Germany
(in German).
12. Moser EM, Urech R, Hack E, Künzli H, Müller E.
Hydrocarbon films inhibit oxygen permeation
through plastic packaging material. Thin Solid Films
1998; 317: 388.
13. Anon, Sidels ACTIS plasma technology. Packag.
Strategies 1999; 17: (5, No. 14).
14. ACTIS. Amorphous Carbon Treatment on Internal
Surface. Product information from Sidel SA, Le
Havre, France, 1999.
15. Jahromi S, Moosheimer U. Oxygen barrier coatings
based on supramolecular assembly of melamine.
Macromolecules 2000; 33: 7582.
16. Jahromi S. A novel high barrier coating for clear
flexible packaging applications. Proceedings of
Flex-Pak Europe ‘99, Amsterdam, The Netherlands,
1999; 179.
17. Ticona product information. Vectran Liquid Crys-
talline Polymer. Exceptional Barrier Packaging
157 Packag. Technol. Sci. 2003; 16, 149–158
Packaging Technology
and Science
Resins for Conventional Film-converting Equip-
ment. Ticona Celanese AG, Frankfurt am Main,
Germany, 2000.
18. Brennan DJ, Silvis HC, White JE, Brown CN. Amor-
phous phenoxy thermoplastics with an extraordi-
nary barrier to oxygen. Macromolecules 1995; 28:
6694.
19. Scherb P. New barrier technologies for PET bottles.
Drink Technol. Marketing 2000; September: 32.
20. Leaversuch RD. Novel epoxy enhances design in
multilayer bottles. Mod. Plastics 2000; February: 58.
21. Dow Plastics product information. Blox 000 and
4000 Series High-adhesion Barrier Resins, and Blox
200 Series Adhesive Resins. Dow Chemical Co.
Midland, MI, 2000.
22. Anon. Developing biodgradable plastics technol-
ogy. CEPMagazine.org, December 2001, 97, 18.
23. McDonald N. Potential of Nodax biodegradable
barrier polymers in flexible packaging appli-
cations. FlexPak Americas 2002 conference pro-
gram, Schotland Business Research, Chicago, IL,
2002.
24. Faisant JB, Ait-Kadi A, Bousmina M, Deschenes L.
Morphology, thermomechanical and barrier pro-
perties of polypropylene – ethylene vinyl alcohol
blends. Polymer 1998; 39: 533.
25. Torradas JM, Zhang D. New laminar oxygen barrier
technology for food packaging applications. Pro-
ceedings of SPE ANTEC, Montreal, Canada, 1991;
1468.
26. De Petris S, Laurienzo P, Malinconico M, Pracella M,
Zendron M. Study of blends of Nylon 6 with EVOH
and carboxyl-modified EVOH and a preliminary
approach to films for packaging applications.
J. Appl. Polym. Sci. 1998; 68: 637.
27. Nir Y, Narkis M, Siegmann A. Permeation through
strongly interacting polymer blends: EVOH/
Copolyamide-6/6.9. Polym. Networks Blends 1997; 7:
139.
28. Citterio C, Selli E, Testa G, Bonfatti AM, Seves A.
Physico-chemical characterisation of compatibilized
poly(propylene)/aromatic polyamide blends.
Angew. Makromol. Chemie 1999; 270: 22.
29. Bonner, JG. U.S. Patent 5 859 129 (to BP Chemicals
Ltd); 1999.
30. Bonner JG, Powell, AK. U.S. Patent 5 792 530 (to BP
Chemicals Ltd); 1998.
31. Anon. LCP plus PET equals increased barrier prop-
erty. Packag. Innovation 1999; March: 5.
32. Flodberg G, Hellman A, Hedenqvist MS, Sadiku ER,
Gedde UW. Barrier properties of blends based on
Copyright © 2003 John Wiley & Sons, Ltd.
10991522, 2003, 4, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/pts.621 by Michigan State University, Wiley Online Library on [17/05/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
J. LANGE AND Y. WYSER
liquid crystalline polymers and polyethylene.
Polym. Sci. Eng. 2000; 40: 1969.
33. Carlblom LH, Seiner JA, Niederst, KW. (PPG Indus-
tries). U.S. Patent 5 902 643; 1999.
34. Defosse, MT. Innovative barrier technologies boost
viability of PET beer bottles. Mod. Plastics 2000;
March: 26.
35. Lange J, Nicolas B, Galy J, Gerard J.-F. Influence of
structure and chemical composition on oxygen
barrier properties of crosslinked epoxy-amine coat-
ings. Polymer 2002; 43: 5985.
36. Hedenqvist YH, Malmström E, Johansson M et al.
Transport properties of hyperbranched and den-
drimer-like star polymers. Polymer 2000; 41: 1827.
37. Lange J, Stenroos E, Malmström E, Johansson M.
Barrier coatings for flexible packaging based on
hyperbranched polyester resins. Polymer 2001; 42:
7411.
38. Pinnavaia TJ, Beall GW (eds). Polymer-Clay
Nanocomposites. Wiley: Chichester, 2000.
39. Gusev AA, Lusti HR. Rational design of nanocom-
posites for barrier applications. Adv. Mater. 2001; 21:
13.
40. Fredrickson GH, Bicerano J. Barrier properties of
oriented disc composites. J. Chem. Phys. 1999; 110:
2181.
41. Anon. High barrier film. Packag. Innovation 1998; 3: 1.
42. Carlblom LH, Seiner, JA. PCT Int. Appl. WO
98/24839 (to PPG Industries Inc.), 1998.
43. Frisk P, Laurent J. U.S. Patent 5 876 812 (to Tetra
Laval Holdings); 1999.
44. Rosen A. U.S. Patent 5 635 011 (to Tetra Laval Hold-
ings); 1997.
45. Matayabas JC Jr. Polymer nanocomposites for high
barrier performance PET container applications.
Proceedings of Nova-Pack Europe ’99, Neuss,
Germany, 1999, 327.
46. Matayabas JC Jr, Turner, SR. Nanocomposite tech-
nology for enhancing the gas barrier of polyethyl-
ene terephthalate. In Pinnavaia TJ, Beall GW (eds).
Polymer-Clay Nanocomposites. Wiley: Chichester,
2000.
47. Gough TC, Jeffels PM, Harrison, AG. U.S. Patent 5
667 886 (to Imperial Chemical Industries plc); 1997.
48. Schwarz P, Mahlke M. Polyamide nanocomposites
for extrusion coating applications. Proceedings of
TAPPI 9th European PLACE Conference, Rome,
Italy, 2003.
49. Harrison AG, Meredith WNE, Higgins, DE. US
Patent 5,571,614 (to Imperial Chemical Industries
plc); 1996.
158 Packag. Technol. Sci. 2003; 16, 149–158