Polymer Degradation and Stability 108 (2014) 151e157

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Polymer Degradation and Stability

journal homepage: www.elsevier.com/locate/polydegstab

Whey protein layer applied on biodegradable packaging film to

improve barrier properties while maintaining biodegradability
Patrizia Cinelli a, 1, Markus Schmid b, c, Elodie Bugnicourt d, Jessica Wildner e,
Agostino Bazzichi f, Irene Anguillesi g, 2, Andrea Lazzeri g, *
a
National Interuniversity Consortium of Materials Science and Technology (INSTM), Via G. Giusti, 9, 50121 Firenze, Italy
b
Fraunhofer-Institute for Process Engineering and Packaging (IVV), Giggenhauser Strasse 35, 85354 Freising, Germany
c
Chair of Food Packaging Technology, Technische Universita €t München, Weihenstephaner Steig 22, Freising 85354, Germany
d
Innovacio i Recerca Industrial i Sostenible (IRIS), Parc Mediterrani de la Tecnologia, Avda. Carl Friedrich Gauss 11, 08860 Castelldefels, Spain
e
Technologie-Transfer-Zentrum Bremerhaven (TTZ Bremerhaven), Food Technology and Bioprocess Engineering, Fischkai 1, D-27572 Bremerhaven,
Germany
f
Laboratori Archa srl, Via di Tegulaia, 10/A, 56121 Pisa, Italy
g
Pisa University, Department of Civil and Industrial Engineering, Via Diotisalvi 2, 56126 Pisa, Italy

a r t i c l e i n f o a b s t r a c t

Article history: The aim of the present study was to verify that a whey protein-based layer can improve oxygen barrier
Received 6 December 2013 properties of commercial compostable plastic film, while not hindering the biodegradability of the
Received in revised form compostable film as well as not affecting the quality of the compost. The whey protein-based coating was
19 June 2014
applied on a biodegradable commercial film certified to meet the requirements of EN13432. Oxygen
Accepted 2 July 2014
Available online 10 July 2014
barrier properties were significantly improved by the presence of the whey protein layer. This result is
particularly important since biodegradable packaging generally lack in maintaining barrier properties
and the use of not degradable materials to improve barrier to gas and water vapour compromises the
Keywords:
Whey protein isolate
composting of the final packaging. In addition to that, it was important to assess the biodegradability of
Barrier the whey protein layer itself since natural polymers may became not degradable if cross-linked or
Packaging blended with not degradable additives. The material based on denatured whey protein and plasticizer
Biodegradable presented fast biodegradability even after application on the commercial film. These positive results have
Poly lactic acid potential to be used in new cost effective and ecological food packaging designs.
© 2014 Published by Elsevier Ltd.

1. Introduction manufacturing to consumption. These performances are commonly

In packaging protection and safety of the product are very
important since the packed food product binds significantly more
resources than its packaging and insufficient protection of the
product leads to the spoilage of food which causes much higher CO2
emissions than the reduction of packaging material could save [1].
For several sensitive food packaging applications, a high gas and
water vapour barrier are the prerequisite conditions for preserving
the quality of the products throughout their lifecycle, from
* Corresponding author. Tel.: þ390502217807; fax: þ390502217903.
E-mail addresses: patrizia.cinelli@diccism.unipi.it (P. Cinelli), markus.schmid@
ivv.fraunhofer.de (M. Schmid), ebugnicourt@iris.cat (E. Bugnicourt), JWildner@ttz-
bremerhaven.de (J. Wildner), agostino.bazzichi@archa.it (A. Bazzichi), irene.
anguillesi@unipi.it (I. Anguillesi), andrea.lazzeri@unipi.it (A. Lazzeri).
1
Tel.: þ39 050 2217869; fax: þ39 050 2218663.
2
Tel.: þ390502217807; fax: þ390502217903.
achieved by the utilization of multilayers films.
Nevertheless combination of different polymers in various layers
hampers recyclability as mono-materials of high purity are needed
for reprocessing. In addition to that, these polymers are neither
renewable nor biodegradable [2,3]. For example a commonly used
barrier polymer is ethylene vinyl alcohol (EVOH) which provides
high oxygen barrier properties when incorporated in multilayer
structures for food packaging applications in order to protect oxygen
sensitive food products. In order to replace non renewable materials
with low carbon footprint materials, current research actions are
focused on the development of systems based on natural polymers
such as proteins, both from animal [4e6] and vegetal sources [7e9].
Proteins have been evaluated for applications in the field of
packaging, since they can be converted using versatile process
options, and additives [4,10], and present appropriate barrier
properties to water and gas permeation. Several studies have been
published on the use of whey protein for application in packaging

http://dx.doi.org/10.1016/j.polymdegradstab.2014.07.007
0141-3910/© 2014 Published by Elsevier Ltd.
152 P. Cinelli et al. / Polymer Degradation and Stability 108 (2014) 151e157
and it resulted very promising as barrier to moisture and oxygen
[11e20], in particular after a denaturation process [21] or in blends
with other polymers [22]. Whey is a by-product of cheese
manufacturing that contains approximately 7% dry matter. In
general the dry matter includes 13% proteins, 75% lactose, 8%
minerals, about 3% organic acids and less than 1% fat. Worldwide
about 180 to 190  106 tons of whey are produced every year but
only 50% is further processed [23].
Whey protein-based coating combines high barrier properties
and good processing when blended with appropriate plasticizers
such as polyols [24,25], and thus is suitable to act as part of new
eco-efficient food packaging concepts.
The time when whey was considered as only a waste product is
long gone. But only 50% of the accruing cheese-whey is treated and
transformed into different food and feed products whereby about
half of this amount is utilized in liquid form, 30% as powdered
cheese-whey, 15% as lactose and its by-products and the remaining
as whey protein concentrates or isolates [26,27].
Whey protein can be separated and purified from the liquid
whey in an efficient membrane filtration process followed by spray
drying to obtain either Whey Protein Concentrate (WPC, protein
concentration 65e80% in dry matter), or Whey Protein Isolate (WPI,
protein concentrations over 90% in dry matter).
A number of authors have also reported the good barrier
properties of whey proteins based coating on paper and on plastic
substrates [28e30]. Previous studies of application of whey based
layer in multi layers films based on polyethylene terephtalate and
polyethylene, have outlined that the whey layer is able to achieve
superior barrier properties compared to other bioplastics and
approached those of synthetic barrier layers, such as ethylene vinyl
alcohol (EVOH) [31].
The present research addresses a preliminary development and
assessment of a completely biodegradable packaging solution
combining whey proteins based coatings with commercial biode-
gradable films based on blends of co-polyester and poly lactic acid
(PLA). Indeed while PLA blends allows the formation of biode-
gradable films and foils, its potential to substitute, for example
polyolefin films, could be increased using whey based formulations
to improve PLA's resistance to gas permeation which, among PLA
functionalities, is often the limiting factor for packaging applica-
tions. The combination of a carrier film such as PLA with a whey
protein-based coating as coated film is promising and relevant for
the compatibility studied here. Such bi-layers could be further
laminated in order to create final laminates for real industrial
applications.
Furthermore, it is well known that protein layers cannot be used
in packaging applications as standalone films due to their brittle-
ness, which can be tackled by the use of plasticizers or blends with
other polymers and their water sensitivity, which can be addressed
by crosslinking or using them in a sandwich configuration [32e39].
Modification of natural materials such as denaturation, blending
with additives, crosslinking etc can affect the final biodegradability
of the resulting protein-based material. It was thus important to
assess that the layer of whey protein was not affecting the
compostability of the final material.
2. Experimental
2.1. Materials and preparation
Multi layer films were produced using as substrate a commercial
film under the trade name Bio-FlexR F 2110 (prev. Bio-FlexR 467F)
provided by FKuR Kunststoff GmbH, Willich, Germany, of thickness
58 mm. The BIO-FLEX® trade name indicates blends of co-polyester
and PLA CAS 9051e89e2, this film is hereafter referred to as PLA.
The aqueous coating solution used for testing, and hereafter
referred to as Whey, mainly comprises whey protein isolate (WPI)
BiPro (10 wt% in aqueous solution) of Davisco Foods International
(Le Sueur, MN, USA) (dry protein pureness 97.4%; N 6.38). Sorbitol,
supplied by Merck KG (Darmstadt, Germany), was used as plasti-
cizer at 100 wt% based on protein content in the aqueous solution
and mixed with the denatured whey protein solution as reported
elsewhere [13,40,41].
The layer of whey protein was coated onto the substrate film
using an A4-A3 sample size control coater of Erichson GmbH & Co.
KG, Hemer, Germany. The Whey dry coating thickness was 10 mm
leading to a total laminate structure (PLA/Whey) thickness of
68 mm.
The films were dried at 23  C and 50% RH until the samples reached
the equilibrium moisture content at the given temperature and hu-
midity but at least for one week. These samples were used for mea-
surements of permeability, mechanical properties and degradation.
2.2. Methods
Oxygen permeability of the substrate and the coated PLA/Whey
films were measured according to DIN 53380-3 (DIN, 1998) at 23  C
and 50% RH using an Ox-Tran 2/20 (Mocon Inc., Minneapolis, MN,
USA). The coated side of the films was exposed to flowing oxygen
gas and the other side to flowing nitrogen gas. Resulting oxygen
permeability of multilayer films was deduced in terms of cm3
(STP)$m2 d1 bar1 and used for further calculations regarding
permeability of the single whey protein layer. A Whey-coated
polymer film can be considered as a 2-layer-structure, compara-
ble to a laminated material [14,26]. The following equations (1) and
(2) can be used:
d d1 d2
¼ þ (1)
P P1 P2
1 X di 1 1 1
¼ ¼ þ þ þ… (2)
Qtot Pi Q1 Q2 Q3
where d represents the thickness of each layer, i, (d ¼ S di) and P
is the oxygen permeability of each layer. Subscript 1 stands for
the polymer film and subscript 2 for the Whey layer coating on
the surface.
Oxygen permeability values of whey-based coatings are con-
verted to a thickness of 100 mm (Q100) in order to allow direct
comparison of different materials independently of the coating
thickness according to the following equation (3).
Q 100 ¼ Q  ðd=100Þ (3)
Film thicknesses were measured with the instrument Mahr
Millimar C1216 of Mahr GmbH (Go € ttingen, Germany) after oxygen
transmission tests. The thickness of the whey layer coating was
calculated by subtracting the base for PLA film. Five random posi-
tions on the film were measured and averaged.
Samples of PLA films and PLA/Whey films were stamp cut in dog
bone shaped specimen: 11.5 cm length, 2.5 cm wide; 4.0 cm neck
length, 0.6 cm neck wide and used for tensile tests with an Instron
4302 tensile machine (Instron, Norwood, MA, USA), 1 kN cell Load,
running at 10 mm/min.
Scanning electron microscopy (SEM) was a JEOL JSM-5600LV
(Tokyo, Japan), samples were gold sputtered before the analysis
with an Edwards Sputter Coater (Edwards Ltd., Crawley, England).
Film samples with PLA and Whey were analysed for total
organic carbon (TOC) content by a modified method of EN13137
(coulometric). The carbon dioxide released by the combustion in
 P. Cinelli et al. / Polymer Degradation and Stability 108 (2014) 151e157 153

oxygen containing gas flow, free of carbon dioxide at 900e1500  C

is measured by coulometry and indicates the TOC directly. Usually
silicate in the soil does not burn, which prevents the measurement
of TOC in the compost soil with the applied method. Therefore
water soluble fractions of carbon were determined photometrically
(Dr. Lange Test-Kit) in compost soil samples. Nitrogen is reported as
total Kjieldahl nitrogen.
In order to attest the degradability of the Whey when applied on
a film they were performed both disintegration and mineralization
tests. For disintegration tests, PLA and PLA/Whey layer film samples
were buried in compost according to ISO 20200, Plastics e Deter-
mination of the degree of disintegration of plastic materials under
simulated composting conditions in a laboratory-scale test. The
composition of the synthetic compost soil is reported in Table 1.
The compost was kindly provided by the Compost plant “Pian
delle Cortine”, Siena, Italy, based on mixtures of garden waste and
solid municipal waste, with a carbon/nitrogen ratio of 38. This
compost is applied in agriculture. The compost was sieved with Fig. 1. Vessels used in the test.
ASTM E11 tests sieve with mesh aperture of 75 mm, before use.
In the standard applied, the plastic material recovered from the
sieving procedure with ASTM E11 tests sieve N 0.10, with mesh
aperture of 2.0 mm, is considered to be non disintegrated material. Four vessels were prepared (Fig. 1):
The material which passed through the sieves is considered to
be disintegrated. The degree of disintegration D is calculated, in 1 Sample 1 Eluate (blank, to check the activity of the medium
percent, using the equation (4): alone)
2 Sample 2 Eluate plus 1 g of virgin standard cellulose (positive
control)
D ¼ ðmi  mrÞ=mi  100 (4) 3 Sample 3 Eluate plus 1 g of PLA based sample (pieces of
1  2 cm)
mi is the initial dry mass of the test material; mr is the dry mass of 4 Sample 4 Eluate plus 1 g of PLA based sample coated with Whey
the residual test material recovered by sieving. Sample of PLA based (pieces of 1  2 cm)
film and PLA/Whey film were tested by Thermal Gravimetric
Analysis as raw materials and as fragments recovered after the The test was performed in dark glass vessel connected with an
disintegration tests by a TA Instrument Q500 (TA Instruments, New Oxitop instrument, commonly used to determine the biological
Castle, DE, USA), in nitrogen flow at 10  C/min rate, from 25  C to oxygen demand (BOD). This method allows to indirectly determine
600  C. The compost was monitored during the test and analysed at the consumption of organic carbon by absorption of carbon dioxide,
the end of the test, the extract of the compost at 60 %RH was diluted evolved in the mineralization reaction, on sodium hydroxide as
at 30% by weight with water and used for germination test on 10 well as the consumption of oxygen by the microbial flora and its
seeds of cress seed (lepidum sativum), in 10 cm diameter petri transformation in carbon dioxide. The tested samples were kept
dishes, stored in the dark for 48 h at 28  C, each sample was tested under moderate vascular stirring at room temperature (20e22  C),
in three replicates, the germination percentage was calculated for 21 days. The moderate vascular stirring was selected in order
versus the 100% of control (distilled water). not to induce mechanical degradation in the samples due to the use
In this study we used an automated method for testing the of magnetic stirrers.
biodegradability of films based on PLA and PLA/Whey. The positive
reference was standard cellulose. For this test it was used an
inoculum extracted by a sample of mature compost. The compost
was humidified up to 85% RH by addition of sterile water, and
incubated at 4  C for 24 h, then the water phase was extracted
(eluate) by pressing of the matrix and centrifuged at 300 rpm in
order to separate from the particulate material (precipitate and
floating). The recovered eluate was clarified by filtration on fast
filter paper (Whatman n 41), and then the pH was recorded (6.8) in
order to correct it, if it was not in the optimal range as indicated in
the protocol of these type of tests that is fixed at 6.5e7.5.

Table 1
Composition of synthetic solid waste.

Material Dry mass (%)

Sawdust 40
Rabbit-feed 30
Ripe compost 10
Corn starch 10
Saccharose 5
Corn seed oil 4
Urea 1
Fig. 2. SEM Micrograph (200) of PLA film without (left) and with (right) whey layer
Total 100
coating.
154 P. Cinelli et al. / Polymer Degradation and Stability 108 (2014) 151e157

Table 2 [43] of the coating on the carrier film. Likewise recently published
Mechanical properties of the tested films. studies indicate that the Q100 values of similar Whey protein for-
Sample Elongation Tensile strength (MPa) Young's modulus (MPa) mulations can be more than one order of magnitude higher
at break (%) (20e200 cm3 (STP)$m2 d1 bar1) when the films are produced as
PLA 246 20.5 850 cast films in petri dishes where no film orientation takes place and
PLA/Whey 222 8.6 144 much slower curing and drying is applied [31,45].
Mechanical properties were tested and results are reported in
Table 2. The application of Whey on PLA had a moderate effect on
Table 3 elongation at break, while inducing a significant reduction in ten-
Total content of organic carbon and Kjieldahl nitrogen in the films. sile strength at break and in the elastic modulus in the longitudinal
Sample Mean value of total Mean value C/N ratio direction. The mechanical properties of the films are nevertheless
Kjieldahl nitrogen of TOC [g/100 g] [g/100 g] still compatible for application in packaging.
[g/100 g] Table 3 reports the results of analysis on the samples of the PLA
PLA based film 0.09 21.48 e based film used for the tests: a film prepared by casting of Whey
Whey Cast Film 7.76 18.06 2.3 with same composition as the one applied on the PLA based film,
PLA/Whey 1.44 23.36 16.2 and the composition of the PLA/Whey. The ratio between the total
organic carbon and the nitrogen content of the samples was
3. Results and discussion calculated as a compostable indicator for the samples. As the ni-
trogen content of PLA based films was below the detection limit the
It has been previously demonstrated that when the Whey is ratio was not calculated.
applied on a polyethylene terephtalate (PET) film it is possible to As expected raw PLA based films have no content of nitrogen,
achieve barrier properties to oxygen approaching those of com- while the Whey has a relatively consistent content of nitrogen due
mercial materials such as EVOH and even better than polyamide to the presence of protein. In PLA/Whey the nitrogen content is
[42,43]. obviously lowered by the presence of PLA ratio which has no
The preliminary attempt to apply the Whey coating on films contribution to nitrogen. The value of nitrogen content in compost
based on PLA carried out manually at lab scale was promising and soil is in agreement with values expected for this material. The C/N
the application method will be improved in further studies aimed ratio is frequently used as maturity indicator of compost. Usually
at reaching oxygen-barrier properties similar to those obtained for large proportions of the initial organic matter is mineralized during
Whey-coated PET, as is under development in the running Euro- the composting process, resulting in a faster decrease of TOC at the
pean project Wheylayer2 [44]. The coating appears homogeneous beginning of the process due to the degradation of the most easily
as can be observed in Fig. 2 showing SEM micrograph of uncoated biodegradable organic matter fractions. In parallel the Nitrogen
and coated PLA substrate. concentration tends to increase during the composting process
The PLA based substrate film has an Oxygen Permeability (OP) of since less N than C is lost during composting.
512 cm3 (STP)$m2 d1 bar1, while the PLA/Whey film shows an The C/N ratio is frequently used as maturity indicator. A C/N ratio
OP of 80 cm3 (STP)$m2 d1 bar1. An optimization of the process is smaller than 25, and generally smaller than 20 or 15, is character-
expected lead to significantly higher improvement of the barrier istic of mature composts. Decomposing microbes are the most
properties of PLA based films. However, the Whey performance active and efficient when the C/N ratio is 30:1. C/N ratios of 20e35
can be calculated from the equations mentioned above. The are optimum [46].
10 mm thick Whey coating has a calculated OP of 94.8 cm3 (STP)$ Both PLA based film and PLA/Whey disintegrate according to ISO
m2 d1 bar1 and the 100 mm normalized Whey Q100 value which standard since in all the replicates the amount of sample retrieved
can be derived from the OP values mentioned above is 9.5 cm3 was lower than 10% of the starting material, ranging between 3 and
(STP)$m2 d1 bar1 and thus already really good in comparison 6%. Samples of PLA based films and PLA/Whey layer films were
with other biopolymers. Similar whey protein formulations when disintegrated by ISO 20200 test, and both met the normative
used as film coating of petrochemical based substrates such as specifications for disintegration of over 90% of the starting weight
PET provided lower Whey layer Q100 values from 0.4 up to 7.9 [13]. in about 30 days. Image of the starting compost and of compost
However, a direct comparison of the results of this study to the after different durations where PLA and PLA/Whey layer were
existing literature is not possible since processing parameters, respectively buried are shown in Fig. 3.
scale, measurement conditions and methods differ even though the By thermal gravimetric analysis it was outlined that degraded
formulations are quite similar. The processing itself has a huge in- films show a weight lower than the non-degraded material: the
fluence as reported in a related patent on in-process denaturation

Fig. 3. a) Compost at time 0, b) Compost where PLA was degraded (90 days), c) compost where PLA/Whey was degraded.
 P. Cinelli et al. / Polymer Degradation and Stability 108 (2014) 151e157
Fig. 4. TGA curve of PLA and PLA/Whey, before and after disintegration test.
degraded samples begin to lose weight around about 100  C
compared to 220  C in the case of non-degraded samples (Fig. 4).
The films based on PLA with whey and those without, once
degraded, present the same weight loss curves, attesting for the
complete removal of the Whey due to its fast degradation in soil.
The SEM micrographs of the samples recovered from the
compost show the presence of fungi, actinomicetes and micro or-
ganism on the surface and in the bulk of both samples: PLA (Fig. 5)
and PLA/Whey (Fig. 6).
The contents of water soluble organic and inorganic carbon
are slightly higher for the compost where PLA/Whey layer was
degraded (Fig. 7), thus providing a higher content of water soluble
Fig. 5. Micrograph PLA degraded samples a) surface, b) fractured sample.
Fig. 6. Micrograph PLA/Whey degraded samples a) surface, b) fractured sample.
155
nutrients in the compost, most likely induced by the degradation of
the protein-based material (Whey layer).
The content in saturated (20%) and unsaturated fatty acid (80%)
is also almost the same in the three samples (Fig. 8). Thus there is
no significant difference in the quality of the compost where the
PLA/Whey layer was degraded when compared with the compost
where the PLA film was degraded. Likewise the results of the tests
on germination on cress seeds outlined a percentage not signifi-
cantly different for the compost where the PLA (93%) or the PLA/
Whey films (95%) were degraded.
In the present study we also used a rapid method for testing the
biodegradability of films based on PLA and PLA/Whey since the
classic method based on “ISO 14855 Biodegradability in Controlled
Composting Conditions” is long and time consuming e the test can
be carried on up to 6 months e and a considerable amount of
samples are required to perform the test.
The rapid test, performed in liquid medium has several ad-
vantages: liquid medium allows working with homogeneous
substrates avoiding the formation of anaerobic areas and prefer-
ential pathways for the passage of air; it is possible to work in a
small scale without dehydration due to the transfer of air; the
reduced size of the test allows to perform a large number of tests
and controls, also under stirring; at the end of the test it is possible
to recover the material that may be still present in order to make
quantitative analysis or other tests useful to characterize the
material.
In the following figures the curve of oxygen consumption versus
time are reported for the 5 samples tested. The x-axis represents
the time passed from the beginning of the test expressed in mi-
nutes, the y axis displays the oxygen consumption expressed in mg/
L, which is directly related to the mineralization of the organic
carbon present in the sample, thus to the mineralization of the
sample, as previously described.
156 P. Cinelli et al. / Polymer Degradation and Stability 108 (2014) 151e157
Fig. 7. Content of water soluble organic and inorganic carbon in the compost samples.
The tests were stopped when the pressure inside the vessels
was not changing any longer in significant amount, since this is an
evidence of a stop in the production of carbon dioxide thus of a
slowdown of the mineralization of the sample.
Fig. 9 reports the oxygen consumption of the inoculum, thus of
the organic matter present in the inoculum. The value of oxygen
consumption recorded (50 mg/L of oxygen) represents the blank
sample thus the value of oxygen consumption to be subtracted by
the consumption of the investigated samples. The addition to
the incoculum of a easily degradable substance such as cellulose
(positive reference) induces a strong increase in the oxygen de-
mand, which arrives to a maximum of 2400 mg/L (Fig. 9). The
maximum oxygen demand is outlined by the white line, while the
grey line evidences the time required for the cellulose sample to
reach the plateau phase which is associated with the completed
degradation of the sample. The corresponding time of 18 days is
compatible with literature data of cellulose degradation. Analysing
the oxygen consumption of the samples based on PLA it is easily
observed that the oxygen demand (120 mg/L) is almost the same at
the inoculum, thus of the blank reference (Fig. 10). It is infact well
known that PLA has a lag phase (about 15e20 days) for biodegra-
dation due to the time required for the hydrolytic attack to form the
biodegradable oligomers [47].
Thus in the time frame of this test, the mineralization of PLA had
not yet started. The sample based on PLA coated with whey present
a significant oxygen demand (260 mg/L) thus attesting for the
Fig. 8. Content in saturated and unsaturated fatty acids in the compost samples.
Fig. 9. Oxygen consumption for inoculum (light grey) and cellulose (white line) in
liquid-phase biodegradation tests.
mineralization of part of the sample, that is to be considered the
one represented by the Whey layer. We can then assess that they
Whey is completely mineralized in 20 days of test. The test was
then stopped (21 days) and the remaining samples were retrieved
by filtration and weighted after drying, results of weight loss are
reported in Table 4.
The difference in weight of the PLA/Whey film and the PLA
based film was in agreement with that calculated for the whey layer
applied on it, thus confirming the results of the mineralization
tests.
4. Conclusions
As opposed to other existing synthetic barrier polymers, the
application of a whey protein-based coating on a commercial film
based on PLA and co-polyester, certified as compostable, does not
jeopardize the composting of the coated material while leading to a
significant improvement of barrier properties to oxygen permeation.
The compost quality was not affected by the presence of frag-
ments of the films, and in particular no significant differences were
observed in the quality of the compost where the films based
respectively on PLA, and PLA/Whey were disintegrated. Further
work and study are ongoing in order to optimise the application
of the Whey on PLA based commercial films as well as other
Fig. 10. Oxygen consumption for not coated- (light) and whey coated PLA (dark) in
liquid-phase biodegradation tests.
 P. Cinelli et al. / Polymer Degradation and Stability 108 (2014) 151e157
Table 4
Data of sample recovered after degradation.
Sample Macroscopic appearance Initial weight of Weight of
the sample (g) residue (%)
Cellulose Reduced amount of 1 15
cellulose pulp
PLA Scraps of original material 1 86
with same appearance than
the starting material
PLA-Whey Scraps with 1 74
a wrinkled appearance
when compared with
the starting material
biodegradable film substrates that would result in fully compost-
able packaging solutions with further improved barrier properties
to oxygen permeation thanks to the use of whey layer in multilayer
films as internal layer, being thus protected from scratching, water,
and direct contact with the packed food.
Acknowledgements
The authors acknowledge Dettmer Verpackungen GmbH, Lohne
(Oldenburg), Germany, for providing the PLA based film used for
the present study. The authors wish to acknowledge the funding
from the European Community's Seventh Framework Programme
for the research leading to these results under WHEYLAYER “Whey
protein-coated plastic films to replace expensive polymers and
increase recyclability GA 218340-2, and WHEYLAYER2 “barrier
biopolymers for sustainable packaging” GA 315743”.
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