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Materials Development Department, Fraunhofer Institute for Process Engineering and Packaging IVV, Giggenhauser Strae 35, 85354 Freising, Germany
Chair of Food Packaging Technology, Technische Universitt Mnchen, Weihenstephaner Steig 22, 85354 Freising, Germany
Food Technology Department, University of Applied Sciences Fulda, Marquardstrae 35, 36039 Fulda, Germany
d
Faculty of Mechanical Engineering, University of Applied Science Kempten, Bahnhofstrae 61, 87435 Kempten, Germany
b
c
A R T I C L E I N F O
A B S T R A C T
Article history:
Received 29 March 2015
Received in revised form 14 July 2015
Accepted 9 August 2015
Available online xxx
The aim of this study was to evaluate the inuence of relative humidity (RH) on the oxygen permeability
and water vapour transmission rate (WVTR) of whey protein coated Polyethylene terephthalate (PET) or
whey protein monolayer lms. Furthermore, the activation energies for the permeability of oxygen,
carbon dioxide and nitrogen as well as the permselectivities under different set of temperatures were
measured. The results showed that the permeability values through the whey protein coating and whey
protein lm increased with increasing RH. The water vapour permeability measured at 50% RH of
(9.3 0.6)10 cm3 (STP) cm cm2 s1 Pa1 increased to (16.2 0.9)10 cm3 (STP) cm cm2 s1 Pa1 at 85%
RH. An increase in temperature showed an expected increase of the permeability in both uncoated PET
and the whey protein monolayer. The permselectivity of whey protein lm was determined and the
calculated ratios of the permselectivity (P(N2)/P(O2)/P(CO2):1/(46/(3435)) differed from the simplied
ratios given in the literature (P(N2)/P(O2)/P(CO2):1/4/16). Furthermore the calculated activation energy
values for whey (51 kJ mol1) were in agreement with other studies.
2015 Elsevier Ltd. All rights reserved.
Keywords:
Whey protein lms
PET coatings
Permselectivity
Oxygen permeability
Activation energy
1. Introduction
A multitude of different synthetic polymers were developed in
the last century and are now being processed into packaging
materials and used as or in laminates (Welle, 2007). Increasingly, biobased polymers are the focus of research and development work
(Schmid et al., 2012; Belyamani, Prochazka, Assezat, & Debeaufort,
2014; Kurek, Galus, & Debeaufort, 2014; Marcos et al., 2014; Perone
et al., 2014). An example is whey protein (WP) (McHugh & Krochta,
1994; Schmid, Krimmel, 2014; Schmid, Sngerlaub, 2014). The
barrier properties of WP and the inuence of the processing
conditions have been examined by various research groups (Fang,
Tung, Britt, Yada, & Dalgleish, 2002; de Paula Herrmann, Yoshida,
Antunes, & Marcondes, 2004; Hong & Krochta, 2004; Kokoszka,
Debeaufort, Lenart, & Voilley, 2010; Cinelli et al., 2014; Hammann, &
Schmid, 2014; Schmid, Hammann, 2014). However, there is still a
lack of data about: (1) the permselectivity, (2) the activation energy
(EA) for permeation and (3) the inuence of the relative humidity
(RH) on the oxygen (O2) and water vapour (WV) barrier. Information
about these properties facilitate the design of tailor-made packaging
materials for specic goods.
The manuscript applies standard models and theories about
permeation based on Ficks laws and Grahams solution-diffusion
model which are described elsewhere (Barrer, 1941; Crank, 1979;
Fick, 1855; Graham, 1866; Koros William, 1990; Krevelen, 1990;
Langowski, 2008; Vieth, 1991).
(1) Permselectivity. The term permselectivity describes the
permeability ratio of different permeates. The ratio of P(N2):P(O2):
P(CO2) is for many polymers in the range of 1:4:16 (Mller, 2013).
(2) Activation energy. The permeability (Q) of a material is a
function of the temperature (T) and is described by Arrhenius
equation Eq. (2) (Arrhenius, 1889). Q increases exponentially with
T. The EA is a measure of the energy barrier that needs to be
overcome for Q (McKeen, 2012). Eq. (1) is valid for polymers for a
given morphological state. Polymers are in a glassy state below the
glass transmission temperature (Tg) and are in rubbery state above
22
USA, residual moisture 5 g/100 g), was used to build the base of
the WP solution for the application. The plasticiser, glycerol (Merck
KGaA, Darmstadt, Germany), was used to prevent brittleness of the
lms. The barrier properties were tested for (1) WPI coated on a
PET substrate and (2) a monolayer WPI-lm. The substrate was
needed because the monolayer WPI lm was more fragile and
could not be used for all Q testing devices. (1) PET, thickness
(d) = 11.5 0.5 mm, Mitsubishi Polyester Film GmbH, Wiesbaden,
Germany, was used as the substrate. The liquid WPI solution
was applied on the surface. In combination with PET, the WPI was
23
Table 1
Performed experiments.
Sample
24
The results also show that the Q of all permeants through PET is
higher than through the WPI lm of approximately 20 mm
thickness. This means that the barrier properties of WPI towards
the chosen test gases are higher than that of PET.
The calculated permselectivities are shown in Table 2. The error
ranges are calculated by error propagation according to Gau
(Eden & Gebhard, 2011). For both measured samples, the ratio of
the permselectivity differed from the simplied ratio of 1:4:16 (N2:
O2:CO2) (Mller, 2013). However, the results are in the range for the
results of another study on crystalline PET.
The permselectivity O2/N2 of the WPI lm increases with
increasing T. This behaviour can be explained with the help of the
Eq. (5) that displays the calculation of the ratio of permeability
between the two gases O2 and N2: an increasing permselectivity
O2/N2 implies a higher activation energy for O2 compared to N2. In
contrast, the permselectivity CO2/N2 of the WPI lm is nearly
constant with increasing T and therefore the activation energy for
CO2 and N2 should be in the same range.
Eq. (5): calculation of permselectivity O2/N2
these values was calculated, and the error bars were represented
with the minimum and maximum value.
Fig. 1. Q of N2, O2 and CO2 through uncoated PET (11.40 0.26 mm) at different T.
25
Fig. 2. Q of N2, O2 and CO2 through a WPI lm (dft = 24.15 4.24 mm) at different T.
than the functions of the other gases. For both samples (the
uncoated PET and the WPI lm) the EA is calculated as described in
the introduction and the values are compared in Table 3.
Generally, a higher EA indicates a higher change of Q when T
changes. This was veried with regards to the values of EA for PET.
The measured values were compared to the determinations of
Hong and Krochta (2003). They investigated the O2 barrier
properties of WPI coatings on polypropylene lms (PP). Their
calculated EA of the WPI coating was 47.73 3.77 kJ mol1 and
therefore veries the values calculated in this study.
When the EA for the PET used is compared to that of other
studies it can be concluded that the results of this study are slightly
lower than the values published in other studies. This could be
explained by the fact that other studies did not use the same PET
grade and the relative error of the manometric measurement
method.
Table 2
Permselectivity of N2, O2 and CO2 through uncoated PET and a WPI lm at different T.
WPI lm
PET
This study
23 C
N2Q: N2Q
O2Q: N2Q
CO2Q:
N2Q
35 C
40 C
Other studies (Brandrup & Immergut, 1975; Michaels, Vieth, & Barrie, This study
1963)
25 C
23 C
1.00 0.19
1.00 0.14
1.00 0.13
1
7.40 1.33
6.92 0.95 6.52 0.93 2.235.39
32.74 5.87 27.57 4.37 28.21 3.93 23.1026.15
35 C
40 C
1.00 0.17
1.00 0.19
1.00 0.13
4.22 0.71
5.66 0.77 5.72 0.59
33.52 4.08 34.55 4.74 34.07 3.31
Fig. 3. ln(P) against on 1/T of N2, O2 and CO2 Q measurements of WPI lm (Arrhenius plot).
26
Table 3
Activation energy of Q for N2, O2 and CO2 for different commodities.
Activation energy/kJ mol1
WPI lm
PET
This study Other study (Michaels et al., 1963; Brandrup, & Immergut, 1975; Polyakova, Liu, Schiraldi, Hiltner, This study Other study (Hong, & Krochta, 2003)
& Baer, 2001)
Amorphous
Crystalline
34.26
N2
O2
28.81
CO2 23.06
32.7
32.3
18.4
26.4
37.6
27.6
30; 32.5
36.01
50.73
33.35
47.73 3.77
Fig. 5. WVT through a WPI lm with different moisture gradients (columns with
different letters are signicantly different (p < 0.05).
Fig. 4. WVT through WPI coated and uncoated PET with different moisture gradients (columns with different letters are signicantly different (p < 0.05)).
27
thickness and its error range. It can be clearly seen that Q increases
with increasing RH. This can be explained by the water vapour
sorption isotherms of whey protein lms (unpublished data). The
water content in WPI based lms can increase by approximately
30% (w/w) at 85% RH compared to the equilibrium moisture
content at 50% RH. This leads to increased permeability due to the
higher water content in the WPI based coatings. In addition,
previous studies of Bugnicourt et al. (2013) showed similar
moisture-sensitive behaviour of WPI layers. With increasing RH,
the WPI layer also showed decreasing barrier properties towards
O2 measured according to DIN 53380-3 (DIN, 1998). Considering
the difference in Q between the coating and the lm, no clear trend
was visible. All O2Q100 values, measured at different RH, of the
coatings were higher than these of WPI lms. This indicates a
slightly higher moisture resistance of the WPI lm than the coated
WPI layer on PET. As the lm has obviously better barrier
properties towards O2 with increasing RH than a coated WPI
layer, adhering of a WPI lm to a substrate should be considered
rather than applying it via coating.
In summary, it can be stated that the Q of either a WPI coating or
a WPI lm is affected by the surrounding RH. For greater insight,
higher numbers of determinations are recommended.
4. Conclusions
Due to denaturation, WPI is able to form coherent lms having
excellent barrier properties towards non-polar gases. In contrast,
28
the WVTR through these lms is relatively high because WPI forms
moisture-sensitive polymers.
The goal of this study was to study the fundamental properties
of WPI layers, either as lms or applied as coatings. Different
temperatures (23, 35, 40 C) and different RH (0, 35, 50, 75, 85% RH)
were studied using WPI lms (monolayers) and coatings (part of a
multilayer).
The permselectivity of a WPI lm was described for the rst
time. The calculated ratios of permselectivity (P(N2)/P(O2)/P
(CO2):1/(46/(3435)) differed from the simplied ratios for
standard polymers found in the literature, namely (P(N2)/P(O2)/
P(CO2):1/4/16). These observations are important for the selection
of suitable headspace gas compositions in modied atmosphere
packaging (MAP). Due to the signicantly higher CO2 permeability
in comparision to O2 and N2, a headspace gas composition with
high CO2 concentrations could potentially lead to collapsing of the
package. Therefore, these new data gained in this study are of high
industrial relevance and should be considered when WPI based
barrier materials are used for MAP concepts.
Additionally, the different EA values for the permselectivity of
permeants were determined with respect to varying T. An increase
in T resulted in a denite increase of Q through both uncoated PET
and the WPI monolayer, which points to a dependency of Q on the
surrounding T. Regarding the calculated EA of both polymers,
statements about the degree of that dependency can be made. The
relatively high EA values of the WPI layer cause greater dependency
of Q on T.
The measurements at different RH showed clear results. Q
values for both O2 and WV through the WPI coating and the WPI
lm increased with increasing RH. However, the coating showed a
greater increase than the lm, indicating that the substrate
inuences the properties of the coating. The denatured WPI layer is
still not soluble, but is strongly affected by moisture. Therefore it
should be used in combination with hydrophobic polymers.
For further investigations it would be interesting to develop a
process for determining the breakthrough time for a WPI coating
for different permeates, which would make it possible to calculate
the diffusion coefcient and the solubility coefcient for gases and
water vapour.
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