Test Method

Testing limonene diffusion through food contact polyethylene

by FT-IR spectroscopy: Film thickness, permeant concentration
and outer medium effects
David Cava, Ramon Catala, Rafael Gavara, Jose M. Lagaron
*
Packaging Laboratory, IATA-CSIC, Apartado Correos 73, 46100 Burjassot, Spain
Received 12 November 2004; accepted 14 December 2004
Abstract
A number of relevant factors not usually considered in the analysis of the transport properties of aroma components through
food packaging lms have been the subject of this study, using infrared spectroscopy as the main probing tool. More in
particular, the diffusion behavior of limonene in low density polyethylene (LDPE) has been analyzed by transmission FT-IR
spectroscopy as a function of sample thickness, permeant concentration and the outer medium. From the results, a surprising
reduction in diffusion (D) and permeability (P) coefcients with reducing lm thickness was found, which is most likely
attributed to morphological differences arising during cast lm extrusion. Moreover, the limonene desorption kinetics were
found to slow down considerably when desorption of the volatile was carried out in water as compared to desorption in air.
Finally, the sorption kinetics of limonene in LDPE were found to be much slower when the polymer was put in contact with
pressed orange juice (similar to a real juice packaging case), than when it was put in contact with the pure volatile. Aremarkable
observation arising from this work is that the diffusion coefcient of limonene in LDPE can vary by up to two orders of
magnitude depending on the testing conditions, mainly limonene concentration but also polymer morphology and,
consequently, these observations may well account for some of the extensive variability reported for this permeant in the
existing literature.
q 2005 Elsevier Ltd. All rights reserved.
Keywords: Transport properties; Polyethylene
1. Introduction
In many cases, the reason why consumers accept or
reject a packaged foodstuff is related to food quality issues
like organoleptic alterations. The aroma of a foodstuff
consists of a mixture of numerous volatile compounds, but
as these components are usually present in very small
quantities, tiny changes in their concentration prole can
produce signicant alterations in the perception of the
product, causing important economic losses. In citric fruit
juices, avor alterations are more relevant than in other
products, because avor is one of their most appreciated
characteristics.
It is during the storage of the juice, mainly inside plastic
containers, when avor alterations are more often produced
and, as a result of that, behavior of packaged products during
shelf-life has been widely studied during the last few
decades. First references related to this topic date from the
1970s [1]; since then, several authors have focused their
research on this food-package interaction. Charara et al. [2]
observed that almost two-thirds of the limonene, the
a-pinene and the myrcene present in a cold pressed orange
juice were extracted by low density polyethylene (LDPE)
0142-9418/$ - see front matter q 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymertesting.2004.12.003
Polymer Testing 24 (2005) 483489
www.elsevier.com/locate/polytest
* Tel.: C34 96 390 0022; fax: C34 96 363 6301.
E-mail address: lagaron@iata.csic.es (J.M. Lagaron).
lms. More recently, Van Willige et al. [3] found that
somewhat smaller amounts of limonene and a-pinene, ca.
50% of each component, were extracted, compared to the
previous work, after 29 days of dark storage inside LDPE
containers. From these works, and similar ones [4,5], it can
be concluded that when orange juice is stored inside a LDPE
container, signicant percentages of limonene, and other
volatiles, are scalped in the polymer. More recent works [6]
have again proved that LDPE can sorb a considerable
amount of several citric fruit aroma components, and that
the transport properties of single and mixed components can
easily be followed by FT-IR spectroscopy. A previous study
[6], discusses the prior art, advantages and limitations of the
FT-IR techniques for determination of transport properties
in polymeric lms.
In orange juice, limonene can usually be found in
concentrations two orders of magnitude higher than the
other volatile compounds, and therefore one could easily
believe that changes in its concentration can have a relevant
inuence over avor. Although, recent works have con-
cluded that the sorption of limonene by the package does not
cause relevant sensorial changes in orange juice [3], the
study of the mechanisms of transport of this component is of
great interest, because limonene scalping can affect the
container properties, and for instance, facilitate the loss of
other volatile compounds of more relevance by plasticiza-
tion of the package wall [7].
The transport of aroma components through semi-
crystalline polymeric structures, like LDPE lms, is
believed to take place only across the polymer amorphous
phase, following, to a fair approximation, well-known laws
that rule the transport of low molecular weight substances
across polymeric materials. The most relevant mass
transport properties are solubility, diffusion and per-
meability coefcients. The solubility coefcient (S) is
thermodynamic in nature, and relates to the amount of
permeant sorbed in the polymer with respect to its partial
pressure in the contacting environment, and can generally
be described by Henrys solubility law. The diffusion
coefcient (D), a kinetics parameter, measures the average
ability of scalped molecules to travel across the permeable
phase and is generally described by Ficks laws. The
permeability coefcient (P), evaluates the amount of
permeant traversing the polymer lm and is dened by the
product of D and S.
The transport properties of limonene have previously
been studied as a function of temperature and in a number of
packaging materials. However, the effect of other relevant
factors has not been reported. In this work, the effects of
lm thickness, outer medium composition and volatile
concentration on the transport properties of limonene were
studied. Moreover, this study shows for the rst time the
use of FT-IR to test the transport properties of limonene
in polyethylene from pressed orange juice (real case
scenario).
2. Experimental
A general purpose extruded polyethylene (PE) grade,
with three different thickness (10, 80 and 1000 mm) and a
density of 937,200G500 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 specic characteristics
of the polymer was disclosed. The selected aroma compound,
dl-limonene (d/lZ1) with a purity of 95%, was purchased
from Aldrich and used without further purication.
2.1. FT-IR measurements
Samples, with 15 cm
2
surface area, were measured by
means of transmission FT-IR with a Bruker FT-IR Tensor
37 equipment, with 4 cm
K1
resolution and 3 s as the typical
acquisition time. The measuring chamber was continuously
purged with a high ow rate stream of dry N
2
to maintain a
zero concentration level outside the polymer lm. During
desorption, previously equilibrated samples (constant
weight during successive measurements) were removed
from the volatile liquid phase, thoroughly and quickly wiped
with a wet and then with a dry tissue to remove the volatile
condensate from the surface (this step is considered as time
zero) and were immediately placed into the measuring
chamber to follow the desorption of the volatile.
Thicker samples (1 mm) were also stepwise measured
during sorption in contact with fresh orange juice. During the
experiment, the specimens were periodically extracted from
the solution, thoroughly wiped to remove the excess of
volatile deposited on the surface, FT-IRrecorded and quickly
returned to the juice. Measurements were carried out until no
differences between consecutive spectra were observed.
All FT-IR experiments were carried out at room
temperature (22 8C), were done in triplicate and the data
averaged before tting to the models.
2.2. Gravimetric measurements
Samples (with similar characteristics to those measured
by FT-IR) were weighed with an analytical balance model
Voyager
w
V11140. Weight changes were registered during
limonene sorption/desorption until constant weight. The
treatment applied to each sample, before and after each
measurement, was similar to the one administered to
samples analyzed by FT-IR.
Direct limonene permeability measurements were also
measured by special aluminium cell weight loss exper-
iments developed at our laboratories at 21 8C and at 0%RH
within a desiccator containing silica gel. Films were rst
dried overnight at 50 8C under vacuum to desorb volatiles,
and then sandwiched between the aluminium top (open
O-ring) and bottom (deposit for the limonene) parts of
the cell with screws. A Viton rubber O-ring was placed
between the lm and the top part of the cell to enhance
D. Cava et al. / Polymer Testing 24 (2005) 483489 484
sealing and vacuum silicone was applied to the bottom cell
to x the lm. Finally, the cell was placed in the desired
environment and the solvent weight loss through the lm
was monitored and plotted as a function of time. Cells with
aluminium lms were used as control samples to estimate
solvent loss through the sealing. Limonene vapour per-
meation rates were estimated from the steady-state per-
meation slopes and weight loss was calculated as the total
cell loss minus the loss through the sealing.
2.3. Data analysis
From data obtained during gravimetric and FT-IR
experiments, sorption and desorption curves of limonene
in LDPE can be easily obtained by plotting, as a function of
time, the ratio between the concentration of limonene, or its
absorbance in FT-IR experiments, in the sample versus that
in the saturated polymer. The equivalence between
concentration and FT-IR absorbance parameters can be
easily deduced from LambertBeer laws, and has been
reported elsewhere [8,9].
Thus, D values were obtained from tting the exper-
imental data to Eq. (1) in sorption experiments and to Eq. (2)
during desorption experiments [10]:
A
t
A
e
Z
M
t
M
e
Z1 K
8
p
2
X
N
nZ0
1
2n C1
2
exp
KD2n C1
2
p
2
t
L
2

(1)
A
t
A
e
Z
M
t
M
e
Z
8
p
2
X
N
nZ0
1
2n C1
2
exp
KD2n C1
2
p
2
t
L
2

(2)
where A
t
and A
e
are absorbances at a given time t and at
saturation respectively, and M
t
and M
e
are concentrations of
limonene at a given time t and at saturation, L is lm
thickness, and D is the diffusion coefcient.
2.4. DSC measurements
Sample specimens of typically 10 mg were measured by
means of differential scanning calorimetry (DSC), in order
to check for differences in crystallinity mass fraction.
Experiments were carried out with a PerkinElmer DSC 7
calorimeter. The DSC runs consisted of a rst heating of the
sample from 25 to 200 8C, cooling down to 25 8C and a
subsequent second heating to 200 8C at a rate of 10 8C/min.
All DSC experiments were run at least in duplicate and the
average value was recorded.
The degree of crystallinity was obtained by comparing
the melting enthalpy of the sample with the melting
enthalpy of a pure polyethylene crystal at 290 J/g.
3. Results and discussion
3.1. Sample thickness effect
The diffusion coefcient monitors the average ability of
sorbed molecules to travel across the permeable phase of the
polymer (usually only the amorphous phase) and, as a result
of that, changes in lm thickness should not, to a rst
approximation, affect this coefcient.
In order to check for that, FT-IR spectra of LDPE cast
extruded lms with two different thicknesses (10 and 80 m)
were monitored during limonene desorption. Spectral
subtraction of the pure polymer from the limonene saturated
polymer permitted isolation of the signal of the sorbed
volatile. From the subtraction spectrum, the band at
888 cm
K1
(assigned to CH deformation) was selected for
this study. This band has previously been selected by other
authors to monitor changes in limonene concentration [3]
because, as can be seen from Fig. 1, no asymmetries or
alterations in the position of the band were observed during
Fig. 1. Subtracted FT-IR spectra in the range of the limonene CH deformation mode recorded during desorption from 80 (left) and 10 (right)
microns LDPE lms.
D. Cava et al. / Polymer Testing 24 (2005) 483489 485
desorption, irrespective of sample thickness. Band fre-
quency shifts and band asymmetry are undesirable effects in
terms of mass transport evaluation because linear corre-
spondence between permeant concentration and band areas
cannot be guaranteed due to potential changes in the
absorption coefcient during the experiment [11].
In Fig. 2, the desorption curves as measured by FT-IR on
the 80 and 10 m lms can be seen. Reproducibility of the
experiments was found to be high, the variability was found
to be below 5%. From this Figure, it can immediately be
perceived that there are clear differences between the two
curves, strongly suggesting a thickness effect on limonene
diffusion. Table 1 shows the estimated limonene D values,
which are clearly higher, ca. nine times faster, for the higher
thickness sample.
To corroborate the effect of thickness on diffusion, single
independent direct permeation measurements by weight loss
were also carried out (see Fig. 3). This gure shows that vapor
transmission rate is faster for the thinner sample, however,
when correction for lm thickness is carried out, proper
permeability values can be calculated, i.e. permeability for
the 80 m lm is 14.379!10
K10
G0.8 g m/s m
2
Pa whereas
for the 10 m lm it is 2.3681!10
K10
G0.5 g m/s m
2
Pa. The
permeability is much faster for the 80 m lm indicating that
the faster diffusion is very likely to be responsible for the
observations.
The presence of thickness effects on transport properties
are most likely attributed to morphological differences
between specimens. Thus, it was rst thought that they
could arise as a result of differences in crystallinity between
the lms due to the different processing conditions set
during extrusion, i.e. the crystallinity being higher for the
thinner specimen. To substantiate this, the specimens were
subsequently analysed by DSC to estimate the crystallinity
content in each lm. Table 2 indicates that the thinner lms
are slightly more crystalline; however, the difference seems
very small to account for the observed differences in the
D value. The latter argument is supported by the work of
Perrin et al. [12], which shows that increasing the crystal-
linity of PVA lms from 28 to 58% results in smaller
reductions in water and ethanol D coefcients.
A second argument was then considered, which puts the
observed discrepancy down to signicant morphological
differences arising between the core and skin part of the
lms and, more importantly, to the different level of
orientation. Fig. 4 shows the melting endotherms of the
two samples. From this gure, it can be seen that while only
one broad melting peak is observed in the endotherm of
the 10 m lm, an additional lower melting point broad
contribution appears in the 80 m lm. This observation
time (s)
0 5000 10000 15000 20000 25000 30000
w
e
i
g
h
t

l
o
s
s

(
g
)
0.10
0.08
0.06
0.04
0.02
0.00
10 microns (VTR = 15.57 g/(h*m
2
))
80 microns (VTR = 10.2528 g/(h*m
2
))
Fig. 3. Average vapor transmission rate of limonene trough LDPE
lms of different thickness.
t / L
2
(sec/m
2
)
0.0
500.0x10
9
1.0x10
12
1.5x10
12
2.0x10
12
2.5x10
12
A
t

/

A
e
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
Fig. 2. Normalized desorption curves of limonene from LDPE lms
with 80 (dashed line) and 10 (dotted line) microns thickness.
Table 1
Limonene D-values in LDPE obtained from the various experiments
shown throughout the paper and from the consulted literature
D value!10
14
(m
2
/s)
Conditions
22 10 m lm desorbed in air
199 80 m lm desorbed in air
6 80 m lm desorbed in water
419 1 mm lm during sorption of pure limonene
4 1 mm lm during sorption from a cold pressed
orange juice
5 Sorption of limonene vapor (conc. 0.719 mg/l)
from a nitrogen stream[18]
43 Sorption from a mixture of limonene and
methanol [7]
Table 2
Crystallinity and melting point (M
p
) obtained from DSC exper-
iments
Crystallinity (%) M
p
(8C)
80 m lms 32.38G0.22 109.78G0.25
10 m lms 33.59G0.13 109.28G0.25
D. Cava et al. / Polymer Testing 24 (2005) 483489 486
suggests a higher heterogeneity in the population of polymer
crystals, in terms of both crystal size and/or orientation, for
the thicker lms. During cast lm extrusion, the skin of the
processed sample coming out of the at die is more quickly
cooled at the roll surface and crystals tend to deform and
orient in the machine direction, while the core of the sample
tends to cool down somewhat more slowly and results in less
oriented morphologies. As the sample becomes thinner
(downgauging) a higher skin/core volume ratio and higher
orientation is expected to occur, because a higher lm
deformation is often required to decrease cast lm thickness
during extrusion. As oriented crystals (more likely in the
skin of the sample and in thinner samples) have higher
melting point and are known to impose a more efcient
tortuous path for the permeants to travel across, they result
in lower diffusion coefcients and in more homogeneous
crystalline morphologies as observed in Fig. 4.
3.2. Outer medium effect
Experiments planned to characterize mass transport are
generally designed in ideal conditions, with a very reduced
number of variables. In this work we also wanted to
determine the effect of the outer medium on the desorption
kinetics, specically, desorption in air versus desorption in
water. One of the boundary conditions that needs to be
satised when tting sorption or desorption data to the
corresponding solution of Ficks second law is that the
permeant concentration at the lm surface is zero. There-
fore, to characterize the transport of a permeant through a
polymer lm one must ensure that the permeant dissipates
immediately upon release from the lm. In a case where the
permeant is not completely dissipated at the interface
between the polymer and the outer atmosphere, i.e. an
equilibrium is reached for the concentration of the permeant
in the two media, the transport process is then governed
by diffusion and partition coefcients. This is, for instance,
the case in a real packaging situation where a permeant
establishes equilibrium between its concentration in the
food and in the package wall. Thus, if immediate dissipation
of the permeant is not satised at the lm surface, changes in
the kinetics of desorption should be expected. To check for
this effect, LDPE lm specimens, previously equilibrated in
pure limonene solutions, were desorbed in water under
standard atmospheric conditions and compared with diffu-
sion in air. To help guarantee the removal of all of the
desorbed volatile, several water ow rates were established
throughout the experiment.
The desorption curves obtained by monitoring the
limonene weight loss in water and in air are plotted in
Fig. 5. As can be seen, desorption in air is considerably
faster than in water. Also, desorption of limonene in water
was found to be independent of increasing the water ow
rate (results not shown). These results appear to suggest that
the D value strongly depends on the composition of the
external environment. The reason for this behavior could lie
in the known fact that limonene is very insoluble in water
and, consequently, the transported limonene molecules will
dissipate very slowly in the water medium. Although a high
ow rate water stream is used to maintain limonene
concentration close to zero, the very low solubility in
water (especially compared to the high compatibility with
LDPE) must result in a signicant reduction of the
concentration gradient at the lm surface. This will help
retain the limonene molecules at the polymer surface, thus
decreasing the effective concentration gradient across the
polymer lm and, hence, lowering the diffusion coefcient.
Another factor to be simultaneously considered is the
potential sorption of water molecules on the polymer lm
during limonene desorption creating a cross diffusion event.
Fig. 5 shows that the specimens immersed in water did not
reach the initial sample weight in the time scale of the
experiment shown. To further investigate that, the
specimens were removed from water and monitored in air
by FT-IR spectroscopy. The spectra showed that there still
was limonene present in the sample and no water bands
Temperature (C)
60 80 100 120
N
o
r
m
a
l
i
z
e
d

H
e
a
t

F
l
o
w

E
n
d
o

U
p

(
W
/
g
)
0.5
1.0
1.5
2.0
2.5
Fig. 4. DSC endotherms of 80 (thicker line) and 10 (thinner line)
microns thickness LDPE lms.
time
1/2
(sec
1/2
)
0 50 100 150 200 250 300
M
t
/
M
e
0.0
0.2
0.4
0.6
0.8
1.0
Fig. 5. Limonene desorption curves from LDPE lms in water
(dotted line) and in air (continuous line).
D. Cava et al. / Polymer Testing 24 (2005) 483489 487
could be detected. This could indicate that a cross diffusion
event may not be a major driving force for the lower
diffusion coefcient of limonene in water.
3.3. Concentration effect
The transport of limonene through packaging materials
has been the subject of numerous studies. Some of these
studies measured limonene diffusion directly from orange
juice [3,5,13], others from pure components [14] or from
mixtures of various volatile compounds [15,16]. Never-
theless, and to the best of our knowledge, there are no
studies explicitly dealing with the effect of concentration on
limonene diffusion. In a previous work, limonene D values
obtained during desorption from LDPE samples saturated in
the pure component were, for the rst time, compared to
those obtained from desorption of binary and ternary
mixtures of limonene and other citric fruit juice volatile
compounds, nding only slight changes in D values, which
were attributed to interactions between the mixture
components [6].
In this context, Fig. 6 shows the sorption curves of
limonene as measured from a pressed orange juice by FT-IR
spectroscopy and from the pure component by weight gain
on 1 mm thick LDPE specimens.
Fig. 7 shows the subtracted FT-IR spectrum showing
characteristic limonene bands in the saturated sample.
Thicker polymer sheets were used in this case because
the concentration of limonene in the pressed orange juice is
comparatively so small that the limonene signal falls below
time (sec)
0 2e+4 4e+4 6e+4 8e+4
Pure limonene solution
M
t
/
M
e
0.0
0.2
0.4
0.6
0.8
1.0
time (sec)
0 2e+6 4e+6 6e+6 8e+6
Experimental data
Best fit
Orange juice
A
t
/
A
e
0.0
0.2
0.4
0.6
0.8
1.0
Fig. 6. Experimental data and theoretical sorption curves obtained for LDPE sheets (1 mm thick) equilibrated in limonene (right) and in an
orange juice (left).
0
.05
.1
.15
1700 1600 1500 1400 1300 1200 1100 1000 900 800
A
b
s
o
r
b
a
n
c
e
Wavenumbers (cm
-1
)
Fig. 7. Subtracted spectrum of the PE sample equilibrated in the juice showing a band prole characteristic of limonene in terms of band
positions and band intensity ratios.
D. Cava et al. / Polymer Testing 24 (2005) 483489 488
the limit of detection of the technique for thinner samples.
FT-IR spectroscopy was not used to analyze limonene
sorption for the pure component because the uptake was
now so large that it would yield overabsorbance in the
infrared spectrum. For the pure component a simple weight
gain gravimetric method was more suitable.
Although, an anomalous behavior has extensively been
reported during sorption of this permeant in polyethylene
[17], the sorption curves in Fig. 6 were best tted to the
appropriate solution of Ficks second law. Thus, even
though the sorption data is not well tted with the Fick
model it permits obtaining an estimation of the diffusion
coefcient and, as Table 1 shows, the values of D were
found to be very different between the two cases. The large
difference observed between the pure component and the
component in a pressed orange juice may have to do with the
non-availability of limonene in the liquid aqueous phase of
the juice, as this is mostly found within the suspended solid
particles. Moreover, notice in Table 1 the similarity between
the diffusion coefcient from the juice and that derived from
a low concentration of limonene vapour. Also note that
thicker compression molded polymer sheets (1 mm plates)
do have a higher diffusion coefcient than oriented cast
extruded lms. In spite of that, it appears that polymer
morphological differences result in smaller diffusion
coefcients differences than concentration effects.
Acknowledgements
The authors would like to thank Mr Y. Saito of Central
Research Laboratory of NIPPON GOHSEI (Japan) for
supplying extruded samples. Moreover, the authors would
like to thank the GV (project Groups 03011) the MCYT
(projects MAT2003-08480-C03 and AGL2003-07326-C02-
01) and the MEC (D.C. fellowship) for nancial support.
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