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Peliculas Multicapa
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Food Hydrocolloids
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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
Available online 4 February 2018 (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.
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, coated laminated films manufactured at a semi-industrial scale.
followed by spray drying (Foegeding, Davis, Doucet, & McGuffey, Moreover, Shin et al. (2002) reported the fabrication of LLDPE/corn
2002). Whey protein-based films have received increasing atten- zein/ethylene vinyl acetate and LLDPE/chitosan/ethylene vinyl ac-
tion as they can be importantly used in the food packaging industry. etate films through plasma source ion implantation. However,
Whey protein-based films have not only functional benefits of multilayer plastic films manufactured by using various surface
transparency, flexibility, lack of color, and lack of odor but also treatment methods and their comparative studies have not yet
outstanding oxygen and aroma-barrier properties (Galietta, Di been investigated.
Gioia, Guilbert, & Cuq, 1998; Peelman et al., 2013). This study aims to develop the high oxygen-barrier multilayer
Most industrial synthetic polymers are low-surface-energy (low films with WPI coating layer (PET/WPI/nylon/LLDPE) using PET film
wettability) materials and have hydrophobic surfaces. Therefore, it as a substrate and to improve compatibility of the developed films
is very difficult to apply water-based coatings directly on such with water-based coating of WPI by applying three types of surface
synthetic polymers. Modification of polymer surfaces for coating treatments (corona discharge, plasma, and primer coating) to hy-
application by increasing their surface energy is important (Awaja, drophobic PET film. The resulting films were investigated in terms
Gilbert, Kelly, Fox, & Pigram, 2009; Kostov et al., 2010). Many at- of (1) change in wettability of PET films, (2) surface structure of the
tempts have been made to modify polymer surfaces by using surface-pretreated PET films with WPI coating layer (PET/WPI), and
methods such as corona discharge, flame, plasma, and chemical (3) oxygen transmission rate (OTR), surface morphology, and me-
treatments (Hong & Krochta, 2004). Plasma treatment has been chanical properties of PET/WPI/nylon/LLDPE films.
widely used to synthetic polymers for improving their compati-
bility with surface coating materials. Through the interaction be- 2. Materials and methods
tween surface and active species (excited atoms, electrons,
photons, and free radicals) generated by discharges at plasma 2.1. Materials
treatment, the chemical and physical modifications of polymeric
plastic surfaces are performed and the modified surfaces become Commercial WPI with protein content of >90% (Hilmar 9410,
more reactive without losing any of their inherent characteristics. Hilmar Ingredients, Hilmar, CA, USA) was used as the film-forming
Plasma active species are combined with oxygen in air, and oxygen- matrix. Sorbitol obtained from Sigma-Aldrich (St. Louis, MO, USA)
containing functional groups formed on the polymeric surface lead was used as a plasticizer to overcome WPI film brittleness. A
to increase surface energy (De Geyter et al., 2008; Kostov et al., commercial PET film (thickness ¼ 12 mm; Hyosung Inc., Seoul, Ko-
2010; Wei, 2004). Corona discharge treatment is a surface modifi- rea), nylon film (thickness ¼ 15 mm; Hyosung Inc., Seoul, Korea),
cation technique used to treat polymeric plastic surfaces to improve and LLDPE film (thickness ¼ 70 mm; Dae Ryung Precision Packaging
their adhesive bonding, ink printability, lamination to other poly- Industry Co., Ltd., Gwangju, Korea) were used to manufacture the
mers, and wettability from the viewpoint of coating application. proposed multilayer film with WPI coating layer.
Surface energy, which is generated by surface oxidation and
introduction of polar functional groups (phenolic hydroxyl, 2.2. Preparation of WPI coating solution
carbonyl, and carboxyl functionalities), was increased through
corona discharge treatment (O'Hare et al., 2002). To form new Dispersion stability of the WPI coating solution was adjusted by
functional groups on polymeric plastic surfaces, corona discharge pH alteration and thermal cross-linking. These adjustments affect
treatment has been used conventionally. As the surface polarity the final structure and function of WPI films. The WPI coating so-
increases, intermolecular forces and adhesion strength between lutions were prepared by dissolving 40 g of WPI powder in 450 ml
layers' increase (Awaja et al., 2009). of distilled water. Finally, 40 g of sorbitol were added to this
Pretreatment of polymeric plastic surfaces with solvent-based mixture as a plasticizer. To achieve complete aqueous dispersion of
primers has been attempted to improve their adhesion property. WPI, 10 ml of 1 N sodium hydroxide (NaOH) was added to the
The ethylene-acrylic acid (EAA) primer solution is useful and mixture to increase its pH from 7 to 9. The WPI coating solution was
commercially available with various acrylic acid contents, and can stirred at a constant speed of 300 rpm by using a mechanical stirrer,
be used in various industrial fields. A copolymer of ethylene and and simultaneously heated from room temperature to 90 C by
acrylic acid represents combined characteristics from both of using a heating mantle. After heating for 30 min at 90 C, the WPI
polyethylene and acrylic acid. Moreover, it is chemically resistant to coating solution was cooled to room temperature and filtered using
organic solvents by polyethylene and widely used for preparing a sieve with mesh sizes of 125 mm to remove impurities.
plastic films and for coating applications. Because it is substantially
soluble in the polyethylene phase, this copolymer solution acts as 2.3. Surface treatments
an adhesion promoter. The carboxylic acid groups (‒COOH) of
acrylic acid act as reaction sites (Scaffaro, La Mantia, & Castronovo, 2.3.1. Corona discharge treatment
2004; Walters & Hirt, 2006). Commercial corona discharge-treated PET films measuring
Generally, multilayer films are used as food packaging materials 12 mm in thickness were obtained from Hyosung Inc. (Seoul, Korea).
rather than single films. Also, the structure of the polyethylene Corona discharge treatment has been widely applied to various
terephthalate (PET)/WPI/nylon/linear low-density polyethylene synthetic polymers and plastic films for the purpose of their good
(LLDPE) multilayer film was designed to be similar to one of the adhesion property as to modify surface by electrical discharge. PET
packaging multilayer films commonly used in the food industry films were subjected to corona discharge using a Bare Roll Corona
(PET/nylon/LLDPE). Based on the PET/nylon/LLDPE packaging sys- treater device (Enercon Industries Co., Menomonee Falls, WI, USA).
tem, WPI layer was added because of its high oxygen-barrier The device generator was equipped with the Insulated gate bipolar
properties. Studies on the manufacture of multilayer films by transistor (IGBT) output amplifier and an automatic control of the
applying protein-based coatings as oxygen-barrier materials have frequency in 20 kHz. The gas flow rate was 20 ml/min.
been reported. Bae et al. studied the potential of PET/fish gelatin-
nanoclay composite/low density polyethylene (LDPE) laminate 2.3.2. Plasma treatment
films (Bae, Park, Darby, Kimmel, & Whiteside, 2009). Schmid et al. PET films (non-corona discharge-treated, 12 mm thickness;
(2012) reported the excellent barrier properties of whey protein- Hyosung Inc.) were prepared for plasma treatment which was
E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7 3
carried out using an atmospheric-pressure plasma system measured using image analysis of the liquid drop profile. Mea-
(Dawonsys Co., Ltd., Ansan, Korea) at the Plasma Technology surements of WCA of PET films pretreated with three different
Research Center (NFRI, Gunsan, Korea). The films were exposed to types of surface treatments were carried out at least three times.
an electrode for generating N2 plasma under atmospheric pressure
to modify their wetting property. Atmospheric-pressure plasma is 2.6. Fourier-transform infrared with attenuated total reflection
generally induced by an electrical discharge passing through a (FTIR-ATR) analysis
working gas. Before starting the experiments, PET films were
placed on a stage. A distance between electrode and stage was To observe surface chemical composition of the PET films and
adjusted by 3e5 mm. After filling the chamber with working gas the PET/WPI bilayer films subjected to various surface pre-
generated by N2 gas purging of 300 L min1, the working pressure treatments, the FTIR-ATR measurements were performed using an
was kept constant at 1 atm during plasma treatment. Then, the FTIR spectrometer (Cary 630, Agilent Technologies Inc., Santa Clara,
plasma was generated at an electrode power of 1 kW and an elec- CA, USA) in the ATR mode. The spectra were recorded in the
trode voltage of 7 kV and the films were exposed to the plasma for transmittance mode at 4000e700 cm1 with 32 scans and a reso-
2 s. lution of 4 cm1.
3. Results and discussion 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
3.1. Contact angle measurements 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
WCA measurement is the most common method for confirming 722 cm1 is owing to the phenyl ring deformation and vibration of
change on wettability after surface treatments. Generally, a lower CH2 bending group (Fang, Yang, Liu, Shao, & Zhang, 2013). Ac-
WCA corresponds to higher hydrophilicity in the case of polymer cording to the spectra of single PET films with various surface
surfaces. The obtained WCA values of PET films after each surface treatments (corona discharge, plasma, and primer coating), there
treatment are listed in Table 1. The decrease in WCA can be were no significant changes among the PET films with and without
explained by the increased number of hydrophilic functional surface treatments (data not shown) although each treatment gave
groups on the modified surface (De Geyter et al., 2008; Kostov et al., a rise to chemical modifications on the film surface. In fact, it is
2010; Shin et al., 2002). known that the surface treatments affect the change in peak in-
The WCA of the PET films subjected to plasma treatment was tensity rather than the basic structure of spectrum compared with
lower than that of the PET films subjected to corona discharge those of untreated films, depending on the applied degree of
treatment. This is because lower values of WCA indicate the pres- treatment power (Ding, Shao, & Bai, 2014; Fang et al., 2013).
ence of multiple hydrophilic groups on the surface. Generally, the However, in this study, the application of various surface treat-
formation of hydrophilic groups by plasma treatment can be ments and their different degree did not show significant change.
explained by the plasma active species induced by physical and The FTIR spectra of the WPI coating solution and WPI side of the
chemical changes in the PET film surface (Yang, Chen, Guo, & PET/WPI films are shown in Fig. 1A. A broad band around 3500-
Zhang, 2009). Because plasma active species were combined with 3000 cm1 was observed in the spectrum of WPI coating solution,
oxygen in air, functional groups such as hydroxyl, carbonyl, which is ascribed to the stretching vibration of hydroxyl groups and
carboxyl, and ester groups containing oxygen were formed on the asymmetric and symmetric stretching vibrations of the N-H bonds
surface of PET films (Kostov et al., 2010). By contrast, auto-adhesion in amino groups (Fig. 1A, e) (Bagheri, Madadlou, Yarmand, &
on polymer films subjected to corona discharge treatment can Mousavi, 2013; Bahram et al., 2014; Winkler, Vorwerg, & Schmid,
generally be explained by hydrogen bonding through carbonyl and 2015). Similar bands could be found in the spectra of PET/WPI
phenolic hydroxyl groups which was formed because of corona films (WPI side) (Fig. 1A, b-d), however, intensity of the peaks was
discharge treatment (Briggs, Kendall, Blythe, & Wootton, 1983). decreased. It might be postulated that the -OH and -NH groups of
Moreover, carboxyl groups were induced on the polymer surface the protein could interact with polar groups (mainly C]O, -COOH,
owing to an increase in the scission of polymer chains because of and -OH groups) of PET films subjected to various surface treat-
corona discharge treatment (Briggs, Rance, Kendall, & Blythe, 1980). ments (Fig. 1B). Sudhamani, Prasad, and Sankar (2003) reported a
Lynch, Spence, Baker, and Postlethwaite (1999) stated that similar result that the interaction between gellan and poly-
atmospheric-pressure plasma treatment, which controls chemical vinylalcohol led to significant changes in the -OH stretching region
elements on a surface affected by inert gases in the plasma system, and the intensity of absorption bands owing to hydrogen bonding
is more efficient compared to corona discharge treatment (Lynch (Sudhamani et al., 2003). The slight bands at 2923 cm1, 2852 cm1,
et al., 1999). Based on these results, we could suggest that plasma and 1742 cm1 are attributed to asymmetrical and symmetrical CH2
treatment is a more efficient method for improving wettability of stretching and C]O stretching of lipids in WPI powder, respec-
PET film surface. In contrast, the WCA of the PET films subjected to tively (Fig. 1A, e) (Ye, Zhou, Shi, Chen, & Du, 2017). The band range
primer coating significantly increased. around 1700-1600 cm1 is mainly known as the amide 1 region in
An increase in the number of hydrophilic groups ultimately the a-helical component of a-lactalbumin and b-lactoglobulin
leads to an increase in the intermolecular force between the sub- secondary structures (Fig. 1A, e), and the sharp peak at 1639 cm1
strate films and the coating materials, as well as an increase in (Fig. 1A, e) corresponds to the C]O stretching vibrations of peptide
adhesion strength (Awaja et al., 2009). Subsequently, increased bonds (Fig. 1B) (Ahmadi, Madadlou, & Sabouri, 2015; Madadlou
adhesion strength of the films subjected to three different types of et al., 2014). Compared to the spectrum of the WPI coating, slight
surface treatments was verified from their tensile strength and or profound changes in peak intensity and peak shifts were
elongation at break. 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
3.2. Fourier-transform infrared with attenuated total reflection
PET showed a decrease in peak intensity compared to the others,
(FTIR-ATR)
indicating the high intermolecular interaction between -OH and
-NH groups of protein and polar groups of PET films. High inter-
After one side of surface-treated PET films was coated by WPI
molecular interaction can prevent the oxygen molecules from
solution, the surface analysis of PET/WPI bilayer film was per-
moving through the free volumes (Vartiainen, Laine, Willberg-
formed using the FTIR-ATR spectra (Fig. 1). €inen, Pitka
€nen, & Ohra-aho, 2017). Subsequently, this high
Keyrila
FTIR spectrum of an untreated single PET film is shown in
intermolecular interaction contributes to the strong oxygen-barrier
property of PET/WPI/nylon/LLDPE multilayer films previously
Table 1 subjected to corona discharge treatment on PET.
Change in water contact angle of polyethylene terephthalate (PET) films by
surface treatment methods. 3.3. Oxygen transmission rate (OTR)
Surface treatment Contact angle ( )
Whey protein-based films are well known as excellent oxygen-
Untreated 66.4 ± 0.6b
Corona discharge treated 64.8 ± 0.2c barrier materials (Hong & Krochta, 2004; Schmid et al., 2012;
Plasma treated 57.9 ± 1.5d Winkler, Vorwerg, & Schmid., 2015). To observe the oxygen-
Primer coated 90.1 ± 0.6a barrier property of WPI coating as a barrier layer of PET/nylon/
a-d
Within the same column, different lowercase letters indicate significant LLDPE films, OTR measurements of PET/WPI and PET/WPI/nylon/
differences (P 0.05). 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.
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- previously subjected to primer coating on PET.
ously subjected to plasma and corona discharge treatments on PET The oxygen-barrier properties of the PET/WPI/nylon/LLDPE
had very low OTRs of 0.151 ± 0.011 and 0.166 ± 0.090 cc/ films were significantly improved by corona discharge and plasma
m2$day$atm, respectively. By contrast, the PET/WPI/nylon/LLDPE treatment. Owing to increased wettability resulting from corona
films previously subjected to primer coating treatment on PET had discharge and plasma treatments, the increase in intermolecular
high OTR of 0.859 ± 0.246 cc/m2$day$atm. From our OTR mea- interaction between PET and WPI films corresponds to a decrease in
surement, the OTR of free-standing WPI film was 0.010 ± 0.006 cc/ free volume (Awaja et al., 2009; Vartiainen et al., 2017). Moreover,
m2$day$atm. Because WPI coating was applied to PET/nylon/LLDPE the increased wettability was attributed to evenly distributed and
films, the OTRs of PET/WPI/nylon/LLDPE films previously subjected homogeneous coating layers on PET films subjected to various
to primer coating, corona discharge, and plasma treatments on PET surface treatments. Consequently, the oxygen-barrier properties of
showed about 43, 211, 234 times lower OTR values, respectively, the PET/nylon/LLDPE films previously subjected to corona
than those of the PET/nylon/LLDPE films without WPI layer. discharge and plasma treatments on PET were substantially better
Moreover, the PET/WPI/nylon/LLDPE films composed of PET and than those of the PET/nylon/LLDPE films previously subjected to
nylon films are expected to be resistant to oxygen gradients. The primer coating treatment on PET.
oxygen-barrier properties of both synthetic films and biopolymers
have been determined by the degree of crystallinity and solubility 3.4. Surface morphology
of oxygen (Vartiainen et al., 2017). Degree of crystallinity of WPI
films can be controlled by heat treatment. Under the application of Through the microscopic analysis, the adhesion properties of
appropriate heat treatment to hydrated whey protein, the intra- the PET/nylon/LLDPE and the PET/WPI/nylon/LLDPE films were
molecular interactions of whey protein-based polymer chains found to be good, as shown in Fig. 2. Furthermore, scanning elec-
broke down and an open linear structure and a dense network of tron micrographs of the cross-sections of the PET/WPI/nylon/LLDPE
whey protein matrices were created. Moreover, as crystal sites of films are very useful for understanding their mechanical properties
whey protein matrices were increased, free volumes of those were and OTR. In the case of PET/nylon/LLDPE films (Fig. 2aec), WPI film
reduced during heat treatment (Perez-gago & Krochta, 2001; layers were not presented. Although WPI film layers were present
Vartiainen et al., 2017). Polar functional groups formed by each in the PET/WPI/nylon/LLDPE films previously subjected to various
surface treatment on PET films played important roles in surface treatments on PET, no apparent difference was observed
strengthening the intermolecular interactions with WPI films by between the PET/nylon/LLDPE films and PET/WPI/nylon/LLDPE
preventing the transport of oxygen molecules through the free films (Fig. 2def). Because very thin WPI film layers (4.24 ± 1.59 mm
volumes (Vartiainen et al., 2017). In the case of PET/WPI/nylon/ thickness) were covered by synthetic films, they were not clearly
LLDPE films previously subjected to primer coating on PET, EAA identified in the images of PET/WPI/nylon/LLDPE films previously
solution was used as the primer coating. However, EAA copolymer subjected to various surface treatments on PET (Fig. 2def). Fig. 2
has a very high OTR of 2549e4569 cc/m2$day$atm (McKeen, 2012). clearly shows that both PET/nylon/LLDPE films and PET/WPI/
Therefore, it could be suggested that high OTR value of EAA nylon/LLDPE films were formed uniformly. That is, each film layer
copolymer rarely affected OTR of PET/WPI/nylon/LLDPE films was evenly distributed. The WPI film layers were significantly
6 E. Joo et al. / Food Hydrocolloids 80 (2018) 1e7
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 7
films and PET/WPI/nylon/LLDPE films showed good layer integrity Kostov, K. G., dos Santos, A. L. R., Honda, R. Y., Nascente, P. A. P., Kayama, M. E.,
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