Overview

Structural characteristics deŽ ning high barrier

properties in polymeric materials
J. M. Lagaron, R. Catala and R. Gavara

The packaging industry has dramatically increased the number of packaging systems and designs made of plastics
over recent decades. Plastics, in contrast with more traditional packaging materials such as glass and metals, are
permeable systems that permit the exchange of low molecular weight compounds, e.g. gases and vapours, between
the inner and the outer atmosphere. Despite this drawback, the availability of shapes and forms in which they can be
manufactured, their ease of processing and handling, low price, excellent chemical resistance, etc., have made them
very attractive in many packaging Ž elds. Consequently, much industrial and academic research has been devoted to
understanding the mechanisms of mass transport in polymers, to enable design of materials with improved barrier
properties. The present paper reviews some of these developments, and highlights the structural factors that cause
polymers to behave as high barrier materials, taking as benchmark the properties of one of the most widely used
family of high barrier materials, the ethylene – vinyl alcohol copolymers. MST/5992

Keywords: Polymers, High barrier properties

The authors are at the Packaging Laboratory, Institute of Agrochemistry and Food Technology, CSIC, Apdo. Correos 73, 46100
Burjassot, Spain (lagaron@iata.csic.es). Manuscript received 25 September 2003; accepted 8 October 2003.
# 2004 IoM Communications Ltd. Published by Maney for the Institute of Materials, Minerals and Mining.

use of plastic materials.1 – 3 In this respect, it has become a

Nomenclature topic of industrial and social awareness because of links
with current issues such as food commercialisation, food
aPA amorphous polyamide shelf life extension, quality and safety. Furthermore, it has
EPDM ethylene propylene diene monomer also become very relevant to a number of other applications
EVOH ethylene – vinyl alcohol copolymers including gas separation membranes, packaging of health
HDPE high density polyethylene care and pharmaceutical goods and chemicals and housing
LCP liquid crystal polymer of fuels (including oxygenated fuels) in tanks and lines in the
LDPE low density polyethylene automotive Ž eld.
LLDPE linear low density polyethylene The reasons for the more recent interest in the develop-
PA polyamide ment of high barrier polymers and polymer based structures
PAN polyacrylonitrile are associated with a widespread trend to implement poly-
PA6 polyamide 6 (nylon) meric materials in an ever increasing number of applica-
PC polycarbonate tions. It is common knowledge that the attractiveness of
PE polyethylene plastics lies in their versatility and ability to offer a broad
PET polyethylene terephthalate variety of properties, and yet be cheap and readily processed
PHA polyhydroxyalkanoates and conformed into a myriad of shapes and sizes. However,
PK aliphatic polyketone copolymers polymers have a number of limitations for certain applica-
PLA polylactic acid tions when compared with more traditional materials such
PMMA polymethyl methacrylate as metals and alloys or ceramics. Among some of these
PP polypropylene limitations relevant to the subject of the present paper are
PS polystyrene their permeability and comparatively low thermal resis-
PVC polyvinyl chloride tance, and the strong interdependence between these two
PVDC polyvinylidene chloride properties. The permeability of plastics to the exchange of
PVOH polyvinyl alcohol gases and vapours imposes a number of challenges in those
applications where a high barrier, ideally impermeability,
is required. These applications were traditionally assumed
by, for instance, tinplate and glass in the food packaging
Ž eld. However, polymer scientists, engineers and technol-
Introduction ogists in industry and academia have devoted a great deal of
effort and resources to pushing the limits of plastics
HIGH BARRIER CONCEPT performance towards impermeability, chie y because of
the overwhelming pressure exerted by the numerous other
A ‘high barrier’ is without doubt a very desirable property
advantages associated with the use of plastics in high barrier
to be exhibited by polymeric materials intended for use in
applications.
many packaging applications. The term high barrier is
usually applied in cases of low to very low permeability of a
material to low molecular weight chemical species, such as
gases and organic compounds. However, this property has PHENOMENOLOGY OF MASS TRANSPORT
perhaps never attracted so much industrial attention as over IN POLYMERS
recent decades, when it began to be associated with some According to the above, barrier properties in polymers are
modern food and beverage packaging technologies making necessarily associated with their inherent ability to permit

DOI 10.1179/026708304225010442 Materials Science and Technology January 2004 Vol. 20 1

2 Lagaron et al. High barrier properties in polymeric materials
the exchange, to a higher or lower extent, of low molecular
weight substances through mass transport processes such as
permeation. The permeation of low molecular weight
chemical species through a polymeric matrix is generally
envisaged as a combination of two processes, i.e. solution
and diffusion.4 A permeate gas is Ž rst dissolved into the
upstream face of the polymer Ž lm, and then undergoes
molecular diffusion to the downstream face of the Ž lm
where it evaporates into the external phase again. A
solution – diffusion mechanism is thus applied, which can be
formally expressed in terms of permeability P, solubility S
and diffusion D coefŽ cients by
P~DS : : : : : : : : : : : :
The permeability coefŽ cient P derives from application of
Henry’s law of solubility to Fick’s Ž rst law of diffusion,
according to
q ç c SDp Dp
J~ ~{D ~D ~DS
At ç x l l
ql
)P~DS~ : : : : : : :
AtDp
where J is the permanent  ux, q is the heat quantity, A is the
cross-sectional area, t is the time, c is the concentration,
x is the direction of mass transport, p is the pressure and l is
the thickness.
The solubility coefŽ cient S is thermodynamic in nature,
and is deŽ ned as the ratio of the equilibrium concentration
of the dissolved penetrant in the polymer to its partial
pressure p in the gas phase (Henry’s law). In polymers,
Henry’s law is usually obeyed at low penetrant concentra-
tions, i.e. when S is independent of concentration (or of the
partial pressure). The diffusion coefŽ cient D characterises
the average ability of the sorbed permeate to move through
the polymer chain segments, and is determined from Fick’s
Ž rst law of diffusion, i.e. the  ux of the permeant J is pro-
portional to the local gradient of concentration c through
the thickness of the polymer Ž lm l. During sorption kinetic
experiments, if Fickian transport (case I) is assumed, a
linear behaviour in the penetrant uptake versus t1 /2 curve at
small times is usually observed.5 Case II diffusion is deŽ ned
when linear behaviour is observed in the uptake versus t
curve. This behaviour is observed in a number of systems,
and is associated with large uptakes and plasticisation of the
structure by the penetrant. When complex sorption
behaviours, e.g. sigmoidal shapes, are observed, it is usually
assumed that an ‘anomalous’ or non-Fickian transport
occurs. Nevertheless, from recent studies, better rationalisa-
tion of these ‘anomalous’ behaviours has been achieved,
whereby contributions from the effect of macroscopic
elastic constraints arising during the swelling process
(geometric effects) in adsorption experiments have been
pointed out.6 ,7
Concerning mechanisms of the mass transport process
through polymeric materials, two general approaches can
be found, namely (a) molecular models studying the speciŽ c
penetrant and chain motions in conjunction with the
corresponding intermolecular forces, and (b) ‘free volume’
models which pay attention to the relationships between the
transport coefŽ cients and the free volume present in the
polymeric matrix, without consideration of molecular scale
mechanisms (see Ref. 8 for a review of these).
It is also relevant to emphasise here that the mass trans-
port mechanisms as well as their dependence on permeant
partial pressure and testing temperature are thought to be
generally different depending on whether the polymer is
in a rubbery or glassy state. Rubbery polymers are above
their glass transition temperature Tg , and therefore
exhibit very short relaxation times and respond quickly to
physical changes. Thus, the absorption of small molecules
or penetrants causes immediate adjustments to a new
Materials Science and Technology January 2004 Vol. 20
equilibrium state and, consequently, there appears to exist
a unique mode of penetrant transport for these polymers.
Moreover, rubbery polymers are more amenable to showing
upwardly in ecting permeability responses with increasing
penetrant partial pressure owing to plasticisation. This is
typically the case with d-limonene, a common  avour
component in fruit juices, contained in polymers such as
polyethylene and polypropylene. By comparison, glassy
polymers are below their Tg , and hence require, on average,
long timescales to relax fully. Gas transport then typically
occurs in glassy polymers under non-thermodynamic equili-
brium conditions. In this case, penetrant molecules can
: : : (1) allocate to holes on irregular cavities with very different
diffusional mobilities, and consequently more than one mode
of transport may be accessible. A ‘dual mode sorption’ model
describes satisfactorilythe dependence of transport properties
on penetrant partial pressure in glassy polymers. This model
postulates the existence of two different molecular popula-
tions dissolved in a glass: one dissolved by an ordinary
dissolution process which can typically follow Henry’s law
: : : (2) (c~Sp), and the other dissolved in a limited amount of Ž xed
microcavities which can be described by a Langmuir type
isotherm
CH bp
c~ : : : : : : : : : : : : : : (3)
1zbp
where CH is the hole saturation constant and b is the hole
afŽ nity constant. More complex sorption behaviours have
also been postulated for other glassy materials. For
instance, a modiŽ ed dual mode model requiring Langmuir
and Flory – Huggings equations was suggested to explain
the sorption of water in an amorphous polyamide.9
The present paper Ž rst gives an overview of some relevant
structural factors deŽ ning and/or altering high gas barrier
properties in polymers, and then comments on recent
developments in the Ž eld.
Structural factors determining high
barrier properties
The main structural factor determining inherent high barrier
properties in polymers is fundamentally the chemistry, but
there are also other relevant factors having a signiŽ cant
impact on barrier properties for a given chemistry, including
polymer morphology (crystallinity, thermal history, mole-
cular orientation, etc.), polymer molecular architecture
(branches, molecular weight and tacticity), polymer plasti-
cisation and others.
CHEMISTRY IS KEY
Nowadays, there is a large number of chemical combinations
and high throughput and selective catalyst technologies,
accessible via cutting edge polymer chemistry, to generate
polymeric materials with tailormade structures and proper-
ties. As would be reasonable to expect, then, the chemistry is
the basic and main deŽ ning factor determining barrier
properties in polymeric materials. Thus, by varying the
chemistry of the macromolecule,often by simply adjusting the
pendant group along the polymer chain, a signiŽ cantly large
variation in barrier properties can be achieved. Figure 1
shows that the barrier properties to oxygen increase by more
than Ž ve orders of magnitude as a result of a change in the
functional group present in a repetitive basic ethylenic unit.
Some commonly employed acronyms applied to well known
commercial plastics are also indicated in Fig. 1; generic
names for the acronyms used throughout the paper are
listed in the ‘Nomenclature’ above.
 Lagaron et al.
1 Given functional groups pendant from a basic ethylenic
polymer chain and their relative oxygen permeability:
note that values along x axis are equally spaced for illus-
trative purposes and therefore are not properly scaled
Associated with the signiŽ cant changes in barrier proper-
ties resulting from chemistry variations are, for instance, the
introduction of apolar voluminous groups at the low barrier
side of the permeability spectrum, or the incorporation of
small and strongly self-interacting chemical groups at the
high barrier side of the permeability spectrum. As is well
known, most polymeric materials comprise exceedingly
long, high molecular weight molecules (called polymer
chains) which, for the case of the most widely used plastics,
the thermoplastics family, do not possess in the amorphous
state intermolecular links other than secondary forces of,
for example, the van der Waals type. Consequently, the
presence of these various pendant groups can either disrupt
or enhance the high intermolecular cohesion necessary to
maintain high barrier efŽ ciency against the transport of low
molecular weight substances.
Moreover, the chemistry also deŽ nes the afŽ nity between
a potential permeant and the polymer matrix. As the pro-
cess of permeation is a bimodal process comprising solution
and diffusion, low solubility based on the chemical disparity
of a permeant and the polymer matrix will also result in low
permeability, irrespective of whether the kinetics of diffu-
sion are going to be favourable to permeant transport. The
present paper concentrates, owing to its relevance and ease
of generalisation, on the barrier properties of non-interacting
chemicals, as is usually the case for permanent gases.
A physical quantity termed the cohesive energy density
can be a useful parameter to help explain, quantify or even
predict the behaviour in terms of barrier properties of
polymeric materials. The cohesive energy of a substance in a
condensed state is deŽ ned as the increase in internal energy
per mole of substance if all the intermolecular forces are
eliminated. For low molecular weight substances, this
energy can be experimentally calculated from the heat of
evaporation. However, for polymers, the cohesive energy
density (deŽ ned as the cohesive energy per unit volume) can
be estimated using additive group contribution models such
as those devised by, for instance, Van Krevelen for cohesive
energy and Traube for molar volume.1 0 These models
propose contribution values for each of the chemical entities
building up the polymer chain. Consequently, this para-
meter informs about the strength of the interaction between
molecules, and how this interaction changes when different
chemical groups are added to the polymer chain. The
cohesive energy density is often given as the square of the
solubility parameter.
Another important factor strongly associated with
barrier properties is the free volume. The free volume com-
prises the microcavities present in a polymeric material.
Permeants make use of these cavities, whether permanent or
High barrier properties in polymeric materials 3
2 Oxygen permeability P versus ratio of fractional free
volume (FFV)/cohesive energy density (CED) for some
widely used commercial polymers: unpublished data
after Duc et al.
transient, to diffuse through the polymer matrix. The
transport properties of a permeant are therefore dependent
on the number and size of these microcavities. This concept
is usually expressed through the so called fractional free
volume parameter Vf , and is indeed strongly related to
chemistry (cohesive energy density), but is also related to a
number of other relevant factors having an impact on
barrier properties, for example thermal history, polymer Tg ,
crystallinity and/or conformational order, etc. The frac-
tional free volume can be readily determined by the
following simple expression
V {V0
Vf ~ : : : : : : : : : : : : : (4)
V
where V is the speciŽ c volume of a particular polymer
sample determined from the density, and V0 is the speciŽ c
volume at zero solubility (volume exclusively occupied by
polymer chains). The latter parameter can be experimen-
tally determined by, for instance, extrapolation of experi-
mental data,1 1 or can be estimated from additive group
contribution models.1 0
A very useful concept for free volume is that proposed by
Cohen and Turnbull12 ,13 and Fujita,1 4 through a general
expression
D!exp({Bd =Vf ) : : : : : : : : : : : (5)
In this expression, D is the diffusion coefŽ cient and Bd is a
constant that depends only on the size of the penetrant
molecule. This model has been shown adequately to des-
cribe the transport kinetics of organic vapours and small gas
molecules in a number of polymers.
More recent efforts, however, have led to the develop-
ment of an experimental methodology based on a technique
called positronium annihilation spectroscopy. This metho-
dology provides an experimental approach to determine
free volume, as it enables measurement of hole size on a
nanoscale and free volume fraction.1 5 Nevertheless, the
absolute value of the fractional free volume cannot be
directly obtained from only positron lifetime measurements.
Despite this, a recent study making use of positronium
annihilation spectroscopy showed that there exists an
excellent correlation between oxygen permeability and a
relative fractional free volume parameter as determined by
this technique in a number of EVOH copolymers.1 6 From
the experiments, it was clear that the fractional free volume
in these materials concerns mainly the free volume size, as
only the free volume size and not the orthopositronium o-Ps
lifetime intensity, i.e. the number of holes, varied across
composition in these polymers.
It is relevant, therefore, to realise that high barrier
polymers are the result of a permeable structure (amor-
phous phase) with a high cohesive energy density and very
low fractional free volume. Figure 2 plots the oxygen
Materials Science and Technology January 2004 Vol. 20
4 Lagaron et al. High barrier properties in polymeric materials
permeability of a number of plastics versus the ratio of
the fractional free volume/cohesive energy density. From
Fig. 2, it can be seen that the high barrier EVOH copolymer
(with 32 mol-% ethylene) is one of the most efŽ cient oxygen
barrier materials owing to its high intermolecular cohesion
and low fractional free volume. Consequently, this material
is being increasingly introduced in packaging applications
where high barrier properties to gases are required. In
contrast, polymers such as HDPE have much lower gas
barrier properties owing to low intermolecular cohesion and
large fractional free volume. However, high intermolecular
cohesion can be distorted by, for instance, chemical alter-
ations in the material (polymer degradation) as a result of
thermal treatments.1 7
Polymer chain rigidity or polymer Tg also plays a relevant
role in barrier properties since, as explained above,
penetrant transport mechanisms are greatly altered depend-
ing on whether the permeation process occurs above
(rubbery state) or below (glassy state) the polymer glass
transition temperature. There is a very general trend which
indicates that the higher is the polymer Tg , the lower is the
gas permeability and the better is the permselectivity.
However, this does not apply to common polymers such as
PS or PC, which are very rigid glassy materials with Tg
values above 100°C and very high permeability. This is of
course a consequence of the voluminous side groups, which
indeed reduce chain segment mobility owing to steric
hindrance but in turn generate large fractional free volumes.
On the other hand, polymers such as EVOH copolymers,
PK copolymers or PVDC have lower Tg values than, for
instance, PS, PC or other materials including PET, and yet
have outstanding barrier properties. This is again a result of
very high cohesive energy density and low fractional free
volume exhibited by the former materials.
POLYMER MORPHOLOGY
An important issue implicit in all the above considerations
is the well known characteristic that polymers are not
able to crystallise fully, some of them being in fact totally
amorphous. Many polymers used in packaging applications
have therefore a semicrystalline nature, and hence are, from
a structural viewpoint, heterogeneous materials. These
polymers contain, under the most simplistic two phase
model visualisation, both a fraction of chain segments com-
prising highly packed and conformationally ordered three-
dimensional structures, the polymer crystalline fraction x,
and another fraction in an amorphous state without
conformational regularity and lateral order. As a large
body of experimental evidence suggests that polymer
crystals are impermeable to the transport of most low
molecular weight substances, it is broadly accepted that the
amorphous phase is the only phase available for permeation
of these substances (shown schematically in Fig. 3).
It is therefore this particular structural feature, i.e.
polymer crystallinity, together with a low intermolecular
cohesion between polymer chains in the amorphous phase,
that best deŽ nes many of the most characteristic polymer
properties including permeability. However, polymer crys-
tals not only Ž ll the molecular structure of semicrystalline
materials with microscopic impermeable blocks, but also
affect the surrounding amorphous phase. To begin with, the
presence of crystallinity, its morphology (for instance
crystal width/thickness ratio) and orientation present
additional considerations in terms of permeability, as the
penetrant molecules have to circumvent the crystallites and
thereby travel through a more tortuous diffusive path
than in a fully amorphous material. This effect is usually
accounted for in calculations of the transport coefŽ cients
(see equation (6) below for diffusion) by the so called
tortuosity or geometric impedance factor b. Thus, the
tortuosity factor is in essence the path length that a
Materials Science and Technology January 2004 Vol. 20
3 Schematic diagram of gas permeation process through
amorphous phase only
permeant has to travel across a Ž lm thickness divided by its
actual thickness. Furthermore, and as noted above, the
presence of these crystalline blocks also affects the
surrounding conformationally disordered amorphous
phase. The constraining effects imposed by crystals to the
chain segments in the amorphous phase depend typically on
factors such as crystal surface area and penetrant size. This
phenomenon is substantiated from extensive mechanical
and transport data, which indicate clearly that the
segmental mobility of the non-crystalline fraction is much
less than that in the fully amorphous polymer.1 8 ,1 9 This
effect is taken into account in calculations of the transport
coefŽ cients (see equation (6)) by the so called chain
immobilisation factor t
Damorphous
Dsemicrystalline ~ (1{x) : : : : : : : (6)
bt
As a result of this, being aware of the implications of
crystallinity and its morphology for the barrier properties is
a relevant issue, because by adequate processing (thermal
history) of polymers these parameters can be optimised to
obtain specimens, based on the same chemistry, with
enhanced permeability.
Polymer molecular orientation as a result of drawing or
processing leads generally to an increase in barrier proper-
ties. This is usually attributed to (a) orientation induced
crystallisation, (b) fractionation and alignment (perpendi-
cular to the permeant transport) of the crystals in the
straining direction (increase in the tortuosity factor) and (c)
to densiŽ cation (reduction in free volume) of the amor-
phous phase owing to an increase in conformational order
in the non-crystalline chain segments. A recent paper1 1
reported that oxygen permeability, diffusivity and solubility
parameters decreased with the amount of uniaxial orienta-
tion in PET owing to conformational transformations of
glycol linkages from gauche to trans. Orientation is then
seen as the process of decreasing excess free volume,
bringing the non-equilibrium glassy polymer closer to the
equilibrium condition.
A special case in barrier properties is that of liquid crystal
polymers. These materials can have gas barrier properties as
good as those of high barrier EVOH copolymers. Liquid
crystal polymers are often termed ‘mesomorphic’ because
they have structures between those of amorphous polymers
 Lagaron et al. High barrier properties in polymeric materials 5

against the transport of oxygen. This is also the case, albeit

to a lesser extent, for other polar polymers such as the
polyamide family. Thus, it is often the situation that high
barrier polymers to gases have very low barrier performance
to polar solvents such as water. This behaviour is associated
with the disruption by moisture of the existing polymer
intermolecular self-association promoted by, for instance,
hydrogen bonding in EVOH, PVOH and PA.2 3 – 2 5 As
opposed to this behaviour, polymers such as polyoleŽ ns, PE
and PP have low barrier properties to gases owing to weak
self-association, but are extremely good barrier materials to
water as a result of their oleŽ nic hydrophobic character.
Table 1 gives typical oxygen permeability and water permea-
bility values for a number of commercial polymers and
multilayer structures used in food packaging applications.2 6
An exceptional case is that of amorphous polyamide
4 Oxygen permeability P versus water activity for given (aPA) and some polyimides, for which oxygen permeability
ethylene – vinyl alcohol copolymers (EVOH) with vary- decreases with increasing relative humidity.8 For aPA, even
ing contents of ethylene though the presence of moisture decreases to a high extent
the polymer Tg , the oxygen permeability does not increase
with no regular order and those with a three-dimensional but surprisingly decreases (see Table 1). Recent spectro-
crystal lattice. The unique packing arrangement of these scopic work suggests that moisture has a speciŽ c interaction
polymeric systems has raised some fundamental questions with this particular polymer.2 7 The results indicate that
about the permeation mechanisms of low molecular weight moisture molecules do not disrupt the originally existing
molecules, i.e. whether they behave more like glasses or hydrogen bonding intermolecular interactions between
conventional crystals.8 amide groups but rather link to the few remaining free
amide groups, and most of the sorbed water molecules self-
associate, forming clusters, which all together act as a free
POLYMER MOLECULAR ARCHITECTURE volume blocking mechanism to the diffusion of oxygen
Some relevant routes to modify the molecular architecture molecules.
of polymers, and hence the barrier properties, include
copolymerisation, i.e. introduction of a few side groups or
branches along the main chain, or modiŽ cation of the
molecular weight or the stereoisomerism. Linear polyethy- Recent developments in the Ž eld
lene (HDPE) is more crystalline than both branched
polyethylenes (e.g. LLDPEs and LDPE) and ultrahigh Recent developments in the high barrier Ž eld come mainly
molecular weight polyethylenes, and is therefore found to from three sources, namely (a) new polymers, (b) polymer
be more dense, less permeable and stiffer, albeit less tough. blends and (c) nanocomposites. Polymeric materials for
Moreover, the homogeneous or heterogeneous character of high barrier applications are challenged today by a broad
the incorporation of branches along the polymer chains has range of stringent property requirements, including ease of
a large impact on properties, including barrier proper- processing, higher barrier properties to permanent gases, to
ties.2 0 ,2 1 The new polyoleŽ ns obtained by single site catalyst moisture and to low molecular weight organic compounds,
technologies can lead to very low density materials with excellent chemical resistance, permselectivity, low relative
unprecedented very low barrier properties, which in thin humidity dependence for barrier performance and ease of
Ž lm form can serve as excellent packaging materials for recycling and biodegradability. Among the new high barrier
products that have breathing necessities, e.g. fruit and
vegetables. Another signiŽ cant factor is the stereoisomerism Table 1 Water permeability P (at 38 C and 90% relative
(tacticity). This results from the various stereochemical humidity) and oxygen permeability P (23 C) of a
arrangements that can be present along the polymer number of commercial plastics and multilayer
backbone and that cannot be changed by rotation along structures: data from Ref. 26
the C-C bond. A polymer in which the pendant groups
contain the same conŽ guration is said to be isotactic. Oxygen P, 1021 m3 m
(m2 s Pa) 2 1
Polymers in which alternate carbon atoms have the same Water P, 1018 kg m
conŽ guration are called syndiotactic, and in which the Material (m2 s Pa) 2 1 Dry Wet
conŽ guration is random are called atactic. The atactic
conŽ guration is in principle more permeable, as it usually PVOH 485 000 0.17 900
EVOH 17 000 0.77 91
yields amorphous polymers (e.g. PS or PMMA). PAN 2420 1.9 ¼
PAN (70%AN) 8250 10 .5 31
PVDC 30 .53 4.5 ¼
POLYMER PLASTICISATION PA6 20 600 52 225
In this context, it is relevant to add here that polymer aPA 2420 83 60
PET 2300 135 ¼
plasticisation (Tg depletion) owing to polymer – permeant PP 726 6750 ¼
interactions or polymer and surrounding media chemical PC 19 400 10 500 ¼
interactions has very detrimental effects, which usually lead LDPE 1200 21 500 ¼
to losses in intermolecular cohesion and a decrease in LCP 10 0.42 ¼
PET ± PVDC 170 17 .5 ¼
overall barrier performance. As an example, Fig. 4 shows PA ± PVDC 160 18 .2 ¼
the variation in oxygen permeability of a number of EVOH PP ± PVDC 43 25 ¼
copolymers as a function of the percentage of relative PET (metallised) 58 3.5 ¼
humidity present in the environment.2 2 PET ± AlO x ± PE 21 7 15
PET ± SiOx ± PE 16 4.9 ¼
From Fig. 4, it can be readily observed that relative PA ± SiOx ± PE 32 7.7 ¼
humidity has a tremendous detrimental impact on the PP ± SiOx ± PE 13 81 ¼
outstanding barrier capacity of these EVOH copolymers

Materials Science and Technology January 2004 Vol. 20

6 Lagaron et al. High barrier properties in polymeric materials
5 Modelling of oxygen permeability for various disposi-
tions of EVOH – amorphous polyamide (aPA) blend
components facing transport of oxygen gas as func-
tion of volume fraction of EVOH: experimental data
(indicated by arrow) for 80/20 EVOH – aPA and EVOH –
ionomer melt mixed blends recently developed in pre-
sent authors’ laboratory are also provided35
polymers being developed are materials such as the PK
copolymers (aliphatic polyketones).2 8 ,2 9 These semicrystal-
line materials have an outstanding range of mechanical,
thermal and high barrier properties (comparable to some
EVOH copolymers), chemical resistance and reduced
relative humidity dependence for barrier properties, which
give them signiŽ cant commercial potential in a broad range
of engineering, barrier packaging, Ž bre and blend applica-
tions. Other new ranges of promising materials currently
being investigated for packaging applications are those
derived from biomass, and, therefore, to a higher or lower
extent readily biodegradable/compostable.3 0 ,3 1 Among
these materials, it is possible to Ž nd: (a) polymers
synthesised from bioderived monomers such as polylac-
tates; (b) polymers produced directly by organisms such as
PHAs, bacterial cellulose, etc.; and (c) polymers derived
directly from biomass such as polysaccharides (cellulose,
starch, chitosan). These polymers can have excellent barrier
properties to gases, for instance in the case of plasticised
chitosan, albeit the barrier performance is dramatically
reduced in the presence of moisture. However, other poly-
mers such as the PHAs have very high water barrier
properties. Hence, in principle, a biomass derived high
barrier multilayer system could be developed whereby an
inner layer of plasticised chitosan could be sandwiched
between high moisture barrier PHA layers. An interesting
property of some of these biobased polymers, e.g. PLA and
starch, is that the permeability of carbon dioxide compared
to that of oxygen (permselectivity) is higher than that of
most conventional mineral oil based plastics. This is of
interest for some food packaging applications where a high
barrier to oxygen is required, but CO2 generated by the
product should be allowed to exit the package head space to
avoid package swelling. These materials still suffer, how-
ever, from high production costs, competing with the
conventional plastic materials now on the market.
Blending of polymers is another route for accessing the
desired balance of properties, by controlling the polymer
phase interaction and/or morphology.3 2 Figure 5 shows an
example of modelling of the barrier properties of EVOH –
aPA blends as a function of blend composition and blend
constituent disposition facing oxygen transport. High
barrier blends of EVOH with an ionomer and an amor-
phous polyamide have recently been developed in the
present authors’ laboratory.2 4 ,2 5 These blends show excel-
lent barrier properties to gases compared with neat EVOH
(see experimental results for EVOH – aPA 80/20 blends in
Fig. 5), and yet much better thermoformabilitythan EVOH
alone to produce thermoformed multilayer rigid food
Materials Science and Technology January 2004 Vol. 20
containers.3 3 – 3 5 Also, a large number of blends have been
developed in which a high gas barrier polymer such as
EVOH is added to improve the barrier properties of a low
gas barrier material and, conversely, in which a high water
barrier polymer is added to a high gas barrier material to
reduce relative humidity dependence of the barrier proper-
ties of the latter.2 4
More recently, there has been a signiŽ cant increase in the
amount of research devoted to enhancing relevant polymer
properties, mainly mechanical and barrier properties, but
also surface hardness, thermal stability and Ž re retardancy,
by dispersing low loadings (usually less than 5 wt-%) of
exfoliated clay platelets with thickness on a nanometre scale
and with high aspect ratios in a conventional polymer
matrix. Gas and water vapour permeabilities have been
found to decrease, in some cases, to a large extent in the
nanocomposites owing to, among other parameters,
increased tortuosity factors.3 6 For example, an EPDM –
clay nanocomposite with a 4 wt-% loading had decreased
N2 permeability by 30%, compared with EPDM alone.3 7
Oxygen permeability decreased by a factor of three in
polyester – clay nanocomposites at 2.5 wt-% loading.3 4 A
60% reduction in the water permeability was measured in a
5 wt-% loaded poly(vinyl alcohol) – sodium montmorillo-
nite nanocomposite, and the material still retained its
optical clarity.3 8
There are also a large number of technological develop-
ments making use of existing materials and associated with
modern packaging technologies, aimed to tailor designs to
speciŽ c performances and packaged product needs. These
developments include (a) multilayer systems comprising
various polymeric materials made by lamination, coextru-
sion or coinjection, (b) aluminium metallised polymeric
Ž lms obtained by vacuum deposition technologies and (c)
oxide (AlOx or SiOx ) coated polymeric Ž lms. Multilayer
systems in the food packaging Ž eld usually comprise high
gas barrier polymers such as EVOH or PA sandwiched
between structural layers of other polymers, which usually
provide the assembly with a high barrier to moisture as well
as having other properties, i.e. thermal, mechanical, optical
or processing properties, printability, thermosolderability,
etc. Coating plastics with vacuum deposited aluminium
seeks to increase barrier properties to gases, moisture and
organic vapours, and results in better  exibility, consumer
appeal and lower enviromental impact owing to a reduction
in metal consumption and better recyclability than in the
case of conventional lamination with aluminium foil.3 9 On
the other hand, the metal coating of polymeric Ž lms imposes
reductions in  exibility, stretchability and thermoformabil-
ity compared with the performance of the polymer Ž lms
alone. Moreover, aluminium coatings render the package
opaque, and it cannot be microwaved. To circumvent these
problems, oxide coated polymer Ž lms can be obtained that
exhibit transparency and high barrier properties, albeit they
can be susceptible to coating microcraking during proces-
sing or handling.
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Materials Science and Technology January 2004 Vol. 20