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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
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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