You are on page 1of 9

Food Packaging and Shelf Life 6 (2015) 2129

Contents lists available at ScienceDirect

Food Packaging and Shelf Life


journal homepage: http://www.elsevier.com/locate/fpsl

Permeation of water vapour, nitrogen, oxygen and carbon dioxide


through whey protein isolate based lms and coatings
Permselectivity and activation energy
Markus Schmida,b,* , Wiebke Zillingera,c , Kajetan Mllera,d, Sven Sngerlauba,b
a

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,

* Corresponding author at: Materials Development Department, Fraunhofer


Institute for Process Engineering and Packaging IVV, Giggenhauser Strae 35, 85354
Freising, Germany. Fax: +49 (0) 8161 491 555.
E-mail addresses: markus.schmid@ivv.fraunhofer.de (M. Schmid),
wiebke.zillinger@ivv.fraunhofer.de (W. Zillinger),
kajetan.mueller@ivv.fraunhofer.de (K. Mller), sven.saengerlaub@ivv.fraunhofer.de
(S. Sngerlaub).
http://dx.doi.org/10.1016/j.fpsl.2015.08.002
2214-2894/ 2015 Elsevier Ltd. All rights reserved.

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

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129

Tg. The Tg of lms made from the major component of WP


(b-lactoglobolin) is reported to be approx. 47  C at 43% RH. Thus,
it can be assumed that plasticised WP based lms are in rubbery
state under ambient conditions (Sothornvit, Reid, & Krochta,
2002).
Eq (1): Arrhenius equation

After logarithmical conversion (see Eq. (2)) and by given respect


to the determinations, ln(P) against 1/T is plotted in a diagram
which results in a linear curve (function of x). P0 represents the yaxis intercept from the regression line and is displayed by the table
calculation software just like the value of the slope. Looking closer,
it comes clear that Eq. (2) follows the form of a normal straight line
in which x is represented by 1/T, the y-axis-intercept equals ln(P0)
and the slope is EA/R. As the universal gas constant and the slope
could be read from the diagram, EA could be calculated via Eq. (3).
Eq. (2): formation of Arrhenius equation

2. Material & methods


2.1. Materials
In the present study a whey protein isolate (WPI) (BiPro
supplied by Davisco Foods International Inc., Le Sueur, Minnesota,

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

Eq. (3): activation energy

(3) Inuence of relative humidity on barrier properties. The


inuence of the water vapour (WV) partial pressure on Q can be
differentiated into three cases. (1) The O2 and WV Q are
independent of the RH for polymers that do not interact with
WV such as non-polar polymers (e.g. polyethylene). (2) Polar
polymers interact with WV, thus Q increases with higher WV
pressure (Kucukpinar, & Doruker, 2004). This behaviour was
observed for the WV permeability coefcient (P) of chitosan, ethyl
cellulose and polyamide 6 (Wellons, & Stannett, 1966; Marais et al.,
2000; Cerruti, Laurienzo, Malinconico, & Carfagna, 2007). (3) For
some polymers Q rst decreases and then increases with higher
WV pressure. Examples are the WV Q of glassy poly(acrylonitrile)
(PAN), nylon 6,6 and some aromatic polyamides and the oxygen
permeability (O2Q) of ethylene-vinyl alcohol copolymer and
polyamide 6 (Barrie and Machin, 1969; Alfageme, Iriarte, Iruin,
Etxeberria, & Uriarte, 1999; Zhang, Britt, & Tung, 2001; Hu et al.,
2005; Muramatsu et al., 2003; Cerruti et al., 2007). Polyethylene
terephthalate (PET) is a promising substrate for WP coatings, the
aforementioned properties tested on PET were therefore the
subject of this study.

applied as a part of a multilayer (hereafter called the coating). (2)


Monolayer lms were produced by coating poly(tetrauoroethylene) (PTFE, d = 500  20 mm, Sahlberg GmbH & Co., KG,
Feldkirchen, Germany). The WPI layer was removed after drying
(hereafter called the lm).
Both substrates were corona pre-treated to a surface energy
>40 mN/m in order to achieve suitable wettability for the WPI
solution for even spreading. Regarding the PTFE surface, the effect
of the enhanced surface energy diminishes during the time of
storage of the samples. Furthermore, due to the marked nonadhesiveness of PTFE, it was possible to remove a coherent WPI
lm from that substrate.
2.2. WPI solution preparation
A standard denatured WPI solution was used for all samples,
since denaturation of the proteins is a prerequisite for building
coherent lms. An aqueous solution of WPI (10% w/w) was heated
to 90  C and stirred (Thermomix 31-1 heating stirrer, Vorwerk
Deutschland Stiftung & Co., KG, Wuppertal, Germany) for 30 min to
ensure denaturation of all protein fractions (Schmid, Eib, & Reinelt,
2015). The solution was then lled into a glass ask and placed in

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129

an ultrasonic water bath (DT 514H, Bandelin electronic GmbH &


Co., KG, Berlin, Germany) to degas the solution and cool it to room
temperature (23  C). Then, the plasticiser was added (66.7% based
on WPI content) and the mixture was stirred for another 30 min.
The degassing was then repeated to remove any air bubbles that
could cause defects in the subsequent coating process. The solution
was usable for 48 h.
2.3. WPI coating on the substrate
During the coating process, the WPI solution was spread evenly
on the different substrates (PET & PTFE) using a coating unit (CUF 5,
Sumet Messtechnik, Denklingen, Germany.) The same parameters
were used for all the samples: speed of application 20 mm/s;
sample length 330 mm; contact pressure 20 N; drying temperature
105  C; drying interval 8.5 min. After the coating process, all
samples were stored horizontal side by side, not stacked, at 23  C
and 50% RH for at least ve days. Within the storage time, the
samples gained equilibrium moisture. The samples of the coated
PET were used for investigations of the bilayer, whereas the layer
on the PTFE was removed from the substrate and used as a sample
lm.
2.4. Barrier properties
For testing the barrier properties, three methods were applied:
(1) a manometric method for O2, nitrogen (N2) and carbon dioxide
(CO2), (2) an O2specic carrier gas method and (3) the water

vapour transmission rate (WVTR) was determined using a


gravimetric method.
(1) Manometric method. The determinations were performed
according to DIN 53380-2 (GDP/E measuring device, Brugger
Feinmechanik GmbH, Mnchen, Germany) at three temperatures:
23  C, 35  C and 40  C and with three different dry gases: N2, O2 and
CO2, respectively. An uncoated PET lm was compared to a WPI
lm of approximately 20 mm thickness.
The measurement was based on an absolute pressure difference
between the two sides of the sample. While the gas oats on the
upper side, there is vacuum on the other side tted with the
pressure sensor. The measuring area of the above device is
sandblasted. Due to the softness of the WPI lm and the vacuum
during the measuring process, the lm is placed in the spaces of the
sandblasted area and therefore alters the measuring area and
results. Therefore, a piece of thin silk paper (0.33  100 m roll,

23

Hahnemuhle FineArt GmbH, Dassel, Germany) with a size of


measuring area was placed between the sandblasted surface and
the smooth WPI lm. These measurements were performed and
reported as mean value of two replications.
(2) Oxygen-specic carrier gas method. This method was only
applied for the PET lms and WPI coatings, because the WPI lms
were relatively thin and therefore mechanically sensitive to
damage. With this method the inuence of the RH on O2Q was
characterized. The barrier properties of this WPI coating were
calculated from the multilayer. For the O2Q tests, a process
following the instructions of DIN 53380-3 (Ox-Tran, Mocon Inc.,
Minneapolis, Minnesota, USA) was chosen. During these measurements, one side of the sample was exposed to owing O2, whereas
the other side faced a owing carrier gas such as N2. The adjusted
RH values were 35%, 50% and 75%. The method was not suitable for
testing WPI coatings at 0% RH because the measuring device was
not designed for long measurement times at low RH, in accordance
with DIN 53380-3, as this would damage the sensor. These
measurements were performed with at least two fold determinations.
(3) Gravimetric determination of water vapour transmission
(WVT). The gravimetric method was applied for PET lms and WPI
coatings and lms (WPI layer thickness circa 20 mm). The barrier
properties of the WPI coating was calculated from the multilayer
and compared with a WPI lm of the same thickness (Eq. (4)). The
temperature during the measurements was set to 23  C for all
determinations.
Eq. (4): total permeability of a multilayer

The WVT determinations were performed according to DIN


53122-1. In this method a metal screw cup (Fraunhofer IVV,
Freising, Germany) with adjusted RH of 0% (silica gel) is sealed with
the sample and placed in a room having a specic RH. Because of
the pressure gradient, WV permeates into the shell, which can be
recorded as an increase in weight of the shells. The pressure
gradients for these determinations were set at 50% RH ! 0% RH and
85% RH ! 0% RH. For each sample at least a threefold determination was performed. The experiments are summarised and
presented in Table 1.
2.5. Thickness measurements
The thicknesses of the lms were measured with a thickness
measuring device (Precision Thickness Gauge FT3, Rhopoint
Instruments, Queensway, East Sussex, UK). A mechanical device

Table 1
Performed experiments.
Sample

O2, manometric method


CO2, manometric method
N2, manometric method
O2, O2-specic carrier gas method
WVTR

WPI lm (24.15  4.24 mm)

WPI coating (24.15  4.24 mm) on PET (11.40  0.26 mm)

PET (11.40  0.26 mm)

(23, 35, 40)  C; 0% RH


(23, 35, 40)  C; 0% RH
(23, 35, 40)  C; 0% RH
23  C, (35, 50, 75)% RH
23  C; 85 ! 0; 50 ! 0% RH

23  C, (35, 50, 75)% RH


23  C; 85 ! 0; 50 ! 0% RH

(23, 35, 40)  C; 0% RH


(23, 35, 40)  C; 0% RH
(23, 35, 40)  C; 0% RH
23  C, (35, 50, 75)% RH
23  C; 85 ! 0; 50!0% RH

24

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129

measures the thickness at ve points on the sample. The


corresponding analyse system calculates the arithmetic mean
and the standard deviation of the ve measurements. To gain the
dry lm thickness (dft) of certain WPI coatings on PET, the values of
uncoated PET were subtracted from the values determined for the
multilayer samples.

Statistical analyses were performed using the statistical


software Visual Xsel 12.1 (CRGraph, Mnchen, Germany). The
determinations concerning the inuence of changing RH were
statistically evaluated by calculation of the arithmetic mean and
standard deviation. For statistical comparison, Students t-test was
performed with a signicance level p  0.05. Due to quantity
restrictions, the characterisations concerning the EA and the
permselectivity were nished after two fold determinations.
Statistical evaluation was not possible with less than three values.
In order to gain a base for comparison, the arithmetic mean of

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.

3.2. Activation energy

2.6. Statistical analysis

3. Results and discussion


3.1. Permselectivity
Figs. 1 and 2 show the Q of N2, O2 and CO2 through uncoated PET
and through a WPI lm at different temperatures and 0% RH. It can
be seen that the N2Q shows the lowest values and the CO2Q shows
the highest values. The O2Q lies between these values. This order
represents the permselectivity.

By taking the above-mentioned results for Q and plotting ln(P)


against the reciprocal temperature (1/T [1/K]), as already described
in the introduction, a linear curve is obtained as shown in Fig. 3.
The error range of these values is calculated with the help of R2,
which is also shown in the gure.
By plotting ln(P) against 1/T, the values of the slopes and the
intercepts of the lines should be in the same order as the
permeabilities. Looking closer at Fig. 3 it comes clear that the O2Q
function of the WPI lm has a greater slope and higher intercepts

Fig. 1. Q of N2, O2 and CO2 through uncoated PET (11.40  0.26 mm) at different T.

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129

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.

3.3. Inuence of relative humidity on the water vapour transmission


rate and on the effective water vapour permeability coefcient
Fig. 4 visualises the measured values of the WVTR through
coated and uncoated PET with different RH gradients at 23  C. The
thickness of the coating is shown in parentheses. As four fold
determinations were performed, statistical evaluation was possible. The error bars represent the standard deviation of the values.
The results were used to calculate P, which is presented later.
The results showed that WVTR of both WPI coated and
uncoated PET increases with increasing RH. The difference
between the samples, measured with the different humidity
gradients, is signicant due to the given signicance level, whereas
the samples among each other show no signicant difference.
Though, the inuence of coating seems to be negligibly small.
Considering Fig. 4, it can be seen that the WVTR for the coated PET

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

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129

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

is lower compared to the uncoated sample with a gradient of


50% ! 0% RH. It can be hypothesised that this effect might be
attributed to the enhancement of the barrier due to the WPI layer.
In contrast, the coated sample shows a higher WVTR with a bigger
RH gradient. This could be explained by the interaction of the WPI
coating with humidity. However, due to the fact that there is no
signicant difference compared to the uncoated sample, the
slightly higher increase of the WV permeation could be related to
measuring uncertainties.
Due to the higher WVTR of the coated sample compared to the
uncoated sample for the 85% ! 0% RH gradient, the barrier
properties of the WPI coating could not be calculated from the
multilayer and so these values were not considered further.
According to 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. Thus, the substrate is limiting the permeability at high
RH.
Fig. 5 shows the effective P (Peff) through a WPI lm measured
with different moisture gradients at 23  C. The WPI lm was on the
humidied side (50% RH or 85% RH) whereas the PET substrate was
on the dry site. For this reason, it was assumed that the WPI had RH
in the layer of 50% RH or 85% RH. These values were taken for the
calculation of the Peff. As these values were measured with four
fold determination, statistical evaluation was performed. The error
bars represent the standard deviation.
The higher the RH the samples were exposed to, the higher the
WVP. There is a progressively increased WV absorption by WP

30; 32.5

36.01
50.73
33.35

47.73  3.77

lms and coatings at increasing RH (Berlin, Anderson, & Pallansch,


1968; Berlin, Kliman, Anderson, & Pallansch, 1973). The results for
the WVP for WPI at 50% RH of (9.3  0.6)10 cm3 (STP) cm cm2
s1 Pa1 and at 85% RH of (16.2  0.9)10 cm3 (STP) cm cm2 s1
Pa1 were in the range of another study. The results for PET at 50%
RH of (2.0  0.2)11 cm3 (STP) cm cm2 s1 Pa1 and at 85% RH of
(2.1  0.1)11 cm3 (STP) cm cm2 s1 Pa1 were also in the range of
other studies which measured values of (1.33.4)11 cm3 (STP) cm
cm2 s1 Pa1 (Marais et al., 2000; Yasuda, & Stannett, 1962).

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)).

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129

27

Fig. 6. O2Q through coated and uncoated PET at different RH.

3.4. Inuence of the relative humidity on the oxygen permeability


The O2Q through PET is also affected by the RH. Fig. 6 displays
the O2Q of uncoated and coated PET lms (the thickness of the
coating is written in parentheses) with increasing humidity at
23  C. Due to the fact that there was only two fold determination,
statistical evaluation was not possible. The error bars display the
measured minimum and maximum values.
The results show that the inuence of increasing RH on O2Q is
different for uncoated and coated PET lms. While the Q through
uncoated PET decreases at higher RH, the Q through the coated
sample increases.
PET is a polymer that interacts with humidity. The anomaly of
the barrier properties of PET at higher RH has been observed by
Auras, Harte, and Selke (2004).
As expected, the increased Q through the coated sample is due
to the applied WPI layer and its residual moisture content. The fact
that even the highest Q of the coated sample is lower than the
lowest value of the uncoated samples justies a closer look at the
WPI coating itself. Therefore, the Q values of the WPI coating were
calculated from the multilayer and are shown in Fig. 7 along with
the values for a WPI lm. Both values (coating and lm) are
presented after transformation of the Q values to a thickness of
100 mm (Q100) in order to have a standard base for comparison.
The error bars display, via error propagation, the calculated
error ranges of the specic values. Therefore, these values could be
counted as the minimum O2 permeability, WPI lms could possibly
perform. The calculation of the error ranges considered the lm

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,

Fig. 7. O2Q100 comparison of WPI coating and WPI lm.

28

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129

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.
References
Alfageme, J. A., Iriarte, M., Iruin, J. J., Etxeberria, A., & Uriarte, C. (1999). Watertransport properties in polyetherimide blends with a liquid crystal polymer.
Journal of Applied Polymer Science, 73, 323332.
Arrhenius, S. (1889). ber die Dissociationswarme und den Einuss der Temperatur
auf den Dissociationsgrad der Elektrolyte. Zeitschrift fur physikalische Chemie, 4,
96116.
Auras, R., Harte, B., & Selke, S. (2004). Effect of water on the oxygen barrier
properties of poly(ethylene terephthalate) and polylactide lms. Journal of
Applied Polymer Science, 92, 17901803.
Barrer, R. M. (1941). Diffusion in and through solids. Cambridge, Eng: CUP Archive.
Barrie, J. A., & Machin, D. (1969). The sorption and diffusion of water in silicone
rubbers: Part I. Unlled rubbers. Journal of Macromolecular Science, Part B, 3,
645672.
Belyamani, I., Prochazka, F., Assezat, G., & Debeaufort, F. (2014). Mechanical and
barrier properties of extruded lm made from sodium and calcium caseinates.
Food Packaging and Shelf Life, 2, 6572.
Berlin, E., Anderson, B. A., & Pallansch, M. J. (1968). Water vapor sorption properties
of various dried milks and wheys. Journal of Dairy Science, 51, 13391344.
Berlin, E., Kliman, P. G., Anderson, B. A., & Pallansch, M. J. (1973). Water binding in
whey protein concentrates. Journal of Dairy Science, 56, 984987.
Brandrup, J., & Immergut, E. H. (1975). Polymer handbook. New York: John Wiley &
Sons.
Bugnicourt, E., & Schmid, M., et al., (2013). Processing and validation of wheyprotein-coated lms and materials with excellent barrier properties. Advances
in Materials Science and Engineering, 2013, 110.
Cerruti, P., Laurienzo, P., Malinconico, M., & Carfagna, C. (2007). Thermal oxidative
stability and effect of water on gas transport and mechanical properties in PA6EVOH lms. Journal of Polymer Science Part B: Polymer Physics, 45, 840849.
Cinelli, P., & Schmid, M., et al., (2014). Whey protein layer applied on biodegradable
packaging lm to improve barrier properties while maintaining
biodegradability. Polymer Degradation and Stability, 108, 151157.

Crank, J. (1979). The mathematics of diffusion. Oxford: Clarendon Press.


de Paula Herrmann, P. S., Yoshida, C. M. P., Antunes, A. J., & Marcondes, J. A. (2004).
Surface evaluation of whey protein lms by atomic force microscopy and water
vapour permeability analysis. Packaging Technology and Science, 17, 267273.
DIN (1998). Prfung von Kunststoffen Bestimmung der Gasdurchlssigkeit Teil
3: Sauerstoffspezisches Trgergas-Verfahren zur Messung an KunststoffFolien und Kunststoff-Formulierungen. DIN 53380-3. Berlin, Beuth Verlag
GmbH.
Eden, K., & Gebhard, H. (2011). Dokumentation in der Mess-und Pruftechnik. SpringerVerlag.
Fang, Y., Tung, M. A., Britt, I. J., Yada, S., & Dalgleish, D. G. (2002). Tensile and barrier
properties of edible lms made from whey proteins. Journal of Food Science, 67,
188193.
Fick, A. (1855). Ueber diffusion. Annalen der Physik, 170, 5986.
Graham, T. (1866). LXIX. On the absorption and dialytic separation of gases by
colloid septa. Philosophical Magazine Series, 4(32), 503531.
Hammann, F., & Schmid, M. (2014). Determination and quantication of molecular
interactions in protein lms: a review. Materials, 7, 79757996.
Hong, S.-I., & Krochta, J. M. (2004). Whey protein isolate coating on LDPE lm as a
novel oxygen barrier in the composite structure. Packaging Technology and
Science, 17, 1321.
Hong, S. I., & Krochta, J. M. (2003). Oxygen barrier properties of whey protein isolate
coatings on polypropylene lms. Journal of Food Science, 68, 224228.
Hu, Y. S., Mehta, S., Schiraldi, D. A., Hiltner, A., & Baer, E. (2005). Effect of water
sorption on oxygen-barrier properties of aromatic polyamides. Journal of
Polymer Science, 43, 13651381.
Kokoszka, S., Debeaufort, F., Lenart, A., & Voilley, A. (2010). Water vapour
permeability, thermal and wetting properties of whey protein isolate based
edible lms. International Dairy Journal, 20, 5360.
Koros William, J. (1990). Barrier polymers and structures: overview. Barrier
polymers and structures. American Chemical Society 121.
Krevelen, D. W. (1990). Properties determining mass transfer in polymeric systems.
Properties of Polymers, 53, 5583.
Kucukpinar, E., & Doruker, P. (2004). Effect of absorbed water on oxygen transport in
EVOH matrices. A molecular dynamics study. Polymer, 45, 35553564.
Kurek, M., Galus, S., & Debeaufort, F. (2014). Surface, mechanical and barrier
properties of bio-based composite lms based on chitosan and whey protein.
Food Packaging and Shelf Life, 1, 5667.
Langowski, H.-C. (2008). Permeation of gases and condensable substances through
monolayer and miltilayer structures. In O. G. Piringer, & A. L. Baner (Eds.), Plastic
packaging: interactions with food and pharmaceuticals (pp. 297347). Weinheim,
Germany: Wiley-VCH Verlag GmbH & Co. KGaA.
Mller, K. (2013). Multilayer lms for bag-in-container systems used in disposable
kegs: basic principles of possible barrier concepts. Brewing Science 66.
Marais, S., & Nguyen, Q. T., et al., (2000). Permeation of water through polar and
nonpolar polymers and copolymers: determination of the concentrationdependent diffusion coefcient. Journal of Polymer Science Part B: Polymer
Physics, 38, 19982008.
Marcos, B., & Srraga, C., et al., (2014). Development of biodegradable lms with
antioxidant properties based on polyesters containing a-tocopherol and olive
leaf extract for food packaging applications. Food Packaging and Shelf Life, 1,
140150.
McHugh, T., & Krochta, J. (1994). Water vapor permeability properties of edible
whey proteinlipid emulsion lms. Journal of the American Oil Chemists Society,
71, 307312.
McKeen, L. W. (2012). Permeability properties of plastics and elastomers. Waltham:
William Andrew.
Michaels, A. S., Vieth, W. R., & Barrie, J. A. (1963). Diffusion of gases in polyethylene
terephthalate. Journal of Applied Physics, 34, 1320.
Muramatsu, M., & Okura, M., et al., (2003). Oxygen permeability and free volume
hole size in ethylenevinyl alcohol copolymer lm: temperature and humidity
dependence. Radiation Physics and Chemistry, 68, 561564.
Perone, N., & Torrieri, E., et al., (2014). Structure and properties of hydroxypropyl
methyl cellulosesodium caseinate lm cross-linked by TGase. Food Packaging
and Shelf Life, 1, 113122.
Polyakova, A., Liu, R. Y. F., Schiraldi, D. A., Hiltner, A., & Baer, E. (2001). Oxygenbarrier properties of copolymers based on ethylene terephthalate. Journal of
Polymer Science, 39, 18891899.
Schmid, M., & Dallmann, K., et al., (2012). Properties of whey-protein-coated lms
and laminates as novel recyclable food packaging materials with excellent
barrier properties. International Journal of Polymer Science, 2012, 1.
Schmid, M., Eib, S., & Reinelt, M. (2015). Modeling, simulation and experimental
validation of drying and denaturation behavior of whey protein isolate based
coatings. Drying Technol. in press.
Schmid, M., Hammann, F., & Winkler, H. (2014). Technofunctional properties of lms
made from ethylene vinyl acetate/whey protein isolate compounds. Packaging
Technology and Science, 27, 521533.
Schmid, M., Krimmel, B., Grupa, U., & Noller, K. (2014). Effects of thermally induced
denaturation on technologicalfunctional properties of whey protein isolatebased lms. Journal of Dairy Science, 97, 53155327.
Schmid, M., Sngerlaub, S., Wege, L., & Stbler, A. (2014). Properties of
transglutaminase crosslinked whey protein isolate coatings and cast lms.
Packaging Technology and Science 799817.
Sothornvit, R., Reid, D. S., & Krochta, J. M. (2002). Plasticizer effect on the glass
transition temperature of beta-lactoglobulin lms. Transactions of the ASAE, 45,
14791484.

M. Schmid et al. / Food Packaging and Shelf Life 6 (2015) 2129


Vieth, W. R. (1991). Diffusion in and through polymers: principles and applications.
New York: Hanser Gardner Pubns.
Welle, F. (2007). Lebensmittelverpackungen: alltglich und doch unscheinbar.
Chemie in unserer Zeit, 41, 96106.
Wellons, J. D., & Stannett, V. (1966). Permeation, sorption, and diffusion of water in
ethyl cellulose. Journal of Polymer Science Part A-1: Polymer Chemistry, 4,
593602.

29

Yasuda, H., & Stannett, V. (1962). Permeation, solution, and diffusion of water in
some high polymers. Journal of Polymer Science, 57, 907923.
Zhang, Z., Britt, I. J., & Tung, M. A. (2001). Permeation of oxygen and water vapor
through EVOH lms as inuenced by relative humidity. J. Appl. Polym. Sci., 82,
18661872.