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Whey protein-coated high oxygen barrier film

using various surface treatments

Article in Food Hydrocolloids · January 2018

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 Food Hydrocolloids 80 (2018) 1e7

Contents lists available at ScienceDirect

Food Hydrocolloids
journal homepage: www.elsevier.com/locate/foodhyd

Whey protein-coated high oxygen barrier multilayer films using

surface pretreated PET substrate
Eunmi Joo a, 1, Yoonjee Chang b, 1, Inyoung Choi a, Seul Bi Lee c, Dong Hoo Kim d,
Young Ju Choi c, Chan Suk Yoon d, Jaejoon Han a, b, *
a
Department of Biotechnology, College of Life Sciences and Biotechnology, Korea University, Seoul, 02841, Republic of Korea
b
Department of Food Bioscience and Technology, College of Life Sciences and Biotechnology, Korea University, Seoul, 02841, Republic of Korea
c
EverChemTech Co., Ltd., #313, 314, Human Sky Valley, 959, Gosaek-dong, Gwonseon-gu, Suwon-si, Gyeonggi-do, Republic of Korea
d
Agency for Korea National Food Cluster (AnFC), Iksan, 570-749, Republic of Korea

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

Article history: Whey protein isolate (WPI)-coated multilayer films were developed using polyethylene terephthalate
(PET) film as a substrate. To improve the interfacial compatibility between PET film and water-based WPI
coating solution, various surface pretreatments (corona discharge, plasma, and primer coating) were
Keywords: applied to PET. Water contact angles of the plasma-treated PET were significantly decreased by 12.8%
Whey protein related to the untreated PET, suggesting an increment of hydrophilic functional groups. Oxygen trans-
Multilayer film
mission rates of surface-pretreated multilayer films with WPI coating layer [PET/WPI/nylon/linear low-
Surface coating
density polyethylene (LLDPE)] were significantly lower, about 43e234 times, than the multilayer films
Corona discharge
Plasma
without WPI film layer. In addition, tensile strength of the plasma-pretreated PET/WPI/nylon/LLDPE films
was 13.4 and 21.8% higher, elongation at break was 29.7 and 2.6% higher than the corona discharge- and
primer-pretreated films, respectively. Taken together, WPI films are promising candidates for replacing
synthetic oxygen-barrier materials. Specifically, plasma-pretreated PET/WPI/nylon/LLDPE films have a
high potential as high oxygen-barrier packaging materials.
© 2018 Elsevier Ltd. All rights reserved.

1. Introduction chloride are known to create excellent barriers. However, these

In recent years, oxygen-barrier films have become increasingly
important in the food packaging industry. They are used to extend
the shelf life of foods and to prevent food deterioration owing to
problems such as lipid rancidity, microorganism growth, enzymatic
browning reaction, and vitamin reduction (Bonilla, Atares, Vargas,
& Chiralt, 2012; Yang & Paulson, 2000). To prevent food quality
degradation due to the oxygen inflow, multilayer films composed of
various polymers have been developed (Kurek et al., 2012). In food
packaging materials, typical oxygen-barrier films made of synthetic
polymers such as ethylene vinyl alcohol and polyvinylidene
Abbreviations: WPI, whey protein isolate; PET, polyethylene terephthalate;
LLDPE, linear low-density polyethylene; EAA, ethylene-acrylic acid; LDPE, low
density polyethylene; WCA, water contact angle; FTIR-ATR, Fourier-transform
infrared with attenuated total reflection; OTR, oxygen transmission rate.
* Corresponding author. Department of Food Bioscience and Technology, Korea
University, 145 Anam-ro, Seongbuk-gu, Seoul, 02841, Republic of Korea.
E-mail address: jjhan@korea.ac.kr (J. Han).
1
E.J. and Y.C contributed equally to this work.
synthetic barrier materials are relatively expensive and difficult to
separate for recycling (Hong & Krochta, 2004; Scherzer, 1997;
Tihminlioglu, Atik, & Ozen, 2010). Moreover, synthetic polymers
release large amounts of carbon dioxide (CO2) during incineration,
whereas biopolymers produce lower amounts of CO2 and are
capable of rapid degradation (Mulhaupt, 2013). For these reasons,
sustainable and alternative natural packaging materials are needed
to be developed. Therefore, biological macromolecules such as
carbohydrates, proteins, and lipid-based materials have been
considered in the packaging and bioplastic industry.
Whey protein, a by-product of cheese production, has a high
potential as a film-forming agent. Whey is a complex mixture of
globular protein molecules comprising b-lactoglobulin (~50 wt %),
a-lactalbumin (~20 wt %), immunoglobulins (~10 wt %), and bovine
serum albumin (~6 wt %) and other minor protein or peptide
components including lactoferrin, lactoperoxidase, lysozyme, and
growth factors (Anandharamakrishnan, Rielly, & Stapley, 2008).
WPI, one of the most important whey protein products, is a com-
mercial powder with a high protein content (>90 wt %) normally

https://doi.org/10.1016/j.foodhyd.2018.01.027
0268-005X/© 2018 Elsevier Ltd. All rights reserved.
2 E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7
manufactured by ion exchange chromatography or microfiltration,
followed by spray drying (Foegeding, Davis, Doucet, & McGuffey,
2002). Whey protein-based films have received increasing atten-
tion as they can be importantly used in the food packaging industry.
Whey protein-based films have not only functional benefits of
transparency, flexibility, lack of color, and lack of odor but also
outstanding oxygen and aroma-barrier properties (Galietta, Di
Gioia, Guilbert, & Cuq, 1998; Peelman et al., 2013).
Most industrial synthetic polymers are low-surface-energy (low
wettability) materials and have hydrophobic surfaces. Therefore, it
is very difficult to apply water-based coatings directly on such
synthetic polymers. Modification of polymer surfaces for coating
application by increasing their surface energy is important (Awaja,
Gilbert, Kelly, Fox, & Pigram, 2009; Kostov et al., 2010). Many at-
tempts have been made to modify polymer surfaces by using
methods such as corona discharge, flame, plasma, and chemical
treatments (Hong & Krochta, 2004). Plasma treatment has been
widely used to synthetic polymers for improving their compati-
bility with surface coating materials. Through the interaction be-
tween surface and active species (excited atoms, electrons,
photons, and free radicals) generated by discharges at plasma
treatment, the chemical and physical modifications of polymeric
plastic surfaces are performed and the modified surfaces become
more reactive without losing any of their inherent characteristics.
Plasma active species are combined with oxygen in air, and oxygen-
containing functional groups formed on the polymeric surface lead
to increase surface energy (De Geyter et al., 2008; Kostov et al.,
2010; Wei, 2004). Corona discharge treatment is a surface modifi-
cation technique used to treat polymeric plastic surfaces to improve
their adhesive bonding, ink printability, lamination to other poly-
mers, and wettability from the viewpoint of coating application.
Surface energy, which is generated by surface oxidation and
introduction of polar functional groups (phenolic hydroxyl,
carbonyl, and carboxyl functionalities), was increased through
corona discharge treatment (O'Hare et al., 2002). To form new
functional groups on polymeric plastic surfaces, corona discharge
treatment has been used conventionally. As the surface polarity
increases, intermolecular forces and adhesion strength between
layers' increase (Awaja et al., 2009).
Pretreatment of polymeric plastic surfaces with solvent-based
primers has been attempted to improve their adhesion property.
The ethylene-acrylic acid (EAA) primer solution is useful and
commercially available with various acrylic acid contents, and can
be used in various industrial fields. A copolymer of ethylene and
acrylic acid represents combined characteristics from both of
polyethylene and acrylic acid. Moreover, it is chemically resistant to
organic solvents by polyethylene and widely used for preparing
plastic films and for coating applications. Because it is substantially
soluble in the polyethylene phase, this copolymer solution acts as
an adhesion promoter. The carboxylic acid groups (‒COOH) of
acrylic acid act as reaction sites (Scaffaro, La Mantia, & Castronovo,
2004; Walters & Hirt, 2006).
Generally, multilayer films are used as food packaging materials
rather than single films. Also, the structure of the polyethylene
terephthalate (PET)/WPI/nylon/linear low-density polyethylene
(LLDPE) multilayer film was designed to be similar to one of the
packaging multilayer films commonly used in the food industry
(PET/nylon/LLDPE). Based on the PET/nylon/LLDPE packaging sys-
tem, WPI layer was added because of its high oxygen-barrier
properties. Studies on the manufacture of multilayer films by
applying protein-based coatings as oxygen-barrier materials have
been reported. Bae et al. studied the potential of PET/fish gelatin-
nanoclay composite/low density polyethylene (LDPE) laminate
films (Bae, Park, Darby, Kimmel, & Whiteside, 2009). Schmid et al.
(2012) reported the excellent barrier properties of whey protein-
coated laminated films manufactured at a semi-industrial scale.
Moreover, Shin et al. (2002) reported the fabrication of LLDPE/corn
zein/ethylene vinyl acetate and LLDPE/chitosan/ethylene vinyl ac-
etate films through plasma source ion implantation. However,
multilayer plastic films manufactured by using various surface
treatment methods and their comparative studies have not yet
been investigated.
This study aims to develop the high oxygen-barrier multilayer
films with WPI coating layer (PET/WPI/nylon/LLDPE) using PET film
as a substrate and to improve compatibility of the developed films
with water-based coating of WPI by applying three types of surface
treatments (corona discharge, plasma, and primer coating) to hy-
drophobic PET film. The resulting films were investigated in terms
of (1) change in wettability of PET films, (2) surface structure of the
surface-pretreated PET films with WPI coating layer (PET/WPI), and
(3) oxygen transmission rate (OTR), surface morphology, and me-
chanical properties of PET/WPI/nylon/LLDPE films.
2. Materials and methods
2.1. Materials
Commercial WPI with protein content of >90% (Hilmar 9410,
Hilmar Ingredients, Hilmar, CA, USA) was used as the film-forming
matrix. Sorbitol obtained from Sigma-Aldrich (St. Louis, MO, USA)
was used as a plasticizer to overcome WPI film brittleness. A
commercial PET film (thickness ¼ 12 mm; Hyosung Inc., Seoul, Ko-
rea), nylon film (thickness ¼ 15 mm; Hyosung Inc., Seoul, Korea),
and LLDPE film (thickness ¼ 70 mm; Dae Ryung Precision Packaging
Industry Co., Ltd., Gwangju, Korea) were used to manufacture the
proposed multilayer film with WPI coating layer.
2.2. Preparation of WPI coating solution
Dispersion stability of the WPI coating solution was adjusted by
pH alteration and thermal cross-linking. These adjustments affect
the final structure and function of WPI films. The WPI coating so-
lutions were prepared by dissolving 40 g of WPI powder in 450 ml
of distilled water. Finally, 40 g of sorbitol were added to this
mixture as a plasticizer. To achieve complete aqueous dispersion of
WPI, 10 ml of 1 N sodium hydroxide (NaOH) was added to the
mixture to increase its pH from 7 to 9. The WPI coating solution was
stirred at a constant speed of 300 rpm by using a mechanical stirrer,
and simultaneously heated from room temperature to 90  C by
using a heating mantle. After heating for 30 min at 90  C, the WPI
coating solution was cooled to room temperature and filtered using
a sieve with mesh sizes of 125 mm to remove impurities.
2.3. Surface treatments
2.3.1. Corona discharge treatment
Commercial corona discharge-treated PET films measuring
12 mm in thickness were obtained from Hyosung Inc. (Seoul, Korea).
Corona discharge treatment has been widely applied to various
synthetic polymers and plastic films for the purpose of their good
adhesion property as to modify surface by electrical discharge. PET
films were subjected to corona discharge using a Bare Roll Corona
treater device (Enercon Industries Co., Menomonee Falls, WI, USA).
The device generator was equipped with the Insulated gate bipolar
transistor (IGBT) output amplifier and an automatic control of the
frequency in 20 kHz. The gas flow rate was 20 ml/min.
2.3.2. Plasma treatment
PET films (non-corona discharge-treated, 12 mm thickness;
Hyosung Inc.) were prepared for plasma treatment which was
 E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7
carried out using an atmospheric-pressure plasma system
(Dawonsys Co., Ltd., Ansan, Korea) at the Plasma Technology
Research Center (NFRI, Gunsan, Korea). The films were exposed to
an electrode for generating N2 plasma under atmospheric pressure
to modify their wetting property. Atmospheric-pressure plasma is
generally induced by an electrical discharge passing through a
working gas. Before starting the experiments, PET films were
placed on a stage. A distance between electrode and stage was
adjusted by 3e5 mm. After filling the chamber with working gas
generated by N2 gas purging of 300 L min1, the working pressure
was kept constant at 1 atm during plasma treatment. Then, the
plasma was generated at an electrode power of 1 kW and an elec-
trode voltage of 7 kV and the films were exposed to the plasma for
2 s.
2.3.3. Primer coating
EAA primer coating solution was supplied by Everchemtech
(Suwon, Korea). EAA primer solution (20% EAA in water-ethanol
solution) was used to improve compatibility between WPI and
PET films. To prepare PET films for primer coating, EAA primer
solution of 0.5 g was applied to a PET film by using a wire bar coater
(No. 3, RD Specialties, Webster, NY, USA), and the film was dried for
6 h at room temperature.
2.4. Preparation of WPI-coated bilayer and multilayer films
For preparing PET/WPI bilayer films, 50-mm-thick WPI coating
was applied to one side of pretreated three different PET films by
using an applicator (YBA-5, Yoshimitsu Co., Tokyo, Japan) at a speed
of 285 mm/min. After drying for 6 h at room temperature under
45 ± 5% relative humidity, thickness of the dried WPI film layer on
the PET films was 4.24 ± 1.59 mm.
PET/WPI/nylon/LLDPE multilayer films were developed using a
dry lamination method at laboratory scale. For manufacturing
multilayer laminated films (composed of four layers), the adhesive
was prepared by adding 100 g of an adhesion solution (Neoforce®
KUB-385SK, Kangnamchem Co., Ltd., Seoul, Korea) containing
64e66% urethane resin in 103 g of ethyl acetate solvent. To achieve
complete hardening of the adhesive, 15 g of the hardener (Neo-
force® CL-100, Kangnamchem Co., Ltd., Seoul, Korea) with 74e76%
aromatic polyisocyanate resin was added and stirred at 300 rpm
using an overhead stirrer. After stirring for 30 min at room tem-
perature, adhesive preparation was complete. In the first run of
lamination, 3e4 g m2 of the adhesive was applied on a PET/WPI
film by using a wire bar coater (No. 7, RD Specialties, Webster, NY,
USA). Then, lamination between nylon (15 mm) and PET/WPI film
was performed using a laminator (SKY 325R6, GU Electronics, Paju,
Korea) at around 40  C. The laminated PET/WPI/nylon films were
dried in an oven at 70  C to remove ethyl acetate. In the second run
of lamination, 3e4 g m2 of adhesive was applied to a nylon surface
of a PET/WPI/nylon film by using a wire bar coater. Lamination
between LLDPE (70 mm) and the PET/WPI/nylon film was per-
formed using a laminator at around 40  C. Finally, to induce an
aging effect of the adhesive, the laminated PET/WPI/nylon/LLDPE
films (thickness ¼ 108.33 ± 2.89 mm) were dried in an oven at 50  C
for 48 h.
2.5. Contact angle measurements
Surface hydrophilicity or wettability studies of films usually
involve measurement of the water contact angle (WCA) as the
primary data, usually measured using the sessile drop method and
a contact angle meter (drop shape analyzer, DSA-30S, Kruss,
Hamburg, Germany). A syringe was filled with distilled water, and
the volume of each drop was kept constant at 2 ml. WCAs were
3
measured using image analysis of the liquid drop profile. Mea-
surements of WCA of PET films pretreated with three different
types of surface treatments were carried out at least three times.
2.6. Fourier-transform infrared with attenuated total reflection
(FTIR-ATR) analysis
To observe surface chemical composition of the PET films and
the PET/WPI bilayer films subjected to various surface pre-
treatments, the FTIR-ATR measurements were performed using an
FTIR spectrometer (Cary 630, Agilent Technologies Inc., Santa Clara,
CA, USA) in the ATR mode. The spectra were recorded in the
transmittance mode at 4000e700 cm1 with 32 scans and a reso-
lution of 4 cm1.
2.7. Oxygen transmission rate (OTR) measurement
The OTRs of the PET/WPI and the PET/WPI/nylon/LLDPE films
were measured using an oxygen permeation analyzer (OX-TRAN
Model 2/21, Mocon Inc., Minneapolis, MN, USA) under the
measuring range of 0.0005e2000 cc/m2$day$atm according to the
ASTM D 3895-05 standard. In the cases of the PET and PET/nylon/
LLDPE films, OTR was measured using an oxygen permeation
analyzer (OX-TRAN Model 2/61, Mocon Inc.) under the measuring
range of 0.1e2000 cc/m2$day$atm. Each sample was measured at
least twice.
2.8. Surface morphology
The morphology of the PET/nylon/LLDPE and PET/WPI/nylon/
LLDPE films were observed using a scanning electron microscope
(field-emission gun scanning electron microscopy, FEG-SEM, SU-
70, Hitachi Ltd., Tokyo, Japan) operated at 20 kV and by performing
energy-dispersive x-ray spectroscopy analysis. All samples were
prepared by cutting 5 mm  5 mm strips and placing them on a
carbon tape. The samples were coated with platinum under vac-
uum by using an ion coater (Polalis, SEM Total solution Inc., Suwon,
Korea).
2.9. Mechanical properties
Tensile strength and elongation at break were measured using a
universal testing machine (Model 3366, Instron Engineering CO.,
Norwood, MA, USA) according to the ASTM standard method D882-
02. Elastic modulus was calculated by dividing the tensile stress
with the corresponding strain in the initial linear portion of the
stressestrain curve, selecting any point on this tangent. Each
sample was prepared with the dimensions of 25.4 mm  100 mm
and placed between the grip heads of the machine. The thickness of
each sample was measured using a digimatic caliper (Mitutoyo
Corp, Kanagawa, Japan). For sample conditioning, each sample was
stored in a thermo-hygrostat (Labmade011, Sejong Scientific,
Bucheon, Korea) at 25  C and 50% relative humidity for 48 h before
testing. The cross-head speed was set to 500 mm min1, and the
initial gauge length and grip separation were 50 mm. Each sample
was measured at least four times.
2.10. Statistical analysis
Statistical analysis was performed according to the analysis of
variance method by using Statistical Package for the Social Sciences
(SPSS) software version 23.0 (SPSS Inc., Cary, IL, USA). Differences
between means were computed by performing Duncan's multiple-
range tests. The significance level was defined as P  0.05.
4 E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7
3. Results and discussion
3.1. Contact angle measurements
WCA measurement is the most common method for confirming
change on wettability after surface treatments. Generally, a lower
WCA corresponds to higher hydrophilicity in the case of polymer
surfaces. The obtained WCA values of PET films after each surface
treatment are listed in Table 1. The decrease in WCA can be
explained by the increased number of hydrophilic functional
groups on the modified surface (De Geyter et al., 2008; Kostov et al.,
2010; Shin et al., 2002).
The WCA of the PET films subjected to plasma treatment was
lower than that of the PET films subjected to corona discharge
treatment. This is because lower values of WCA indicate the pres-
ence of multiple hydrophilic groups on the surface. Generally, the
formation of hydrophilic groups by plasma treatment can be
explained by the plasma active species induced by physical and
chemical changes in the PET film surface (Yang, Chen, Guo, &
Zhang, 2009). Because plasma active species were combined with
oxygen in air, functional groups such as hydroxyl, carbonyl,
carboxyl, and ester groups containing oxygen were formed on the
surface of PET films (Kostov et al., 2010). By contrast, auto-adhesion
on polymer films subjected to corona discharge treatment can
generally be explained by hydrogen bonding through carbonyl and
phenolic hydroxyl groups which was formed because of corona
discharge treatment (Briggs, Kendall, Blythe, & Wootton, 1983).
Moreover, carboxyl groups were induced on the polymer surface
owing to an increase in the scission of polymer chains because of
corona discharge treatment (Briggs, Rance, Kendall, & Blythe, 1980).
Lynch, Spence, Baker, and Postlethwaite (1999) stated that
atmospheric-pressure plasma treatment, which controls chemical
elements on a surface affected by inert gases in the plasma system,
is more efficient compared to corona discharge treatment (Lynch
et al., 1999). Based on these results, we could suggest that plasma
treatment is a more efficient method for improving wettability of
PET film surface. In contrast, the WCA of the PET films subjected to
primer coating significantly increased.
An increase in the number of hydrophilic groups ultimately
leads to an increase in the intermolecular force between the sub-
strate films and the coating materials, as well as an increase in
adhesion strength (Awaja et al., 2009). Subsequently, increased
adhesion strength of the films subjected to three different types of
surface treatments was verified from their tensile strength and
elongation at break.
3.2. Fourier-transform infrared with attenuated total reflection
(FTIR-ATR)
After one side of surface-treated PET films was coated by WPI
solution, the surface analysis of PET/WPI bilayer film was per-
formed using the FTIR-ATR spectra (Fig. 1).
FTIR spectrum of an untreated single PET film is shown in
Table 1
Change in water contact angle of polyethylene terephthalate (PET) films by
surface treatment methods.
Surface treatment Contact angle ( )
Untreated 66.4 ± 0.6b
Corona discharge treated 64.8 ± 0.2c
Plasma treated 57.9 ± 1.5d
Primer coated 90.1 ± 0.6a
a-d
Within the same column, different lowercase letters indicate significant
differences (P  0.05).
Fig. 1A. The absorption peaks at 1709 cm1 and 1237 cm1 are
ascribed to C]O stretching vibrations and C-O-C vibrations of ester
group, respectively (Fig. 1A, a). The peak at 1091 cm1 is accus-
tomed to ¼C-H- banding group of benzene ring and the peak near
722 cm1 is owing to the phenyl ring deformation and vibration of
CH2 bending group (Fang, Yang, Liu, Shao, & Zhang, 2013). Ac-
cording to the spectra of single PET films with various surface
treatments (corona discharge, plasma, and primer coating), there
were no significant changes among the PET films with and without
surface treatments (data not shown) although each treatment gave
a rise to chemical modifications on the film surface. In fact, it is
known that the surface treatments affect the change in peak in-
tensity rather than the basic structure of spectrum compared with
those of untreated films, depending on the applied degree of
treatment power (Ding, Shao, & Bai, 2014; Fang et al., 2013).
However, in this study, the application of various surface treat-
ments and their different degree did not show significant change.
The FTIR spectra of the WPI coating solution and WPI side of the
PET/WPI films are shown in Fig. 1A. A broad band around 3500-
3000 cm1 was observed in the spectrum of WPI coating solution,
which is ascribed to the stretching vibration of hydroxyl groups and
asymmetric and symmetric stretching vibrations of the N-H bonds
in amino groups (Fig. 1A, e) (Bagheri, Madadlou, Yarmand, &
Mousavi, 2013; Bahram et al., 2014; Winkler, Vorwerg, & Schmid,
2015). Similar bands could be found in the spectra of PET/WPI
films (WPI side) (Fig. 1A, b-d), however, intensity of the peaks was
decreased. It might be postulated that the -OH and -NH groups of
the protein could interact with polar groups (mainly C]O, -COOH,
and -OH groups) of PET films subjected to various surface treat-
ments (Fig. 1B). Sudhamani, Prasad, and Sankar (2003) reported a
similar result that the interaction between gellan and poly-
vinylalcohol led to significant changes in the -OH stretching region
and the intensity of absorption bands owing to hydrogen bonding
(Sudhamani et al., 2003). The slight bands at 2923 cm1, 2852 cm1,
and 1742 cm1 are attributed to asymmetrical and symmetrical CH2
stretching and C]O stretching of lipids in WPI powder, respec-
tively (Fig. 1A, e) (Ye, Zhou, Shi, Chen, & Du, 2017). The band range
around 1700-1600 cm1 is mainly known as the amide 1 region in
the a-helical component of a-lactalbumin and b-lactoglobulin
secondary structures (Fig. 1A, e), and the sharp peak at 1639 cm1
(Fig. 1A, e) corresponds to the C]O stretching vibrations of peptide
bonds (Fig. 1B) (Ahmadi, Madadlou, & Sabouri, 2015; Madadlou
et al., 2014). Compared to the spectrum of the WPI coating, slight
or profound changes in peak intensity and peak shifts were
observed in the spectra of PET/WPI films (WPI side) previously
subjected to various surface treatments on PET (Fig. 1B). Especially,
the PET/WPI films subjected to corona discharge pretreatment on
PET showed a decrease in peak intensity compared to the others,
indicating the high intermolecular interaction between -OH and
-NH groups of protein and polar groups of PET films. High inter-
molecular interaction can prevent the oxygen molecules from
moving through the free volumes (Vartiainen, Laine, Willberg-
€inen, Pitka
€nen, & Ohra-aho, 2017). Subsequently, this high
Keyrila
intermolecular interaction contributes to the strong oxygen-barrier
property of PET/WPI/nylon/LLDPE multilayer films previously
subjected to corona discharge treatment on PET.
3.3. Oxygen transmission rate (OTR)
Whey protein-based films are well known as excellent oxygen-
barrier materials (Hong & Krochta, 2004; Schmid et al., 2012;
Winkler, Vorwerg, & Schmid., 2015). To observe the oxygen-
barrier property of WPI coating as a barrier layer of PET/nylon/
LLDPE films, OTR measurements of PET/WPI and PET/WPI/nylon/
LLDPE films were carried out (Table 2).
 E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7 5

Fig. 1. (A) Fourier-transform infrared with attenuated total reflection (FTIR-ATR) spectra of an untreated polyethylene terephthalate (PET) film (a) and PET/whey protein isolate
(WPI) bilayer films (WPI side) previously subjected to (b) primer coating, (c) plasma treatment, (d) corona discharge treatment, and (e) WPI coating solution. (B) Magnified image of
broad band patterns of PET/WPI bilayer films (4000-2400 cm1) previously subjected to (a) corona discharge (PET/WPI, corona), (b) plasma (PET/WPI, plasma), and (c) primer
coating (PET/WPI, primer) treatments on PET film.

Table 2
Comparison of oxygen transmission rate (cc/m2$day$atm) of substrate PET only, PET/WPI, PET/nylon/LLDPE, and PET/WPI/nylon/LLDPE films previously subjected to various
surface treatments on PET film.

Surface treatment Substrate PET PET/WPI PET/nylon/LLDPE PET/WPI/nylon/LLDPE

Corona discharge treated 126.194 ± 4.518a 0.274 ± 0.074a 35.058 ± 0.039a 0.166 ± 0.090a
Plasma treated 127.318 ± 0.952a 0.195 ± 0.003a 35.313 ± 1.238a 0.151 ± 0.011a
Primer coated 123.990 ± 1.696a 0.969 ± 1.321a 37.194 ± 0.466a 0.859 ± 0.246b
a-b
Within the same column, the different lowercase letters indicate significant differences (P  0.05). Substrate PET, surface-pretreated PET films without WPI film layer; PET/
WPI, surface-pretreated PET films with WPI film layer; PET/nylon/LLDPE, surface-pretreated multilayer films without WPI film layer; PET/WPI/nylon/LLDPE, surface-
pretreated multilayer films with WPI film layer.

As a result of OTR analysis, PET/WPI/nylon/LLDPE films previ-
ously subjected to plasma and corona discharge treatments on PET
had very low OTRs of 0.151 ± 0.011 and 0.166 ± 0.090 cc/
m2$day$atm, respectively. By contrast, the PET/WPI/nylon/LLDPE
films previously subjected to primer coating treatment on PET had
high OTR of 0.859 ± 0.246 cc/m2$day$atm. From our OTR mea-
surement, the OTR of free-standing WPI film was 0.010 ± 0.006 cc/
m2$day$atm. Because WPI coating was applied to PET/nylon/LLDPE
films, the OTRs of PET/WPI/nylon/LLDPE films previously subjected
to primer coating, corona discharge, and plasma treatments on PET
showed about 43, 211, 234 times lower OTR values, respectively,
than those of the PET/nylon/LLDPE films without WPI layer.
Moreover, the PET/WPI/nylon/LLDPE films composed of PET and
nylon films are expected to be resistant to oxygen gradients. The
oxygen-barrier properties of both synthetic films and biopolymers
have been determined by the degree of crystallinity and solubility
of oxygen (Vartiainen et al., 2017). Degree of crystallinity of WPI
films can be controlled by heat treatment. Under the application of
appropriate heat treatment to hydrated whey protein, the intra-
molecular interactions of whey protein-based polymer chains
broke down and an open linear structure and a dense network of
whey protein matrices were created. Moreover, as crystal sites of
whey protein matrices were increased, free volumes of those were
reduced during heat treatment (Perez-gago & Krochta, 2001;
Vartiainen et al., 2017). Polar functional groups formed by each
surface treatment on PET films played important roles in
strengthening the intermolecular interactions with WPI films by
preventing the transport of oxygen molecules through the free
volumes (Vartiainen et al., 2017). In the case of PET/WPI/nylon/
LLDPE films previously subjected to primer coating on PET, EAA
solution was used as the primer coating. However, EAA copolymer
has a very high OTR of 2549e4569 cc/m2$day$atm (McKeen, 2012).
Therefore, it could be suggested that high OTR value of EAA
copolymer rarely affected OTR of PET/WPI/nylon/LLDPE films
previously subjected to primer coating on PET.
The oxygen-barrier properties of the PET/WPI/nylon/LLDPE
films were significantly improved by corona discharge and plasma
treatment. Owing to increased wettability resulting from corona
discharge and plasma treatments, the increase in intermolecular
interaction between PET and WPI films corresponds to a decrease in
free volume (Awaja et al., 2009; Vartiainen et al., 2017). Moreover,
the increased wettability was attributed to evenly distributed and
homogeneous coating layers on PET films subjected to various
surface treatments. Consequently, the oxygen-barrier properties of
the PET/nylon/LLDPE films previously subjected to corona
discharge and plasma treatments on PET were substantially better
than those of the PET/nylon/LLDPE films previously subjected to
primer coating treatment on PET.
3.4. Surface morphology
Through the microscopic analysis, the adhesion properties of
the PET/nylon/LLDPE and the PET/WPI/nylon/LLDPE films were
found to be good, as shown in Fig. 2. Furthermore, scanning elec-
tron micrographs of the cross-sections of the PET/WPI/nylon/LLDPE
films are very useful for understanding their mechanical properties
and OTR. In the case of PET/nylon/LLDPE films (Fig. 2aec), WPI film
layers were not presented. Although WPI film layers were present
in the PET/WPI/nylon/LLDPE films previously subjected to various
surface treatments on PET, no apparent difference was observed
between the PET/nylon/LLDPE films and PET/WPI/nylon/LLDPE
films (Fig. 2def). Because very thin WPI film layers (4.24 ± 1.59 mm
thickness) were covered by synthetic films, they were not clearly
identified in the images of PET/WPI/nylon/LLDPE films previously
subjected to various surface treatments on PET (Fig. 2def). Fig. 2
clearly shows that both PET/nylon/LLDPE films and PET/WPI/
nylon/LLDPE films were formed uniformly. That is, each film layer
was evenly distributed. The WPI film layers were significantly
6 E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7

strength of the PET/WPI/nylon/LLDPE films was lower than that of

Fig. 2. Scanning electron micrographs of cross-section of PET/nylon/LLDPE films with
(a) corona-discharge treatment, (b) plasma treatment, and (c) primer coating treat-
ment; cross-section of PET/WPI/nylon/LLDPE films with (d) corona discharge treat-
ment, (e) plasma treatment, and (f) primer coating treatment.
thinner than the synthetic film layers. Therefore, very thin WPI
films can be identified in PET/WPI/nylon/LLDPE films (Fig. 2def).
With each of the surface treatments on PET films, evenly
distributed WPI films without surface crack and layer separation
were formed. Moreover, the urethane adhesive was covered evenly
during lamination. To prevent a phenomenon of layer's delamina-
tion in multilayer films, it is necessary to ensure adequate adhesion
ability at interfaces between the coatings and the substrate films.
As a result, upon delamination, the multilayer films exhibited
increased OTR and reduced mechanical properties. Overall, the PET/
nylon/LLDPE films and PET/WPI/nylon/LLDPE films previously
subjected to various surface treatments on PET showed good layer
integrity and no delamination.
3.5. Mechanical properties
Tensile strength, elongation at break, and elastic modulus of the
PET/nylon/LLDPE and the PET/WPI/nylon/LLDPE films are summa-
rized in Table 3. For each surface treatment on PET films, the tensile
the PET/nylon/LLDPE films. Reduced tensile strength of the PET/
WPI/nylon/LLDPE films can be attributed to the low physical
strength of WPI films. From the mechanical property measure-
ments, the tensile strength, elongation at break, and elastic
modulus of the free-standing WPI films were 3.84 ± 0.44,
35.34 ± 4.63%, and 1.25 ± 0.24 MPa, respectively. Generally, multi-
layer films including biopolymers are affected by the weak physical
strength of biopolymers (Shin et al., 2002). The tensile strength of
the multilayer films previously subjected to primer coating treat-
ment on PET was higher than that of the other multilayer films. The
tensile strength of the multilayer films depended on the physical
strength of the substrate film, and the addition of adhesion pro-
moters such as EAA primer could improve the mechanical prop-
erties as well as adhesion performance at the interface (Awaja et al.,
2009; Park et al., 2012). By contrast, the tensile strength of the PET/
WPI/nylon/LLDPE films previously subjected to primer coating
treatment on PET was significantly lower (P  0.05) than that of the
PET/nylon/LLDPE films previously subjected to primer coating
treatment on PET. This may be due to lower compatibility at the
interface between the WPI film and PET film subjected to primer
coating treatment. The elongation at break of the PET/WPI/nylon/
LLDPE films previously subjected to plasma treatment on PET
increased considerably (P  0.05) compared to that of the PET/
nylon/LLDPE films. We suggest that the increased surface polarity
due to plasma treatment contributed toward increasing their
adhesion strength to a level sufficient to withstand physical
deformation in comparison to that of the PET/WPI/nylon/LLDPE
films subjected to the other surface treatments. For each surface
treatment on PET films, no statistical difference (P > 0.05) in elastic
modulus of the films was observed in both the PET/WPI/nylon/
LLDPE films and PET/nylon/LLDPE films. Thus, we assumed that the
elastic modulus was not affected by the surface treatments.
Consequently, the tensile strength and elongation at break of
the PET/WPI/nylon/LLDPE films previously subjected to plasma
treatment on PET were considerably higher (P  0.05) than those of
the other PET/WPI/nylon/LLDPE films. The PET/WPI/nylon/LLDPE
film subjected to plasma treatment under the processing condi-
tions described previously were revealed to have the potential for
the enhancement of physicochemical characteristics.
4. Conclusions
In this study, WPI-coated multilayer (PET/WPI/nylon/LLDPE)
films were developed using PET film as a substrate. By the plasma
treatment, WCA of the PET film was significantly decreased
compared to the untreated PET film, suggesting an increase of hy-
drophilic functional groups. Moreover, the oxygen-barrier proper-
ties of the PET/WPI/nylon/LLDPE films previously subjected to
corona discharge and plasma treatments on PET were significantly
improved. Through the microscopic analysis, the PET/nylon/LLDPE

Table 3
Mechanical properties of the PET/nylon/LLDPE films and PET/WPI/nylon/LLDPE films previously subjected to various surface treatments on PET.

Treatment Film construction Tensile strength (MPa) Elongation at break (%) Elastic modulus
(MPa)

Corona discharge treated PET/nylon/LLDPE 54.62 ± 2.76bc 95.67 ± 11.10ab 557.16 ± 190.97a
Corona discharge treated PET/WPI/nylon/LLDPE 51.62 ± 5.30ab 82.01 ± 21.07a 530.30 ± 138.32a
Plasma treated PET/nylon/LLDPE 67.44 ± 0.85d 100.35 ± 13.21ab 530.99 ± 57.11a
Plasma treated PET/WPI/nylon/LLDPE 58.53 ± 3.71c 106.34 ± 13.16bc 571.71 ± 143.82a
Primer coated PET/nylon/LLDPE 72.91 ± 1.53e 124.08 ± 7.26c 526.34 ± 93.93a
Primer coated PET/WPI/NY/LLDPE 48.04 ± 3.78a 103.66 ± 21.93a 437.34 ± 164.61a
a-e
Within the same column, the different lowercase letters indicate significant differences (P  0.05). PET, polyethylene terephthalate; LLDPE, linear low density polyethylene;
WPI, whey protein isolate; PET/nylon/LLDPE, multilayer films without WPI film layer; PET/WPI/nylon/LLDPE, multilayer films with WPI film layer.
 E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7
films and PET/WPI/nylon/LLDPE films showed good layer integrity
with no delamination. Moreover, tensile strength and elongation at
break of the PET/WPI/nylon/LLDPE films previously subjected to
plasma treatment on PET showed significantly higher values than
those of PET/WPI/nylon/LLDPE films previously subjected to corona
discharge and primer coating treatments on PET, respectively.
Taken together, WPI film layers are promising materials for
replacing synthetic oxygen-barrier ones. Especially, plasma-treated
PET/WPI/nylon/LLDPE films have a potential for high oxygen-
barrier packaging materials.
Acknowledgements
This research was supported by the High Value-added Food
Technology Development Program of the Korea Institute of Plan-
ning and Evaluation for Technology in Food, Agriculture, Forestry
and Fisheries (IPET) (315070-3).
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