Polymer Testing 23 (2004) 551557

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Analysis Method
On the applicability of FT-IR spectroscopy to test aroma
transport properties in polymer lms
D. Cava, J.M. Lagaro n

, A. Lo pez-Rubio, , R. Catala, , R. Gavara

Packaging Lab., IATA-CSIC, Apdo. Correos 73, E-46100 Burjassot, Spain
Received 3 October 2003; accepted 19 November 2003
Abstract
The determination of transport properties of aroma components in polymers to be used in packaging applications
remains a challenge, as there is no reliable commercial instrument or standard methodology to be applied. However,
the signicance of such measurements from a product application development point of view seems to be of para-
mount importance. In this pioneering study on the topic, we set the conditions and limitations of the FT-IR tech-
nique, and discuss the potential of a simple methodology to determine aroma transport in polymers. More
specically, we made an attempt to apply the technique in transmission to determine transport coecients of pure
and mixed citric aroma compounds during desorption from polyethylene and compared the results with those
obtained from a conventional gravimetric method.
# 2003 Elsevier Ltd. All rights reserved.
Keywords: Aroma barrier; Plastic packaging
1. Introduction
One of the limiting properties of polymeric materi-
als in the food packaging eld is their inherent per-
meability to low molecular weight substances, i.e.
gases, moisture and organic vapours. This has boosted
the interest to develop new resins with higher barrier
properties and to carry out research aimed at under-
standing the structure/barrier properties relationship.
Barrier properties in polymers are necessarily associa-
ted with their inherent ability to permit the exchange,
to a higher or lower extent, of low molecular weight
substances through mass transport processes like per-
meation. The permeation of low-molecular weight
chemical species most usually takes place through the
polymer amorphous phase and is generally envisaged
as a combination of two processes, i.e. sorption and
diusion. A permeate gas is rst dissolved into the
upstream face of the polymer lm, and then it under-
goes a molecular diusion to the downstream face of
the lm where it is desorbed into the external phase
again. A sorption-diusion mechanism is thus applied,
which can be formally expressed in terms of per-
meability (P), this being the product of the solubility
(S) and diusion (D) coecients, as dened by Henrys
and Ficks laws, respectively [1].
Despite the existence of excellent high barrier mate-
rials to gases in oxygen-sensitive food packaging appli-
cations, including ethylene-vinyl alcohol copolymers,
polyvinylidene chloride, polyamides, polyesters and
nitrile-based resins, some of these materials are, for
instance, easily plasticized by moisture or do not ther-
moseal well and, consequently, in most packaging
applications, are commonly encapsulated in multilayer
structures between hydrophobic, thermosealable poly-
mers like polypropylene or polyethylene.
Polyethylene is, in terms of volume, the most widely
used polymer in food packaging applications. This
polymer is most often used as the inner layer in direct

Corresponding author. Tel.: +34-96-390-0022; fax: +34

96-363-6301.
E-mail address: lagaron@iata.csic.es (J.M. Lagaro n).
0142-9418/$ - see front matter #2003 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2003.11.003
contact with foods due to its excellent water barrier,
inertness and thermosealability characteristics.
Although avor compounds are minority con-
stituents of foodstus, small alterations in the quantity
or relative presence (aroma unbalance) of them can
produce organoleptically detectable changes resulting
in consumer rejection. In order to prevent this deterio-
ration in food quality, adequate packaging designs
should be used to avoid signicant losses of these vol-
atile compounds during product shelf-life. It is well
known that during storage of packaged foods, volatile
compounds can be lost through any of the following
processes: degradation, scalping (retention by the pack-
aging) or permeation. Fruit juices are foodstus where
avor is one of the most appreciated features, and
consequently, the lost of volatile compounds during
packaging is a main concern to manufacturers.
When a fruit juice is packaged inside a plastic con-
tainer, scalping and permeation are the main causes of
volatile compounds losses. As a result, both transport
phenomena have been the subject of numerous research
studies. To carry out these studies, researchers have
been applying dierent techniques. The simplest one is
the monitoring of the weight uptake of a lm in con-
tact with the pure volatile compound. This technique
can be very precise if electrobalances are used, but can
only be applied to one compound at the time. How-
ever, mass transport properties of volatile compounds
may change due to the presence of other volatiles [2],
and consequently, the results obtained for a pure com-
pound may not necessarily be applicable to mixtures of
other volatile compounds, the real case in foods.
Considering this feature, most of the studies carried
out exposed the plastic materials to mixtures of volatile
compounds or real foodstus and made used of gas
chromatography to measure the volatile compounds
taken up by the packaging material [3]. These studies
can either be developed evaluating the loss of volatile
compounds in the liquid matrix or by monitoring the
polymer uptake. Although both methods have been
used, the former one has the disadvantage of diculties
in discriminating whether the volatile has been scalped
in the polymer or lost by degradation or chemical
modication [4]. Thus, in many of these studies the lat-
ter methodology has been preferred. Generally, the GC
technique has mostly been used to evaluate equilibrium
sorption and partition coecients of some aroma com-
pounds present in juices [57]. From these experiments,
it was found that a signicant amount of, for instance,
a-pinene (ca. 80%), limonene and myrcene (ca. 60%),
present on a cold-pressed juice were sorbed in a poly-
ethylene sample in less than a week [7]. In spite of the
great interest of the GC methodologies, they can have
some limitations when applied to, for instance, (i) the
analysis of very thin lms (diculties in handling), such
as those mostly used in many packaging structures, or
(ii) to obtain diusion coecients with accuracy for
volatile systems diusing rapidly given the length of a
typical GC experiment.
As a result, nding new and advantageous char-
acterization methodologies for these materials in terms
of aroma barrier is of signicant relevance. In this
paper we made use of a simple transmission FT-IR
methodology to determine transport properties of citric
juice aroma components in polyethylene. Generally, the
FT-IR technique oers the advantages, when measur-
ing transport properties, of being capable of measuring
the simultaneous permeability of various penetrants
and of assessing the dierent kinds of interactions that
can be established between the polymer and the pene-
trant at dierent stages of sorption, by way of analyz-
ing band shifts and band shape changes. Furthermore,
FT-IR is also advantageous as compared to, for
instance, conventional gravimetry or GC, both because
it is a time-resolved technique and very thin lms can
be easily and precisely evaluated.
Some studies can already be found in the literature
where FT-IR (mostly through the use of an attenuated
total reection, ATR, accessory) has been used to
determine diusion coecients of, mostly, water
vapour in various polymers [2,8,9]. There is also a
recent study where sorption and diusion of several
esters in polypropylene were attempted step-wise dur-
ing sorption using transmission FT-IR, but no com-
parison was traced with other methods [10]. The use of
an ATR accessory has the drawbacks of measuring the
properties of the very near surface of a polymer (in
some cases obtained by casting from solution to
achieve and ensure a good adhesion between the ATR
crystal and the lm) and of having a complex relation-
ship between absorbance and concentration [11]. Most
lms used in food packaging are, however, obtained by
extrusion processes, which yield a thin heterogeneous
sample in terms of morphology along the thickness;
therefore, it is more preferable to measure average
properties across the whole of the lm thickness.
In this paper, we will asses the validity of the FT-IR
technique in transmission to determine the transport
properties of pure standard essence oil aroma compo-
nents present in citric fruit juices and mixtures of these
through an extruded polyethylene lm.
2. Experimental
A general purpose extruded polyethylene (PE) grade
(with 80 lm thickness and a density of
937 200 500 g=m
3
) for use in contact with foods was
kindly prepared and supplied by the Nippon Synthetic
Chemical Industry Co. Ltd (Nippon Gohsei, Osaka,
Japan). No additional information about the polymers
specic characteristics was disclosed. The selected stan-
dard aroma compounds (see formulae in Fig. 1), dl-
552 D. Cava et al. / Polymer Testing 23 (2004) 551557
limonene (95% purity, d=l 1), a-pinene (98% purity),
citral (95% purity mixture of cis and trans isomers) and
linalool (97% purity) were purchased from Aldrich.
Samples (15 cm
2
of surface area and 80 microns
thickness) were measured during desorption at room
temperature (22
v
C) by transmission FT-IR experi-
ments with a Bruker Tensor 37 equipment with 4 cm
1
resolution and 5 s as typical acquisition time. The sam-
ples, previously equilibrated (constant weight during
successive measurements) inside the desired aroma
compounds, were thoroughly wiped o with a tissue to
remove excess volatile deposited on the lm surface
(this step is considered as time zero) and immediately
placed into the measuring chamber continuously
purged with a high ux of N
2
to eliminate the desorbed
volatiles. Comparative weight loss measurements were
carried out in an analytical balance model Voya-
ger
1
V11140. All experiments were carried out in tripli-
cate to check reproducibility and estimate errors. The
saturation or equilibrium absorbance/concentration (at
t 0) was calculated from the best t of the experi-
mental data to eq. (2).
3. Results
Fig. 2 shows typical substraction (from the spectrum
of the completely desorbed polymer) FT-IR spectra of
chosen bands characteristic of the selected aroma com-
pounds obtained at selected intervals during desorption
from the PE sample. In each case, a detailed study of
the corresponding aroma spectrum was carried out,
and the most suitable bands for the analysis were selec-
ted. Table 1 summarises chosen bands and their most
likely molecular vibrational assignment.
Some useful aspects to take into account when
selecting an appropriate band are that, (i) the band
must absorb within the limits of the LambertBeers
law, (ii) it must remain unmodied in terms of band
shifts and prole (see later), and, if possible, (iii) it is
preferable for it to be isolated from others and not
overlap with the polymer spectrum. The calculations
were also made in some cases with other characteristic
bands dierent from the ones gathered in Table 1 and,
in general, yielded analogous results.
In order to obtain diusion coecients (D) from the
experiments in Fig. 2 a mathematical tting of the
desorption data as a function of time to the corre-
sponding solution of Ficks second law needs to be car-
ried out. In order to do that some basic assumptions
have to be considered, namely, (i) the diusion process
must correspond to Fick laws, (ii) equilibrium at the
interphase is reached instantaneously and (iii) mass
transfer only occurs in the lm thickness direction
(ensured if thickness compared to the other two dimen-
sions of the measured lm is considered negligible).
The best solution to Ficks second law to describe
the diusion through a lm with a thickness L, is that
proposed by Crank [1]:
M
t
M
1
1
8
p
2
X
1
n0
1
2n1
2
exp
D2n1
2
p
2
t
L
2
( )
1
This expression was developed to be applied during
sorption experiments. In order to use the expression in
desorption experiments and to apply it to an FT-IR
experiment, some modications become necessary. The
limiting conditions to be considered during a desorp-
tion experiment are:
t 0 0 x L AA
e
t >0 x0; x L A0
When considering these limiting conditions, eq. (1)
becomes eq. (2):
A
t
A
e

8
p
2
X
1
n0
1
2n1
2
exp
D2n1
2
p
2
t
L
2
( )
2
Where A
t
and A
e
are the absorbances (band area) at a
given time t and at saturation or equilibrium sorption,
respectively. Further assumptions for the particular
FT-IR case are constant thickness and absorption coef-
cients across the experiment.
Upon consideration of all of the above and by t-
ting the area of the chosen absorbance band as a func-
tion of time to eq. (2) it is easy to derive the
corresponding diusion coecient. For the tting, only
the rst six terms of the summation in eq. (2) were con-
sidered. The reason for this is that further terms had a
negligible impact on the results. Diusion coecients
Fig. 1. Chemical formulae of the citric fruit juice aroma
compounds used.
D. Cava et al. / Polymer Testing 23 (2004) 551557 553
as determined by FT-IR and gravimetry, and solubility
and permeability coecients are gathered in Table 2.
Fig. 3 shows, as an example, some experimental
results and their tting to eq. (2) for FT-IR and gra-
vimetry data, strongly suggesting a Fickian behavior in
desorption. Similar Fickian behavior was found for all
of the aroma compounds. Fig. 4 shows a comparison
plot between FT-IR and gravimetry ttings for limon-
ene and citral. From the results in Fig. 4 and Table 2,
it can be seen that there is a good correspondence
between the data obtained by FT-IR and those mea-
sured by gravimetry, especially for limonene, pinene
and linalool. In the case of citral, there are some dier-
ences in D between the two techniques, which could be
attributed to a small shift (see Fig. 5) of the C=O
stretching band during the desorption process and to
some shape asymmetry development (see arrow in
Fig. 2c), both of them likely caused by variations in the
relative population of molecules with dierent types of
interaction with the polymer as the experiment pro-
gresses. Although, the band shift is very small, and
arguably smaller than the spectral resolution of the
instrument, this is still real and can be accurately mea-
sured by curve-tting. Curve-tting has proven to
enhance band accuracy determination (at least in rela-
tive terms) well beyond the spectral resolution of the
instrument [12]. The reason why frequency shifts and
changes in band shape (often the case of N-H, O-H
and C=O stretching bands) may result in a decient
correlation with gravimetry, lies in the fact that absorp-
tion coecients change [13], and therefore, during the
course of the experiment the relation between absor-
bance and concentration may be dierent. If one mod-
els the variation of the absorbance coecient with
penetrant concentration, it could potentially be possible
to input the LambertBeer law with the corresponding
Fig. 2. Substraction spectra in absorption taken at several instances during the desorption experiments and showing the selected
bands of (a) linalool, (b) limonene, (c) citral and (d) pinene.
Table 1
Selected IR bands and likely assignments
Aroma compound Band (cm
1
) Assignment
Limonene 888 C-H Deformation
Linalool 920 C-H Deformation
Pinene 3024 C-H Stretching
Citral 1683 C=O Stretching
554 D. Cava et al. / Polymer Testing 23 (2004) 551557
concentration dependency form of the absorbance coef-
cient and, therefore, account for the eect.
A signicant advantage of the FT-IR technique
when compared with gravimetric measurements is the
possibility of studying mixtures of aroma compounds
and their interactions. In order to illustrate this
phenomenon, the diusion of components in binary
and ternary mixtures with equal volumes of the various
components was studied. The dierent types of interac-
tions between the mixture constituents and the polymer
can induce changes in their diusion coecients and,
therefore, the values calculated for the pure compounds
may not necessarily apply in these cases. The blends
used in this study were mixtures of limonene and
pinene (so-called mixture A), of limonene and citral
(so-called mixture B) and a ternary blend of limonene,
Table 2
Diusion (D), solubility (S) and permeability (P) coecients and %mass uptake (g/100 g of polymer) of limonene, linalool, pinene
and citral
Volatile compo-
nent
D (gravimetry)
m
2
=s 10
13
D (FT-IR)
m
2
=s 10
13
S
a
g/(m
3
Pa) %Uptake P (FT-IR)
g m=m
2
s Pa 10
10
Limonene 20.00.4 18.50.6 80040 170.8 151
Linalool 3.40.2 3.80.2 82050 3.20.2 3.10.3
Pinene 9.70.2 9.60.6 24010 12.80.5 2.30.2
Citral 3.50.3 5.50.2 3600200 3.00.2 202
a
Calculated from mass uptakes, polymer density and vapour partial pressures at 20
v
C taken from reference [18].
Fig. 3. FT-IR (right) and gravimetric (left) desorption data (symbols) and best ttings (continuous line) to eq. (2) for limonene.
The rst experimental point at t=0 (equilibrium sorption) was extrapolated from the best tting in both cases.
Fig. 4. Comparison of FT-IR and gravimetric desorption curves for limonene (left) and citral (right).
D. Cava et al. / Polymer Testing 23 (2004) 551557 555
citral and linalool (so-called mixture C). The bands
selected to evaluate each compound were well sepa-
rated in the vibrational spectrum, thus permitting their
simultaneous study. In the ternary mixture however,
the linalool component could not be measured due to
overlapping with the other two components. The D
values obtained for each mixture component are gath-
ered in Table 3.
From the results, it is found that there are some
changes in D for the components in mixture A, parti-
cularly for the pinene. In this mixture, it would appear
that the diusion coecient of limonene (the compo-
nent that diuses more rapidly in the mixture) slows
down slightly compared to pure limonene, whereas the
pinene coecient increases due to, probably, the plasti-
cizing eect of limonene. For the components of mix-
tures B and C, smaller dierences in D values are
found compared to the pure compounds, where again
limonene appears to slow down slightly its kinetics of
diusion.
Having considered all of the above, there are still
some concerns to be taken into account. One of them is
the fact that we are implicitly assuming that data for
desorption can be directly extrapolated to sorption, i.e.
that the diusion coecient is not concentration depen-
dent. This is, of course, very unlikely to be strictly cor-
rect because most penetrants may have, to a certain
extent, the capability of plasticizing and swelling the
polymer, and therefore, the diusion coecient will be
concentration dependent. If the concentration depen-
dence is very large, then the disagreement between
sorption and desorption may be signicant. To get
around these particular cases, it would be preferable to
measure transport properties during sorption and, in
order to do that, it is more convenient and accurate for
fast penetrants to be measured either by ATR or in
transmission, but, making use of a specially designed
cell such as the one described in reference [11]. The
drawbacks associated with the ATR accessory have
already been outlined above.
Nevertheless, from the published data that we are
aware of and for many aroma compounds, the dier-
ence between sorption and desorption diusion coe-
cients is experimentally not so signicant, with
desorption usually slightly faster. For instance, Sadler
et al. [14] reported similar D coecients for limonene
vapour at 14
v
C in low density polyethylene during
sorption and desorption. Balik et al. [2] reported anal-
ogous behavior in sorption and desorption for amyl
acetate in high density polyethylene. Analogous sorp-
tion and desorption experiments were also recently
found for a number of alcohols (methanol, ethanol,
propanol and butanol-1) in spheres of ethylene-vinyl
acetate copolymer [15]. A positive aspect of measuring
lm desorption, is the fact that it is usually more likely
to be described by Ficks laws and, therefore, easier to
model. For instance, it has been reported [2] using FT-
IR-ATR that sorption of limonene in low density poly-
ethylene leads to an anomalous sigmoidal shaped
curve, while from our experiments limonene can be
nicely tted to Fickian behavior during desorption. It is
often the case during sorption experiments that plasti-
cizing agents lead to a sigmoidal shape [16], which may
not necessarily imply a non-Fickian diusion, and that
can be rationalized from recent works [17] as being lar-
gely due to geometrical aspects (release of macroscopic
constraints arising during swelling) occurring during
lm sorption. In these cases, the determination of the
kinetics of transport is far from easy, and it would
therefore be more favorable to circumvent this by car-
rying out desorption experiments.
Another concern relates to the possibility of analyz-
ing mass transport properties or aroma components
present in real foods, which are present at low partial
pressures and, consequently, their uptake is likely to be
very low (at innite dissolution). In these cases, GC is
more favorable because the limit of detection is, for
many substances, set to very low concentrations as
compared to FT-IR. A real challenge is thus imposed
Fig. 5. FT-IR band shifts (of peak maximums) determined
by curve-tting of the selected bands during desorption. Posi-
tive values correspond to shifts towards higher wavenumbers.
Table 3
Diusion coecients m
2
=seg 10
13
of aroma compounds
in mixtures
Volatile com-
pound
Blend A
(lim., pin.)
Blend B
(lim., cit.)
Blend C
(lim., cit., lin.)
Limonene 16.70.5 17.70.5 15.90.6
Pinene 13.71.0
Citral 5.60.2 5.60.2
556 D. Cava et al. / Polymer Testing 23 (2004) 551557
to the IR technique because of both lack of detection
and potentially high overlapping of bands, making
identication or analysis dicult. In such cases, analy-
sis of suciently thick polymer sheets could be pursued
to get higher absorbances from low uptakes or low
absorbance penetrants, i.e. to increase the limit of
detection. In this case, caution should be taken regard-
ing potential longitudinal diusion eects on the mea-
surements.
Acknowledgements
The authors would like to acknowledge Mr. Y.
Saito (NIPPON GOHSEI, Japan) for supplying extru-
ded polyethylene samples and for nancial support.
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