Food Research International 51 (2013) 714–722

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Food Research International

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

Effect of PLA lamination on performance characteristics of agar/κ-carrageenan/clay

bio-nanocomposite film
Jong-Whan Rhim ⁎
Department of Food Engineering, Mokpo National University, 61 Dorimri, Chungkyemyon, Muangun, 534-729, Jeonnam, Republic of Korea

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

Article history: Multilayer films composed of PLA and agar/κ-carrageenan/clay (Cloisite® Na+) nanocomposite films were
Received 18 September 2012 prepared, and the effect of lamination of PLA layers on the performance properties such as optical, mechan-
Accepted 21 January 2013 ical, gas barrier, water resistance, and thermal stability properties was determined. The tensile strength (TS)
of the agar/κ-carrageenan/clay nanocomposite films (67.8 ± 2.1 MPa) was greater than that of PLA films
Keywords:
(43.3 ± 3.6 MPa), and the water vapor permeability (WVP), water uptake ratio (WUR), and water solubility
Agar
κ-Carrageenan
(WS) of the nanocomposite films were higher than those of PLA films. The film properties of the multilayer
Polylactide films exhibited better properties of the component film layers. Especially, the WVP and water resistance of
Clay the bionanocomposite film were improved significantly, while the OTR of the PLA film decreased profoundly
Nanocomposite after lamination with PLA layers. Thermal stability of the bionanocomposite also increased after lamination
Lamination film with PLA layers.
© 2013 Elsevier Ltd. All rights reserved.

1. Introduction have raised interest in using biodegradable packaging materials produced

The main function of food packaging is to maintain the quality and
safety of food products during storage and distribution, and to extend
the shelf-life of food products by controlling the mass transfer of
water vapor, gases (O2, CO2, flavors, and taints), and transmission of
light that may occur between the internal and external environment
of the package (Brown & Williams, 2003; Marsh & Bugusu, 2007;
Mckinlay, 2004; Singh & Singh, 2005). To fulfill the packaging func-
tions, a variety of packaging materials such as paper and paperboard,
plastic, glass, metal, and a combination of the materials of various
chemical nature and physical structures have been used (Marsh &
Bugusu, 2007). Among the four basic packaging materials, plastic-
based materials have been widely used since they are cheap and
convenient to use with good processability, good aesthetic quality,
and excellent physico-chemical properties such as mechanical, barri-
er, optical, and surface properties. Annually, plastics are produced
about 260 million tons worldwide, of which one-third is used in
packaging in the form of films, sheets, bottles, cups, tubs, trays, etc.
(Plackett, 2011; Robertson, 2008).
Recent advance of new food packaging technologies, such as active
and intelligent packaging developed as a response to consumer trends to-
wards minimally processed, fresh, tasty and conveniently packaged food
products (Danielli, Gontard, Spyropoulos, Beuken, & Tobback, 2008;
Imran et al., 2010), and public concerns on the environmental problems
⁎ Tel.: +82 61 450 2423; fax: +82 61 454 1521.
E-mail address: jwrhim@mokpo.ac.kr.
from renewable resources (biopolymers). Biopolymers produced from
various natural resources through direct extraction, chemical synthesis,
or fermentation by microorganisms, such as starch, cellulose, proteins,
polylactide (PLA), and polyhydroxyalkanoates (PHAs), have been consid-
ered as attractive alternatives for non-biodegradable petroleum-based
plastics since they are abundant, renewable, inexpensive, environmental-
ly friendly, and biodegradable (Clarinval & Halleux, 2005; Luckachan &
Pillai, 2011; Siracusa, Rocculi, Romani, & Rossa, 2008; Weber, Haugaard,
Festersen, & Bertelsen, 2002; Zhao, Torley, & Halley, 2008).
However, there are some limitations to the commercial use of
biopolymer films due to their poor mechanical and barrier properties
and high sensitivity to moisture (Cabedo, Feijoo, Villanueva, Lagarón,
& Giménez, 2006; Luckachan & Pillai, 2011; Yoo & Krochta, 2011).
Various efforts have been made to overcome these problems and to
improve the property of biopolymer-based films through not only
physical, chemical, or enzymatic treatments, but also blending with
hydrophobic additives, or making multilayer films with different
film properties (Cabedo et al., 2006; Luckachan & Pillai, 2011; Rhim,
Mohanty, Singh, & Ng, 2006a,b). Recently, nanocomposite technology,
compositing biopolymer with layered silicate clay materials such as
montmorillonite (MMT), has been tested to improve biopolymer
film properties (Bordes, Pollet, & Avérous, 2009; Pandey et al., 2005;
Ray & Bousmina, 2005; Rhim & Ng, 2007; Sorrentino, Gorrasi, &
Vittoria, 2007; Yang, Wang, & Wang, 2007). Though significant
improvements in film properties of biopolymer films have been
reported through using each of the methods, they are still not compa-
rable to those of the commodity plastic films. This indicates more
efficient methods or a combination of the methods are needed to

0963-9969/$ – see front matter © 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.foodres.2013.01.050
 J.-W. Rhim / Food Research International 51 (2013) 714–722
improve the film properties sufficient to substitute for the non-
biodegradable plastic films for packaging use.
To date, PLA is the most widely used biopolymer-based packaging
material with the highest potential for a commercial major scale pro-
duction synthesized from lactic acid which is derived from renewable
resources, such as corn or sugar beets (Garlotta, 2001; Gupta &
Kumar, 2007; Lim, Auras, & Rubino, 2008). Structurally, PLA is a linear
aliphatic polyester, which is a thermoplastic with high-strength,
high-modulus, good processability, being completely biodegradable,
compostable, and biocompatible, and therefore perfectly safe for the
environment and for the food packaging application. PLA presents a
medium water and oxygen permeability level comparable to polysty-
rene (Auras, Harte, & Selke, 2004). In addition, PLA is safe and
“Generally Recognized As Safe” (GRAS) for use in food packages
(Conn et al., 1995). However, its high polarity, brittleness, stiffness,
noise, and low deformation at break limit its use. Considerable efforts
have been made to improve the properties of PLA so as to compete with
low-cost and flexible commodity polymers. These attempts were
carried out either by modifying PLA with biocompatible plasticizers or
by blending PLA with other polymers (Luckachan & Pillai, 2011).
Previously, we prepared blend film with agar and κ-carrageenan
by exploring good compatibility between the carbohydrate polymers
caused by their similarity in chemical structure, and we also prepared
a nanocomposite film by compositing the blend film with layered sil-
icate nanoclay (Rhim, 2012). Though the film properties have been
improved significantly through the blending, and the water vapor
barrier and water resistance properties have been further improved
after formation of nanocomposite with nanoclay, they were not still
enough to compare with those of commodity plastic films. One way
to overcome such weakness of the biopolymer-based packaging
materials is to associate them with a moisture resistant polymer
with good mechanical properties, while maintaining the overall bio-
degradability of the product. For such purposes, multilayer films
formed through coating or lamination methods have been widely
used to combine the properties of two or more polymers into one sin-
gle multilayered structure (Martin, Schwach, Avérous, & Couturier,
2001; Martucci & Ruseckaite, 2010; Park et al., 2012; Rhim et al.,
2006b; Rhim, Lee, & Ng, 2007; Thellen, Schirmer, Ratto, Finnigan,
& Schmidt, 2009).
Various types of food packaging application of multilayer structures
exhibiting with substantially improved gas barrier and mechanical
strength have been explored in the food packaging industry. One of
the traditionally used multilayers is in the form of barrier layer in the
middle and outside structural layers. This is used as a passive barrier
in which the middle layer is composed of high barrier films. Other use
is an active barrier composed of gas (O2 or CO2) scavenger incorporated
film layer. The other use of the multilayer film is the combination of pas-
sive and active barrier. The multilayer films or sheets with improved
barrier or mechanical properties can be formulated into several differ-
ent types of packaging shapes such as bags, pouches, plates, cups,
trays, and clamshells. They are expected to be used for the packaging
of various types of food materials including retail packaging for meats,
cheese, confectionery, as well as fresh fruits and vegetables.
Therefore, the main objective of this study was to prepare multi-
layer films with a blended carbohydrate nanocomposite films (agar/
κ-carrageenan/clay) and PLA to modify the mechanical and barrier
properties of the film for the food packaging application by exploiting
the advantages of each component film.
2. Materials and methods
2.1. Materials
Food grade agar and κ-carrageenan were obtained from Fine Agar
Agar Co., Ltd. (Damyang, Jeonnam, Korea) and Hankook Carragen
(Whasoon, Jeonnam, Korea), respectively. Poly-L-lactide (PLLA, Biomer®
715
L9000), which had a weight-average molecular weight of 200 kDa
and was polymerized mainly (>98%) from L-lactic acid, was obtained
from Biomer Inc. (Krailling, Germany). A natural MMT (Cloisite® Na +:
cation exchange capacity, CEC = 92.6 mequiv./100 g) was pur-
chased from Southern Clay Products (Gonzales, TX, USA). Analytical
grade chloroform and glycerol were purchased from J.T. Baker
(Mallinckrodt Baker, Inc., Phillipsburg, NJ, USA).
2.2. Preparation of films
For the preparation of agar/κ-carrageenan blend films, film solutions
were prepared by dissolving 2 g each of agar and κ-carrageenan in
150 mL of distilled water with mixing vigorously for 30 min at 95 °C
using a magnetic stirrer, and then added 1 g of glycerol as a plasticizer.
For the preparation of the nanocomposite film solution, clay and bio-
polymer solutions were prepared separately as described by Rhim,
Lee, and Hong (2011). First, clay solution was prepared by dispersing
precisely weighed nanoclay (Cloisite® Na+, 5 wt.% of agar/κ-carrageen-
an) into distilled water and swelling for 24 h while stirring using a mag-
netic stirrer then homogenized using a high shear mixing homogenizer
(T25 basic, Ika Labotechnik, Janke & Kunkel Gmbh & Co., KG Staufen,
Germany) at 20,500 rpm for 10 min, and followed by sonication for
10 min using a high-intensity ultrasonic processor (Model VCX 750,
Sonics & Materials Inc., Newtown, CT., U.S.A.). Two grams each of agar
and κ-carrageenan were dissolved into the nanoclay solution with
heating and stirring at 95 °C for 30 min then added 1 g of glycerol.
PLA films were prepared using the solvent casting method (Rhim et
al., 2006a). Four grams of PLA was dissolved in 100 mL of chloroform
while mixing vigorously at room temperature.
All the film preparation solutions were poured onto a leveled Teflon
film (Cole-Parmer Instrument Co., Chicago, IL. USA) coated glass plate
(24 × 30 cm) and then allowed to dry for about 24 h at room tempera-
ture (22 ± 2 °C). The resultant film was peeled off the casting surface.
Double layer (a PLA layer and a nanocomposite layer) and triple
layer (PLA outer layer, a nanocomposite middle layer, and another
PLA outer layer) films were prepared following the method of Rhim et
al. (2006b) with basically the same method as above using the same
amount of solid content as control carbohydrate composite or PLA
films to control the film thickness. For the preparation of double layer
film, first PLA layer was prepared by casting PLA solution (2 g PLA in
80 mL chloroform) and drying, then a nanocomposite film solution
(1 g each of agar and κ-carrageenan with 5 wt.% of clay) was cast over
it. Triple layer film was prepared with the same method except reduc-
ing the PLA content of each outer layer to the half of that of the double
layer film. To remove the remaining solvent which is known to work as
a plasticizer in the solvent cast PLA film (Rhim et al., 2006a), all the PLA
films prepared were vacuum dried at 60 °C.
2.3. Film thickness and conditioning
Film thickness was measured using a micrometer (Dial Thickness
gauge 7301, Mitutoyo, Japan) at an accuracy of 0.01-mm. All film
samples were preconditioned in a constant temperature humidity
chamber set at 25 °C and 50% RH for at least 48 h before further test.
2.4. Color and transparency
Surface color of the films was measured using a Chroma
meter (Minolta, CR-200, Tokyo, Japan). A white standard color plate
(L =97.75, a =−0.49 and b = 1.96) was used as a background for
color measurements. Hunter color values were averaged from five read-
ings of each sample. The total color difference (ΔE) was calculated as
follows:
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ΔE ¼ ðΔLÞ2 þ ðΔaÞ2 þ ðΔbÞ2 ð1Þ
716 J.-W. Rhim / Food Research International 51 (2013) 714–722
where ΔL, Δa, and Δb are difference between each color values of
standard color plate and film specimen, respectively. Transparency of
film samples was determined by measuring the percent transmittance
at 660 nm using a UV/VIS spectrophotometer (Model 8451A, Hewlett-
Packard Co., Santa Alara, CA, USA) (Rhim et al., 2006a).
2.5. X-ray diffraction (XRD) analysis
Structures of pristine nanoclay and agar/κ-carrageenan/clay
nanocomposite films were evaluated with XRD measurements using a
PANalytical Xpert pro MRD diffractometer (Amsterdam, Netherland),
operated at 40 kV and 30 mA, equipped with Cu Kα radiation at a
wavelength of 0.1546 nm. The samples were scanned over the range
of diffraction angle 2θ = 1–10° with a scanning rate of 0.4 /min at
room temperature. The interlayer d-spacing was determined using the
Bragg's diffraction equation:
λ ¼ 2d001 sin θ ð2Þ
where d001 is the interlayer distance of (001) diffraction face, θ is the
diffraction position, and λ is the wavelength (Xu, Ren, & Hanna, 2006).
2.6. Scanning electron microscopy (SEM) analysis
Morphology of impact fracture surfaces of cross-section of
agar/κ-carrageenan/clay nanocomposite, PLA and their multiple
layer films was observed using a FE-SEM (Field Emission Scanning
Electron Microscope; S-4800, Hitachi Co., Ltd., Tokyo, Japan) operated
at Vacc = 1 kV and Ie = 10 μA.
2.7. Tensile properties
Tensile testing was performed in accordance with the ASTM Method
D 882–88 with an Instron Universal Testing Machine (Model 5565,
Instron Engineering Corporation, Canton, MA, USA) equipped with a
0.5 kN load cell. Rectangular strips (150 × 25.4 mm) were cut from
individually prepared film using a precision double blade cutter
(model LB.02/A, Metrotec, S.A., San Sebastian, Spain). Six samples
were tested per film. Initial grip separation was set at 50 mm and
cross-head speed at 50 mm/min. The TS (Pa) was determined by
dividing the maximum load (N) by the initial cross-sectional area
(m2) of the film sample, and the E (%) was determined by dividing
the extension at rupture of the film by the initial length of the film
(50 mm) multiplied by 100.
2.8. Water vapor permeability (WVP)
Water vapor transmission rate (WVTR) of film sample was deter-
mined gravimetrically at 25 °C under 50% RH conditions using water
vapor transmission measuring cup in accordance with the ASTM
E96-95 standard method. Then the WVP (g m/m 2 s Pa) of the film
was calculated using the following equation:
WVP ¼ ðWVTR  LÞ=Δp ð3Þ
where WVTR was the measured water vapor transmission rate (g/m2 s)
through a film, L was the mean film thickness (m) and Δp was the par-
tial water vapor pressure difference (Pa) across the two sides of the film.
In calculating WVP, the effect of the resistance of the stagnant air layer
between the film underside and the surface of the water in the cup was
corrected using the method of Gennadios, Weller, and Gooding (1994).
2.9. Water contact angle (CA)
The CA of water in air on the film surface was measured using a CA
analyzer (model Phenix 150, Surface Electro Optics Co., Ltd., Kunpo,
Korea) after a water drop of ca. 10 μL was placed on the surface of
film using a micro syringe (Rhim et al., 2006b).
2.10. Oxygen transfer rate (OTR)
The OTR of film sample was determined at 23 °C and 0% RH with
an OX-Tran 2/21 (Mocon Inc., Minneapolis, MN) according to the
method of ASTM D3895-95. Aluminum foil masks with an exposure
area of 1 cm 2 was subsequently purged with a carrier gas of N2
containing 2% H2. One side of sample was then exposed to the
permeant gas of O2 (99.95%) at atmospheric pressure. The perme-
ation rate through the specimen was measured until it reached steady
state.
2.11. Water resistance
Water solubility (WS) of films was determined as the percentage of
soluble matter to initial dry matter of film sample (Rhim et al., 2011).
Three randomly selected specimens from each type of film were first
dried at 105 °C for 24 h to determine initial dry matter. Separate films
were immersed in 30 mL of distilled water in a 50 mL beaker. Beakers
were covered with Parafilm “M” wrap (American National Can, Green-
wich, CT) and stored in an environmental chamber at 25 °C for 24 h
with occasional stirring. Undissolved dry matter was determined by
removing the film pieces from the beakers, gently rinsing them with
distilled water, and then oven drying them (105 °C, 24 h). The weight
of solubilized matter was calculated by subtracting the weight of
undissolved dry matter from the weight of initial dry matter and
expressed as a percentage of the initial dry matter content.
Water uptake ratio (WUR) of films was determined gravimetrically.
Pre-weighed squared specimens (25 mm× 50 mm) were immersed in
distilled water. Samples were then removed after 1 h and weighed
after removing the surface water with blotting paper. The WUR was
calculated as follows:
WURð% Þ ¼ ðmt −mo Þ=mo  100 ð4Þ
where mo and mt are the weight of the samples before and after immer-
sion, respectively.
2.12. Thermal stability
The thermal stability of each film was tested with thermogravimetric
analysis (TGA), which was performed in a TGA/DSC 1 Mettler Toledo
thermal analyzer (Schwarzenbach, Switzerland). About 5 mg of each
sample was heated from room temperature to 600 °C at a heating rate
of 10 °C/min under a nitrogen flow (50 cm3/min) to obtain TGA data
without oxidative decomposition. Derivative form of TGA (DTGA) was
obtained using differentials of TGA values, which was calculated using
a forward finite difference method as follows:
 
DTG ¼ wtþΔt −wt =Δt ð5Þ
where wt+Δt and wt are the residual weight of sample at time t+Δt and
t, respectively, and Δt is the time interval for reading residual sample
weight.
2.13. Statistical analysis
All experiments were based on a completely randomized block de-
sign, and were performed in triplicate and mean values with standard
deviations (SD) were reported. One-way analysis of variance (ANOVA)
was performed, and the significance of each mean property value was
determined (pb 0.05) with the Duncan's multiple range test of the
statistical analysis system using the SPSS computer program (SPSS Inc.,
Chicago, IL, USA).
 J.-W. Rhim / Food Research International 51 (2013) 714–722
3. Results and discussion
3.1. Apparent film properties
Free standing flexible films with smooth surface were formed
for agar/κ-carrageenan blend, agar/κ-carrageenan/clay nanocomposite,
and PLA films. Previously, Rhim (2012) found that agar and
κ-carrageenan are compatible to form homogeneously blended films
due to their chemical similarity, and also reported that the blend
polymer formed intercalated nanocomposite film with the MMT clay
(Cloisite® Na +) prepared by the same solution intercalation method.
Apparent color properties and transmittance of the blend, nano-
composite, and PLA films are shown in Table 1. The total color difference
(ΔE) was significantly different in both the blend and the nano-
composite films, which are mainly attributed to the increase in Hunter
b-values, namely, increase in yellowness, of both films. The increase in
yellowness of the blend film is mainly due to κ-carrageenan (Rhim,
2012). Increase in yellowness of the nanocomposite film was more
pronounced due to the inclusion of the nanoclay which has a slightly
yellowish tint.
The agar/κ-carrageenan blend film was highly transparent with
the transmittance at 660 nm of 68.7 ± 1.7%, however, it decreased
down to 19.6 ± 1.3% after formation of nanocomposite with the clay,
which was mainly attributed to the dispersion of not completely
exfoliated nanoparticles in the carbohydrate polymer matrices
(Rhim, 2012). On the contrary, the PLA film prepared by the solvent
cast method was as transparent as polystyrene films with transmit-
tance of 85.2 ± 0.2%. PLA is an inherently polar material due to its
basic repeated unit of lactic acid. The high polarity of PLA leads to a
number of unique properties including the high transparency of the
film (Gupta & Kumar, 2007).
The agar/κ-carrageenan/clay nanocomposite film layers were lam-
inated on one or both sides with PLA film layers without any specific
compatibilizer or tie layer, and the resulting multilayer film had good
visual appearance. PLA, an inherently polar material due to the basic
repeat unit of lactic acid, is likely to adhere to agar/κ-carrageenan
nanocomposite layer firmly through hydrogen bonding interaction.
The total color difference of the nanocomposite films decreased
slightly after formation of multilayer with the PLA film, while the
transmittance of the multilayer films increased due to the transparent
PLA layers. However, the degree of change in ΔE and T660 was depen-
dent on the number of PLA layers. The same phenomenon was also
observed in the multilayer film laminated with SPI and PLA film layers
(Rhim et al., 2007).
3.2. Nanocomposite structure
The XRD patterns for the clay powder (Cloisite® Na +) and corre-
sponding agar/κ-carrageenan/clay nanocomposite are shown in
Fig. 1. The intercalation of polymer chains into the silicate galleries
usually increases the interlayer spacing of the clay, in comparison
Table 1
Apparent color and transmittance of agar/κ-carrageenan blend, agar/κ-carrageenan/clay
nanocomposite, polylactide (PLA), and multilayer films1.
Film2 L a b ΔE
Blend 95.5 ± 0.0b −0.2 ± 0.0b 4.4 ± 0.0b 2.7 ± 0.0b
Nanocomposite 94.7 ± 0.0a −0.3 ± 0.0a 5.6 ± 0.0c 4.2 ± 0.0c
PLA 96.3 ± 0.0c 0.1 ± 0.0c 2.2 ± 0.0a 0.6 ± 0.0a
Double layer 94.9 ± 0.2ab −0.4 ± 0.1a 5.4 ± 0.6c 4.0 ± 0.6c
Triple layer 95.0 ± 0.1b −0.2 ± 0.0b 4.4 ± 0.1b 3.0 ± 0.1b
1 2
Means of replicates ± standard deviation. Any two means in the same column
followed by the same letter were not significantly different (p >0.05) by Duncan's
multiple range test.
2
Agar/κ-carrageenan blend; agar/κ-carrageenan/clay nanocomposite; PLA;
nanocomposite/PLA; and PLA/nanocomposite/PLA.
717
with the interlayer spacing of the pure clay, leading to a shift of the
XRD peak towards the lower values of 2θ. As observed in the XRD pat-
terns, the diffraction peak of the clay shifted into lower angle from
7.85° to 3.19° after formation of nanocomposite, which indicates the
mean interlayer spacing of the (001) plane (d001) for the clay powder
determined using the Bragg's equation increased from 1.12 nm to
2.77 nm after dispersing the silicate layers in the polymer matrix.
This observation indicates the formation of intercalated structure.
However, it is not well ordered intercalated nanostructure because
the width of the basal reflection of the clay powder has been de-
creased after formation of the nanocomposite.
3.3. Film microstructure
The morphology of the laminates, as revealed by scanning electron
micrographs (FE-SEM) of the cross-section of agar/κ-carrageenan/clay
nanocomposite, PLA, and PLA/nanocomposite double layer films are
given in Fig. 2. The SEM image of the nanocomposite film shows a
homogeneously blended layer mixed with agar, κ-carrageenan, and
clay. The SEM image of the multilayer film shows that the outer PLA
layer is being tightly bonded to the inner nanocomposite layer to
make continuous film. Though delamination of laminated film or
sheet prepared with thermoplastic starch and polyesters such as PLA,
poly(ε-caprolactone) (PCL), and poly(hydroxybutyrate-co-valerate)
(PHBV) by coextrusion process has been observed (Martin et al.,
2001; Wang, Shogren, & Carriere, 2000), manual peeling of PLA
layers from the inner nanocomposite layer was not possible. In the
present study, a strong adhesion between each layer of the multilayer
PLA/nanocomposite/PLA film was formed without any adhesives or sur-
face modification (Elsabee, Abdou, Nagy, & Eweis, 2008) with corona
discharge, flame treatment, plasma treatment, or other chemical treat-
ment in the present study. It is mainly attributed to the process of mul-
tilayer film, i.e., by casting the second layer of film solution over the first
dried film layer, any probable irregularities on the dried film was filled
with wet film solution to make tightly bonded film. Similar result was
observed with SPI/PLA (Rhim et al., 2006b) and PLA/gelatin/PLA multi-
layer films (Martucci & Ruseckaite, 2010). They explained each layer
probably worked as an adhesive between film layers, i.e., the middle
layer functioned like water-borne adhesive and the outer PLA layer
worked as a solvent-borne adhesive. It was postulated that the strong
bond strength was caused by means of hydrogen interaction between
carbonyl groups in PLA and hydroxyl groups in carbohydrates and glycer-
ol (Martucci & Ruseckaite, 2010). This would explain the strong adhesion
between each layer of the multilayer film, the consistent film thickness,
good transparency, and desirable mechanical, water vapor barrier proper-
ties of the multilayer film. The thickness of the films determined from the
Intensity (a.u.)
Agar/K-Carrageenan/Clay nanocomposite film
T660
Cloisite Na+
68.7 ± 1.7d
19.6 ± 1.3a
85.2 ± 0.2e
25.8 ± 2.5b
33.2 ± 3.6c
4 6 8 10
2 θ (degree)
Fig. 1. XRD patterns at 2θ of the 001 clay reflection plane for Cloisite Na+ clay and agar/
κ-carrageenan/clay nanocomposite film.
718 J.-W. Rhim / Food Research International 51 (2013) 714–722
nanocomposite film
PLA/nanocomposite double layer film
Fig. 2. SEM images of cross-sectional view of nanocomposite, PLA, and PLA/nanocomposite double layer films.
SEM images using a scale in the SEM was 55, 79, and 76 (15/39/22)μm
for the nanocomposite, PLA, and multilayer films, respectively. The
hydrogen bonding interaction between the layers of the multilayer
film was tested by using FT-IR (data not shown). The FT-IR spectrum of
the blends shows a broad peak at 3600–3300 cm−1 which corresponds
to O\H stretch of hydroxyl present in the agar and κ-carrageenan bio-
polymer. The OH group intensity was reduced with the κ-carrageenan ad-
dition and due to hydrogen bonding between agar and κ-carrageenan.
Also a distinct peak at 1640 cm−1 corresponds to carbonyl group
(C_O). Three important bands at 846, 927 and 1262 cm−1 can be
attributed to D-galactose-4-sulfate, 3,6-anhydride-galactose and ester
sulfate stretching, respectively. Also the PLA/agar/κ-carrageenan shows
a peak at 946 cm−1 which corresponds to D-galactose-4-sulfate group
stretching.
3.4. Thickness and tensile properties
Mean thicknesses for control agar/κ-carrageenan blend, their
nanocomposite, PLA, double layer, and triple layer films measured
using a micrometer were 58.2 ±4.3, 58.6 ± 5.6, 64.3 ±3.0, 57.5± 2.3,
and 65.9 ± 10.6 μm, respectively (Table 2), which are comparable to
those observed by the SEM. The thickness of laminated films was
changed after lamination of the agar/κ-carrageenan nanocomposite
PLA film
with PLA layer depending on the way of lamination, i.e., double or triple
layers, however, the difference in their thickness was not statistically
significant (p > 0.05). In general, the thickness of biopolymer films is
dependent on the solid content (Rhim et al., 2006b). Rhim et al.
(2006b) also found that the thickness of multilayer films composed of
soy protein isolate (SPI) and PLA layers did not change significantly
(p > 0.05) compared with individual component films when prepared
with same solid content and they suggested multilayer films with a
fairly consistent thickness indicate indirectly a likely compatibility
between layers.
Table 2 also shows the results for TS and E for agar/κ-carrageenan
blend, agar/κ-carrageenan/clay nanocomposite, PLA and their multilayer
films. The TS and E of agar/κ-carrageenan blend film were 48.2±4.5 MPa
and 26.3±5.1%, respectively. The mechanical strength of the blend film
increased more than 40% with decrease in resilience by 57% after
formation of nanocomposite with the clay. This is most likely due to the
formation intercalated nanocomposite formed between the clay and
the blend polymer matrices (Rhim, 2012). The enhancement in mechan-
ical properties of polymer nanocomposites is attributed to the high
rigidity (178 GPa), high aspect ratio (100–500), and large surface area
(750 m2/g) of the nanoclay together with the good affinity through
interfacial interaction between polymer matrix and nanoclay (Bordes et
al., 2009; Pandey et al., 2005; Ray & Bousmina, 2005; Rhim & Ng, 2007).
 J.-W. Rhim / Food Research International 51 (2013) 714–722
Table 2
Tensile properties of agar/κ-carrageenan blend, agar/κ-carrageenan/clay nanocomposite,
polylactide (PLA), and multilayer films1.
Film2 Thickness (μm) TS (MPa) E (%)
Blend 58.2 ± 4.3a 48.2 ± 4.5a 26.3 ± 5.1d
Nanocomposite 58.6 ± 5.6a 67.8 ± 2.1c 11.3 ± 1.4b
PLA 64.3 ± 3.0a 43.3 ± 3.6a 4.4 ± 0.2a
Double layer 57.5 ± 2.3a 59.9 ± 0.5b 9.4 ± 2.6b
Triple layer 65.9 ± 10.6a 50.7 ± 8.4a 17.9 ± 1.9c
1 Triple layer
Means of replicates ± standard deviation. Any two means in the same column
followed by the same letter were not significantly different (p >0.05) by Duncan's
multiple range test.
2
Same as in Table 1.
The high value of elastic modulus and huge surface area of MMT enable it
to improve mechanical properties of biopolymers by carrying a signifi-
cant portion of the applied stress (Fornes & Paul, 2003).
On the other hand, the TS and E of PLA film were 43.3 ± 3.6 MPa
and 4.4 ± 0.2%, respectively, which are comparable to those of
PLA films prepared by thermo-compression or extrusion process
(Rhim et al., 2006a). Mechanical strength of the agar/κ-carrageenan
nanocomposite and PLA laminated films exhibited in-between
values of individual component film layers, i.e., 59.9 ± 0.5 and
50.7 ± 8.4 MPa, for double layer and triple layer films, respectively.
The TS of the laminated films increased by 38 and 17% for double
layer and triple layer films, respectively, compared with the PLA
film without sacrificing the film flexibility. On the contrary, the E of
the triple layer film increased significantly (p b 0.05) compared
with neat PLA film or even with the agar/κ-carrageenan nano-
composite film. The increase in flexibility of the multilayer films
may be ascribed to the plasticizing effect of water and hydrophilic
biopolymers (Rhim et al., 2006b). Martucci and Ruseckaite (2010)
also observed 16-folds increase in the TS of gelatin film through
lamination with PLA layers in both sides.
3.5. Water vapor permeability
The WVP values of the test films are shown in Table 3. The
WVP of the agar/κ-carrageenan blend film (1.23 × 10−9 g m/m2 s Pa)
decreased about 20% after formation of nanocomposite with the clay.
The decrease in WVP of the nanocomposite is believed to be due to
the presence of dispersed silicate layers with large aspect ratios in the
polymer matrix which are impermeable to water vapor (Choudalakis
& Gotsis, 2009). This forces water vapor travel through the film to follow
a tortuous path, thus increasing the effective path length for diffusion
(Bordes et al., 2009; Pandey et al., 2005; Ray & Bousmina, 2005; Rhim
& Ng, 2007). It is noteworthy that the WVP value of PLA film
(2.1 × 10 −11 g m/m2 s Pa) was about 50 times lower than that of
agar/κ-carrageenan nanocomposite film. In general, PLA has known to
have moderate barrier properties (WVP and OP) as compared to those
of commodity plastic films such as LDPE, HDPE, PVDC, PS, and PP ().
The WVP of PLA film is about two orders of magnitude higher than
those of commodity plastic films, however, it is about two orders of
magnitude lower than those of usually used natural biopolymer-based
films such as starch, chitosan, SPI, agar, and carrageenan films (Rhim,
2012; Rhim et al., 2006b). Therefore, it is expected the water vapor
barrier property of such biopolymer-based films can be improved by
lamination with more hydrophobic PLA film layers. Lamination of the
agar/κ-carrageenan nanocomposite film with PLA improved water
vapor barrier properties of the nanocomposite film dramatically as
evidenced by a decrease in the WVP value. The water vapor barrier of
multilayer film improved more than 20-fold in comparison with the
nanocomposite films, which was comparable to that of PLA film. This re-
sult indicates that lamination of biopolymer films with hydrophobic
film layers is very efficient method in reducing their barrier properties.
719
Table 3
Water vapor permeability (WVP), water contact angle (CA), and oxygen transfer rate
(OTR) of agar/κ-carrageenan blend, agar/κ-carrageenan/clay nanocomposite, polylactide
(PLA), and multilayer films1.
Film2 WVP (×10−11 g m/m2 s Pa) CA (deg) OTR (cm3/m2 day)
Blend 123.0 ± 5.0d
49.8 ± 1.4 a
0.54 ± 0.03bc
Nanocomposite 101.4 ± 9.0c 54.5 ± 2.5b 0.48 ± 0.00b
PLA 2.1 ± 0.3a 60.0 ± 0.5c 315.02 ± 12.33d
Double layer 4.7 ± 0.3ab – 0.61 ± 0.01c
5.0 ± 0.5ab – 0.03 ± 0.00a
1
Means of replicates ± standard deviation. Any two means in the same column
followed by the same letter were not significantly different (p >0.05) by Duncan's
multiple range test.
2
Same as in Table 1.
Similar results of decrease in the WVP of biopolymer films have been
reported with other biopolymers such as SPI, gelatin, and chitosan
films laminated with PLA layers (Martucci & Ruseckaite, 2010; Park et
al., 2012; Rhim et al., 2006b).
3.6. Water contact angle
Contact angle of water is one of the basic wetting properties of
packaging materials, indicating hydrophilic/hydrophobic properties of
the material. Results of the initial contact angle of water measurements
for the films are also shown in Table 3. The contact angles of water of
agar/κ-carrageenan blend, agar/κ-carrageenan/clay nanocomposite,
and PLA films were 49.8 ± 1.4, 54.5 ±2.5, and 60.0 ±0.5°, respectively.
The CA of PLA film was significantly (p b 0.05) higher than those of the
carbohydrate blend and their clay nanocomposite films. This explains
that PLA film surface is more hydrophobic than the agar/κ-carrageenan
blend or agar/κ-carrageenan/clay nanocomposite films and supports
the fact that PLA film has lower WVP with higher water resistance
than the agar/κ-carrageenan nanocomposite film. Generally, a film
exhibiting a CA less than 65° is considered as hydrophilic (Rhim &
Hong, 2007). This indicates the PLA laminated biopolymer film is still
hydrophilic though its hydrophobicity increased significantly after
lamination. The CA values of the film samples are comparable to those
of other biopolymer and plastic films such as the agar, PHBV, Ecoflex,
and LDPE films (Rhim & Hong, 2007; Rhim et al., 2011) which were
reported as 47.1, 60.4, 57.6, and 85.2°, respectively.
3.7. Oxygen transfer rate
The OTR values of the test films are also shown in Table 3. The OTR of
the agar/κ-carrageenan blend film was 0.54±0.03 cm3/m2.day and it de-
creased slightly (ca. 3%) after formation of nanocomposite with clay. On
the contrary, the OTR value of PLA film (315.02±12.33 cm3/m2 day)
was more than 650 times higher than that of the nanocomposite film.
In general, PLA is not a good barrier against non-polar gases such as
O2 and CO2 (Auras et al., 2004). The OTR of PLA films decreased signifi-
cantly down to 0.61±0.01 and 0.03±0.00 cm3/m2 day for the laminat-
ed films with double and triple layers, respectively, after formation of
multilayer film with the nanocomposite films. Similar results were ob-
served with SPI/PLA (Rhim et al., 2006b) and Chitosan/PLA (Park et al.,
2012) laminated films. Rhim et al. (2006a,b) reported oxygen permeabil-
ity (OP) of PLA film decreased more than 20 times by laminating with SPI
films, and Park et al. (2012) reported the OTR of PLA films coated with
chitosan/clay nanocomposite decreased by 99.5% compared with the
neat PLA film. Such improvement of gas barrier properties of PLA film
through the formation of multilayer films coupled with higher gas barrier
biopolymer films is of great importance for a specific food packaging
application and other applications where high gas barrier is needed
(Marsh & Bugusu, 2007).
720 J.-W. Rhim / Food Research International 51 (2013) 714–722
3.8. Water solubility (WS) and water uptake ratio (WUR)
The WS of a film is used as a measure of resistance of the film against
water. The WS of agar/κ-carrageenan blend, agar/κ-carrageenan/clay
nanocomposite, and PLA films were 53.5 ± 1.0%, 56.3± 0.4%, and
0.9 ± 0.8%, respectively (Table 4). Water resistance of the blend film
was not affected significantly (p b 0.05) by the formation of clay
nanocomposite. However, water resistance of the film increased pro-
foundly by the lamination with PLA layers WS, i.e., the WS decreased
down to 29.4 ± 1.1% and 28.6 ±9.7% for double and triple layered
films, respectively. The WS values of the multilayer film were in
between those of the agar/κ-carrageenan/clay nanocomposite and PLA
films. The solubility of the multilayer film was mainly attributed to
the solubilization of the agar/κ-carrageenan/clay nanocomposite layer
between the PLA layers. However, water resistance of the agar/κ-carra-
geenan/clay nanocomposite films was greatly improved by laminating
with PLA films, which can be properly applied for the food packaging
of high moisture food or use in the high humidity conditions.
The WUR of a film is a measure of water holding capacity or degree
of swelling of the film. The agar/κ-carrageenan blend film is highly
swellable as indicated by the high WUR value with more than 1800%
(Table 4). It reduced to about 1600% after formation of nanocomposite
film with the nanoclay, however, it is still quite high. It is mainly due
to the hydrophilic nature of both component biopolymer films and
the clay which is also hydrophilic. On the contrary, the WUR of PLA
film is less than 1%. The low WUR value of PLA film indicates that the de-
gree of swelling of PLA film in water is negligible, which is attributable
to the hydrophobicity of PLA. The WUR of the agar/κ-carrageenan/clay
nanocomposite film decreased to about 960% and 100% for double
layer and triple layer films, respectively, after laminated with layers. It
is worthwhile to note that the degree of reduction in WUR of the triple
layer film was more profound than that of double layer film due to
protecting the middle bio-nanocomposite film layer polymer against
water by the PLA layer at both sides.
3.9. Thermal stability
The thermal stability of the agar/κ-carrageenan blend, agar/
κ-carrageenan/clay nanocomposite, multilayer, and PLA films was
tested by TGA, and their TGA and DTGA curves with those of neat
agar and κ-carrageenan films for comparison are shown in Fig. 3.
The TGA curves show weight decreasing pattern of thermal decom-
position of the films and the DTGA curves clearly show the maxi-
mum decomposition temperature (Tmax) at each step of thermal
decomposition. The results of TGA and DTGA curves for the thermal
decomposition of the films were summarized in Table 5.
PLA film exhibited one-step thermal decomposition with the maxi-
mum decomposition rate at 364 °C, however, the other films exhibited
multistep decomposition phenomena. The multistep thermal decompo-
sition of the films is mainly due to the thermal decomposition behavior
of the component biopolymer films, i.e., agar and κ-carrageenan films.
Table 4
Moisture content (MC), water solubility (WS), and water uptake ratio (WUR) of agar/
κ-carrageenan blend, agar/κ-carrageenan/clay nanocomposite, polylactide (PLA), and
multilayer films1.
Film2 MC (%, w.b.) WS (%) WUR (%)
Blend 13.5 ± 0.4c 53.5 ± 1.0c 1813.9 ± 144.9e
Nanocomposite 12.2 ± 0.9bc 56.3 ± 0.4c 1615.3 ± 65.1d
PLA 10.1 ± 0.3a 0.9 ± 0.8a 0.8 ± 0.2a
Double layer 11.1 ± 0.9b 29.4 ± 1.1b 958.2 ± 12.7c
Triple layer 10.6 ± 0.4a 28.6 ± 9.7b 106.4 ± 2.2b
1
Means of replicates ± standard deviation. Any two means in the same column
followed by the same letter were not significantly different (p >0.05) by Duncan's
multiple range test.
2
Same as in Table 1.
As shown in the TGA curves, thermal decomposition of agar and
κ-carrageenan films decomposed in three steps. The initial decomposi-
tion of the biopolymer films is attributed to evaporation of moisture
in the films (Barreto, Pires, & Soldi, 2003), which accounted for about
9–12% of mass loss. The second decomposition begins at 180 and
188 °C and gave the maximum degradation rate at 264 and 269 °C for
agar and κ-carrageenan films, respectively, which is attributed to
volatilization of glycerol (boiling point 289 °C) added as a plasticizer
(Martucci & Ruseckaite, 2010). The third and main step of decomposi-
tion, began at temperature of 280 and 282 °C with the maximum degra-
dation rate at 315 and 359 °C, is attributed to the thermal degradation
of the biopolymer chain (Martucci, Vazquez, & Ruseckaite, 2007).
The blend film showed a similar pattern of thermal degradation be-
havior as the component biopolymer films. The thermal stability of the
nanocomposite film was slightly lower the neat blend film until the sec-
ond step of degradation, then exhibited higher stability than the blend
film. Such phenomena have been frequently observed with other
nanocomposite films when small amount of clay (less than 8%) was
added (Pavlidou & Papaspyrides, 2008). Presumably, the clay has dual
effects on the nanocomposite, one is the catalytic effect towards the
degradation of the polymer matrix which would decrease the thermal
stability, and the other is its barrier effect which should improve the
thermal stability (Zhao et al., 2005). As expected, the thermal stability
of the PLA laminated bio-nanocomposite films exhibited in-between
of those of PLA and the bio-nanocomposite film as shown in the TGA
curves. Note that the final residual weight of the PLA-laminated films
was rather high due to the high amount of ash content of agar and
κ-carrageenan, i.e., 16.1 and 39.3%, respectively.
These results indicated that the thermal stability of PLA film was
higher than the biopolymer blend and its nanocomposite films and
the lower thermal stability of those films was improved after forma-
tion of multilayer films with the PLA layers.
4. Conclusions
Blending, formation of nanocomposite with clay, and lamination
with PLA layers have been tested to improve film properties such as
optical, mechanical, barrier, and thermal stability properties of agar
and κ-carrageenan-based film. Simple blending of the biopolymers,
agar and κ-carrageenan, resulted in a limited success. There was a
significant reduction in permeability such as WVTR and OTR of
solvent-cast agar/κ-carrageenan blend films when nanoclays were
incorporated, and the mechanical strength of the nanocomposite
film increased significantly compared to their counterpart polymer
film without clay, which is comparable to plastic polymers except
lower flexibility property. However, the blend film containing
nanoclay did not generally have permeability values enough to the
target values for the gas barrier properties of commodity packaging
films such as polyethylene, polypropylene, and polystyrene. In addi-
tion, both the blend and its nanocomposite films exhibited rather
lower water resistance property due to their hydrophilic nature. In
the present study, the nanocomposite film was laminated with
more hydrophobic PLA layers without adding any compatibilizer or
adhesives, or any film surface modification treatment. The water
vapor barrier and water resistance properties of the resulting lami-
nated films increased profoundly close to those of PLA film, while
the gas barrier property of PLA film increased significantly close to
that of the bionanocomposite film. In addition, the resulting multiple
layer film of sheet are expected to be biodegradable since both com-
ponent layers are environmentally-friendly materials produced from
annually renewable material sources. Consequently, lamination of
the biopolymer film with PLA was the most efficient and feasible
method to improve the film properties by combining the advantages
of individual layer of film. Double layer or triple layer film or sheets
composed with the bionanocomposite film inner layer and PLA
outer layer can be produced in commercial scale with the plastic
 J.-W. Rhim / Food Research International 51 (2013) 714–722 721

a) b)
100 100

80 80

Weight (%)
Weight (%)

60 60 • -carrageenan film

40 Blend 40
Nanocomposite
Double layer agar film
20 Triple layer 20
PLA

0
0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature (oC) Temperature (oC)

0.00 0.000

-0.02 -0.005

DTG (mg/%)
DTG (mg/%)

-0.04 -0.010

-0.06 -0.015

-0.08 Blend -0.020

Nanocomposite
-0.10 Double layer -0.025 agar film
• -carrageenan film
Triple layer
-0.12 PLA -0.030

-0.14 -0.035
0 100 200 300 400 500 600 0 100 200 300 400 500 600
oC)
Temperature ( Temperature (oC)

Fig. 3. TGA and DTGA curves of (a) agar/κ-carrageenan blend, agar/κ-carrageenan/clay nanocomposite, PLA, and their multilayer films, and (b) neat agar and κ-carrageenan films.

processing methods such as coextrusion or lamination coating pro- Acknowledgments

cesses. The multilayer film or sheet can be formulated into several dif-
ferent types of packaging shapes, and they are expected to be used for This research was supported by the Agriculture Research Center
the packaging of various types of food materials for keeping the qual- (ARC 710003-03-2-SB320) program of the Ministry for Food, Agricul-
ity and extending the shelf life of the packaged foods. ture, Forestry and Fisheries, Korea.

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