Food Packaging and Shelf Life 7 (2016) 41–46

Contents lists available at ScienceDirect

Food Packaging and Shelf Life

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

Improvement of water barrier properties of starch films by lipid

nanolamination
Aníbal M. Slavutsky* , María A. Bertuzzi
Instituto de Investigaciones para la Industria Química (CONICET), CIUNSa, Facultad de Ingeniería, Universidad Nacional de Salta, Av. Bolivia 5150, A4408TVY
Salta, Argentina

A R T I C L E I N F O A B S T R A C T

Article history: A nanolaminate consists of two or more layers of material with nanometric dimensions that are
Received 19 October 2014 physically or chemically bonded to each other. Starch based edible films present suitable characteristics
Received in revised form 5 October 2015 for food protection, but their functional properties are affected by film water content. Nanolaminated
Accepted 19 January 2016
films were formulated by coating the starch film with lipid nanolayers in order to improve their water
Available online 2 February 2016
resistance and barrier properties. Lipid nanolayer presence was confirmed by SEM images and contact
angle measurements. Sorption isotherms of nanolaminated films showed an important reduction in film
Keywords:
water adsorption through all the aw range studied. The effect on permeability of the driving force (aw
Nanolaminated film
Starch matrix
difference) and the aw values at each side of the film, were analysed. Water vapour transport was
Lipid nanolayer controlled by water diffusion through hydrophobic nanolayers. Nanolamination of edible films improved
Sorption isotherm the water barrier properties of hydrophilic films by combining starch with lipids materials at nanometric
Water vapour permeability scale.
ã 2016 Elsevier Ltd. All rights reserved.

1. Introduction Spiridon, 2013; Kampeerapappun, Aht-ong, Pentrakoon, & Srikul-

kit, 2007), the introduction of lipids as microdroplets inside the
Nowadays, about 150 million tons of plastics are produced film matrix (Debeaufort, Quezada Gallo, Delporte, & Voilley, 2000;
annually all over the world, and their production and consumption Zahedi, Ghanbarzadeh, & Sedaghat, 2010), and the production of
show a growing trend. Most of these plastics are petroleum based, laminated films that consist in a lipid layer of micrometric
and their production results in increasing use of non-renewable dimensions on a polysaccharide or protein based film (Debeaufort
resource and serious environmental pollution problems (Parra, et al., 2000; Phan The, Debeaufort, Luu, & Voilley, 2008).
Tadini, Ponce, & Luga, 2004). Biopolymers produced from Incorporation of nanofillers such as montmorillonite and
renewable resources are an innovating answer to replace cellulose nanocrystal has been used as an alternative to improve
conventional petroleum based products and fit with a real functional properties of starch based film (Chen, Liu, Chang, Cao, &
sustainable development approach. Biodegradable films based Anderson, 2009; Svagan, Hedenqvist, & Berglund, 2009; Liu,
on starch, can be produced at low cost and large scale. However, the Chaudhary, Yusa, & Tadé, 2011; Slavutsky, Armada, & Bertuzzi,
mechanical and barrier properties of this promising material have 2012; Slavutsky & Bertuzzi, 2014). The decrease in gas or vapour
to be enhanced in order to be able to compete with conventional permeability is due to the increase in tortuosity of the diffusion
petroleum-based polymers (Averous, 2001; Vieira, Da Silva, Dos path of permeant molecules caused by nanoparticles (Slavutsky &
Santos, & Beppu, 2011). Starch is a hydrophilic material and their Bertuzzi, 2014). Besides, nanoclay addition produces an increase in
main functional properties depend on their water content. This is Young’s module and tensile strength and a decrease in film
due to water vapour strongly interacts with polymer matrix elongation as a consequence of film structure reinforcement
affecting their structure (Bertuzzi, Castro Vidaurre, Armada, & (Slavutsky, Bertuzzi, Armada, García & Ochoa, 2014).
Gottifredi, 2007; Perdomo et al., 2009). Many attempts have been Inclusion of lipids into the film can be made by two different
done in order to overcome this problem, such as the incorporation methods: lamination or emulsion. Bi-layer films are obtained by
of nanofiller of organic or inorganic origin (Bodirlau, Teaca, & lamination of a hydrophobic lipid layer over a preformed
hydrophilic film, resulting in the lipid being a distinct layer, of
micrometric thickness, atop the hydrophilic film. On the other
* Corresponding author. Fax: + 54 387 4251006. hand, emulsion films are formed by dispersion of the lipid material
E-mail address: [email protected] (A.M. Slavutsky). throughout the hydrophilic film (Rhim and Shellhammer, 2005).

http://dx.doi.org/10.1016/j.fpsl.2016.01.004
2214-2894/ ã 2016 Elsevier Ltd. All rights reserved.
42 A.M. Slavutsky, M.A. Bertuzzi / Food Packaging and Shelf Life 7 (2016) 41–46

Indeed, the association of lipids with a film forming compound, solution, while still hot, was cast over plastic dishes. Dishes were
such as protein or carbohydrate (biopolymers), is required due to placed in an air-circulating oven at 45
C until films were dry. After
their non-polymeric nature, and thus, the poor mechanical that, dishes were removed from the oven and the films were peeled
resistance of solid fat. Mass transfer resistance of lipid compounds off. Isotropic films were obtained.
against gas and vapour migration is mainly due to their structure
and hydrophobic character. The incorporation of lipid compounds 2.3. Nanolaminated films
in film forming solution, such as sunflower oil and essential lemon
oil, could improve mechanical and barrier properties of hydro- Nanolaminated films consist of oil nanolayers deposited over a
colloids based films (Sánchez-González, Chiralt, González-Martí- starch film support. Starch/ELO/SO films were obtained according
nez, & Cháfer, 2011; Vargas, Albors, & Chiralt, 2011). Furthermore, the following procedure. Starch films were stored at 53% RH for a
essential oil compounds have a well-documented antimicrobial week, before the lipid nanolayers were added. In order to form the
activity. Water vapour barrier efficiency of emulsion-based edible oil nanolayer, starch films were dipped into ELO during 2 min and
films depends on the nature of the lipids, the chain length of the then, they were rinsed with hexane. Hexane was evaporated from
fatty acids and the structure of the dried emulsion which the samples using an air flow at 25
C for 24 h. A second layer of SO
constitutes the film. Several studies showed that bi-layer films was deposited using the same procedure.
are more effective barriers against water vapour transfer than
emulsion films, due to the continuous hydrophobic phase in the 2.4. Characterization of nanolaminated starch/oil films
film (Pérez-Gago and Krochta, 2005). Emulsion-based films reduce
around 10 times the water vapour permeability of hydrocolloid 2.4.1. Scanning electron microscopy (SEM)
based films, while bi-layer films have 10–1000 times better barrier Cross-section and surface of film samples were examined by
efficiency against water transfer than emulsified film (Debeaufort SEM using a JEOL JSM 6480 LV scanning microscope (Japan).
et al., 2000). However, bi-layer films tend to delaminate and Samples were previously stored in a relative humidity controlled
exhibit poor mechanical properties due to the fracture or cracking ambient during a week (53% RH). Films were cryofractured by
of the lipid layer. These problems are related to the low immersion in liquid nitrogen. Samples were stored at 25
Cover
compatibility between the hydrophilic polymeric matrix and the silica gel. Then film samples were mounted on aluminium stubs
lipid layer of non-polymeric characteristics. and coated with gold plasma. Samples were observed using an
A nanolaminated film consists of two or more layers of material accelerating voltage of 15 kV.
with nanometric dimensions that are physically or chemically
bonded to each other (Rubner, 2003). Multilayer films or coatings 2.4.2. Surface properties
of nanometric thickness can be made by successive adsorption of Surface hydrophobicity was evaluated through static contact
oppositely charged polyelectrolytes on a solid support. They could angle measurements. The contact angle was measured by the
be used for potential applications such as food preservation and sessile drop method (Kwok and Neumann, 1999), using a
coatings for implant devices (Rudra, Dave, & Hayne, 2006). goniometer (Standard Goniometer with DROP image standard,
Carneiro-da-Cunha et al., (2010) and De S. Medeiros, Pinheiro, model 200-00, Ramé-Hart Instrument Co., Succasunna, USA). A
Carneiro-da-Cunh, and (2012) Vicente studied the impact of small water droplet was released on the film surface, digital
hydrocolloid deposition, as nanolayers, over PET films. However, pictures were gathered and the image produced was used to
the only mention to a lipid nanolaminated hydrocolloid films was calculate the contact angle. Contact angle measurements were
reported by our group in a previous work (Slavutsky and Bertuzzi, taken at 5 s and 30 s for each type of film. Ten replicates were taken
2015). Nanolaminated films were formulated by coating starch film on each kind of film.
with a lipid nanolayer of sunflower oil, driven by favourable
interfacial forces that interact between oil molecules and the 2.4.3. Moisture sorption isotherms
starch film. The aims of this work were to formulate starch/oil Constant relative humidity environments were established
nanolaminated films combining two different oil nanolayers and to inside sorbostats (glass jars) using salt solutions. The salts used
investigate the improvements on water resistance and barrier (LiCl, CH3COOK, MgCl2, K2CO3, Mg(NO3)2, NaBr, NaCl, KCl) were the
properties of starch based films. different salts recommended by the European project COST-90
(Spiess and Wolf, 1983), to cover a water activity (aw) range from
2. Materials and methods 0.10 to 0.90. Film samples (rectangular strips approximately 2 cm2
area) were first freeze-dried (Thermovac Industries Corp, USA) and
2.1. Materials stored in a desiccator during a week. Samples were weighed and
placed on a plastic lattice by holding it on a tripod inside the
Food grade corn starch (Unilever, Argentina) was used as sorbostats that contain the saturated salt solutions and then the
polymeric matrix for film formulation. Essential lemon oil (ELO) sorbostats were sealed. The sorbostats were kept inside an
was provided by CITROMAX S.A.C.I. (Argentina). Food grade environmental chamber maintained at constant temperature. Film
sunflower oil (SO) was provided by Molinos Río de la Plata samples were equilibrated in the sorbostats for 4 days before their
(Argentina). Glycerol (Mallinckrodt, USA) was added as plasticizer. weights were recorded. The weights of the samples were checked
Hexane was provided by Aldrich (USA). All salts used to obtain during 3 more days. Equilibrium was judged to have been attained
different relative humidity ambient (% RH) were provided by when the difference between two consecutive sample weightings
Aldrich (USA). was less than 1 mg/g dry solid. Data were reported for each relative
humidity as gram of water sorbed/100 g dry film. Absorption tests
2.2. Film forming solution were done in quadruplicate at each aw. The moisture sorption
determination was done at 25
C.
Film forming dispersion was prepared by mixing 5 g of starch, The data obtained were fitted by GAB sorption model, as
100 mL distilled water and glycerol in a concentration of 20% w/w described by Eq. (1):
of starch. The dispersion was gelatinized in a shaking water bath at
w0 C  k  aw
78–80
C during 10 min. This procedure ensures the disintegration we ¼ ð1Þ
ð1  k  aw Þð1  k  aw þ C  k  aw Þ
of starch granules to form a homogeneous solution. Starch
 A.M. Slavutsky, M.A. Bertuzzi / Food Packaging and Shelf Life 7 (2016) 41–46 43

where we is the equilibrium moisture content (g water/100 g dry

film), w0 is the monolayer content (g water/100 g dry film), C is
Guggenhein constant related to sorption heat monolayer, k is a
correction factor related to sorption heat multilayer.
The quality of the fitting was evaluated through the R2 and
through the mean relative percent error (%E) defined as:
Xn  
we;i  wp;i 100
%Error ¼ j j  ð2Þ
n¼1
w e;i n

where n is the number of data points, (we) and (wp) are

experimentally observed and predicted by the model values of
the equilibrium moisture content, respectively. The mean relative
percentage error (%E) has been widely adopted throughout the
literature to evaluate the goodness of fit of sorption models, with a
%E value below 10% indicative of a good fit for practical
applications. Test was performed in starch films and nano-
laminated films at 25
C.
Fig. 1. SEM microphotograph of starch film (cross-section).
2.4.4. Water vapour permeability
The apparatus and methodology described in ASTM E96 (ASTM, saturated solution, Nw is measured value of water vapour
2010) were used to measure film permeability. Film specimens transmission rate (g/mol cm2 s) from surface of distilled water or
were conditioned during 72 h in a chamber at 25
C and 53% RH saturated salt solution to the internal surface of the film (air gap
(Mg(NO3)2 saturated salt solution) before being analysed. Films resistance), hi is air gap between film and surface of distilled water
were sealed on cups containing different saturated salt solution or or saturated salt solution in the cup (cm), c is total molar
distilled water. Test cups were placed in a desiccator cabinet concentration of air and water vapour (g/mole.cm3), D is diffusivity
maintained at constant temperature. Saturated salt solutions were of water vapour in air (cm2/s) and cte is a constant to satisfy unit
used to provide specific relative humidity. In all cases, relative conversions. Test was carried out in triplicate for each film.
humidity inside desiccator cabin was lower than relative humidity
inside the cups. Table 2 shows the range of aw used in each assay. A 3. Results and discussion
fan was used to maintain uniform conditions at all test locations
over the specimen. Weight loss measurements were taken by 3.1. Scanning electron microscopy
continuous weighing of the test cup to the nearest 0.001 g with an
electronic scale (Ohaus PA313, USA). Data were transferred to a Fig. 1 shows the cross section and the surface of a starch film.
computer. Weight loss was plotted versus time and when steady Starch films exhibited a cross section of dense and homogeneous
state (straight line) was reached, 8 h more were registered. aspect and a flat and smooth surface. It is indicative that the starch
Thickness value was the mean of five measurements with an granules were completely disrupted and the starch molecules were
analogical thickness gauge (Digimess, Argentine) and it was used properly solubilized. Fig. 2 shows the cross section of a starch/ELO/
for water vapour permeability calculations. The water vapour SO nanolaminated film. This image points out the formation of oil
transmission rate (WVTR) was calculated from the slope (G) of a nanolayers over the starch film surface. The nanolayer can be
linear regression of weight loss versus time (Eq. (3)) and measured observed in the border of the upper side of the film due its
water vapour permeability (P) was calculated according to Eq. (4): separation from the starch matrix, Fig. 3 corresponds to the surface
image of a nanolaminated film and it exhibits the strong
G
WVTR ¼ ð3Þ attachment between the different layers on the starch matrix.
A
The lipid layers show a wavy surface, which can be clearly seen in
Figs. 2 and 3. This undulation of the surface is distinctly different
WVTR  1
P ¼ cte  ð4Þ
ðpw0  pw2 Þ

Corrected values of water vapour permeability (Pc) were

obtained according the equations proposed by Gennadios, Weller,
and Gooding (1994):
WVTR  l
Pc ¼ cte  ð5Þ
Dpr

Dpr ¼ pw1  pw2 ð6Þ

pw1 ¼ pT  ðpT  pw0 ÞexpðNw hi =cDÞ ð7Þ

where l is the film thickness (cm); A is the area of exposed film

(cm2), pw1 is partial pressure of water vapour at underside of film
(Pa), pT is total atmospheric pressure (Pa), pw2 is partial pressure of
water vapour at the film surface outside the cup (Pa), pw0 is partial
pressure of water vapour in air at the surface of distilled water or Fig. 2. SEM microphotograph of starch/ELO/SO film (cross-section).
44 A.M. Slavutsky, M.A. Bertuzzi / Food Packaging and Shelf Life 7 (2016) 41–46

3.2. Surface properties

The contact angle measurement is a useful tool to determine

the hydrophobic or hydrophilic character of a film surface. The
most wettable surfaces present low values (u < 20
) and the
hydrophobic surfaces, on the contrary, show high values (u > 70
) of
the contact angle. Table 1 shows contact angle measurements
obtained at different times for nanolaminated film samples. Starch
films presented the lower contact angle values at the different
times tested. This indicates the hydrophilic character of starch film.
Andrade and Sima (2005) reported similar values for maize starch
films. Oil lamination over the film surface produced strong
modifications. Starch/ELO films showed an important rise in the
hydrophobic character of the film surface, and thus, a significant
increase in contact angle due to the ELO presence. However, the
addition of the second nanolayer of SO in starch/ELO/SO films
resulted in a decrease in the contact angle. This contact angle value
was close to that obtained for starch/SO films, according to results
Fig. 3. SEM microphotograph of starch/ELO/SO film (surface). described by Slavutsky and Bertuzzi (2015). A similar behaviour
was observed in heparin/chitosan multilayer films and pectin/
chitosan films, where the last layer was dominant in surface
behaviour (Fu, Ji, Yuan & Shen, 2005; De S. Medeiros et al., 2012).
Table 1
Contact angle measurements taken at different times. There are significant differences between contact angle values
taken at different times in starch films due to their hydrophilicity
Film Contact angle
and the high rate of the relaxation phenomena in this material. On
5s 30 s the other hand, no significant differences were observed in contact
Starch 38.2
 1.2 35.3
 1.4 angle of nanolaminated films.
Starch/ELO 72.8
 2.5 71.8
 3.0 The contact angle results showed the development of the
Starch/SO 52.4
 2.1 50.1
 1.9 alternated deposition of ELO and SO layers, which suggest that the
Starch/ELO/SO 58.3
 1.7 55.9
 1.5
layers are progressively built by deposition of the oils. According to
Fu et al. (2005) the wettability of a surface depends on the nature
of the outermost layer and not on the initial substrate film;
from that presented by starch films, which have a smooth, flat however, interpenetration of layers may cause some influence on
surface, confirming the presence of the nanolayers. Fig. 3 shows a that property, especially at the nanoscale. Essential oils are very
zone with incomplete coverage of the lipid nanolayer. Starch is a complex natural mixtures which may contain about 20–60
hydrophilic material (polysaccharide), SO is a hydrophobic components at quite different concentrations. The components
substance (fatty acids) and ELO has an intermediate behaviour include two groups of distinct biosynthetic origin. The main group
(terpenes, alcohols, aldehydes, etc.) according to their composi- is composed of terpenes and terpenoids, and the other of aromatic
tion. Therefore the compatibility between these materials is driven and aliphatic constituents (Bakkali, Averdeck, Averdeck, &
both, by composition and scale of work. As the size of systems goes Idaomar, 2008). The methodology used in the formulations of
down, surface effects become increasingly important. The control starch/ELO films can be responsible of aromatic components
of intermolecular forces and interactions is fundamental for the elimination by evaporation coupled with hexane. Then, only
achievement of the desired deposition. terpenes and terpenoids remain deposited on the starch surface.

Fig. 4. Moisture sorption data of starch films (&), starch/ELO films (*) and starch/ELO/SO films (~). GAB model fit (starch films ; starch/ELO films ; starch/ELO/
SO films ). Bars indicate standard deviation.
 A.M. Slavutsky, M.A. Bertuzzi / Food Packaging and Shelf Life 7 (2016) 41–46 45

Table 2 enthalpy of sorption, then indicates the affinity between water

GAB model parameters of starch films and nanolaminated films.
molecules and the film surface. The obtained values were
w0 C k R2 %E according to the water content of each type of films and showed
Starch 11.352  0.759 0.626  0.085 0.869  0.009 0.983 1.68 the same trend that the monolayer water content (w0). All k values
Starch/ELO 4.677  0.569 0.112  0.017 0.961  0.008 0.954 4.13 were below 1, showing that model selection was correct.
Starch/ELO/SO 3.325  0.416 0.285  0.032 0.890  0.008 0.975 2.43
3.4. Water vapour permeability

Permeability of hydrophilic films depends both, on the relative

Moreover, Mayachiew, Devahastin, Mackey and Niranjan (2010) humidity difference and on the absolute humidity values at both
reported that chitosan might interact with terpens which are the sides of the film (Slavutsky & Bertuzzi, 2012). Water vapour
major components of essential oils, mainly by weak interactions permeability was measured in three different intervals of the water
such as hydrogen bonding. The same type of interaction can be activity range, in order to evaluate the effect of these parameters.
established between starch and ELO in the first nanolayer, ensuring Table 3 shows permeability values obtained for a water activity
the strong adhesion between those materials. In addition, the difference (Daw) through the film of approximately 0.2, in three
adhesion between ELO and SO nanolayers is due to hydrophobic different ranges of aw. Permeability increased with aw values at
bonds. each side of the film, when a similar driving force (Daw) was used.
It is related to the increasing water solubility in the film with aw
3.3. Moisture sorption isotherms showed by the sorption isotherms (Fig. 4). Water molecules
plasticize starch films, even at low relativity humidity gradient.
Moisture sorption experimental values of starch films and Then, permeability increases with increasing film water content.
starch nanolaminated films, as well as their fitting curves using The more plasticized the film, the higher water permeability values
GAB model, are showed in Fig. 4. These results indicate that the were obtained. Starch nanolaminated films presented similar
incorporation of lipid nanolayers produces an important decrease behaviour than starch films, but their permeability values were
on water adsorption of starch films in all the range of aw studied. reduced by half for all driving forces and ranges of aw studied.
The nanolaminated films display a low water uptake up to aw Permeability of nanolaminated films also depended on Daw. These
values of 0.8, taking an exponential growth after this value. The results indicate that nanolaminated films formulated using lipids
increase in moisture content of films based on hydrophobic are capable to repel water molecules. Morillon et al. (2002)
substances, at high aw values, has been studied by several authors. reported a similar behaviour for several lipids compound. They
Morillon, Debeaufort, Blond, Capelle and Voilley (2002) indicated observed that at the same relative humidity gradient, permeability
that some hydrophobic substance containing hydrophilic groups, increase with aw range at each side of the films. Permeability
such as ester groups, carboxyl groups and hydroxyl groups, which values were consistent with the results of contact angle and
can be hydrated at high values of aw. Donhowe and Fennema sorption isotherms of the samples. Starch films exhibited a high
(1992) reported that water content of beeswax film increases hydrophilicity, followed by Starch/ELO/SO and finally Starch/ELO
exponentially at aw around 0.8. These results are according to those with the lowest water affinity. This can be due to water permeation
showed in Fig. 4. The complex chemical composition of ELO and its phenomenon, in nanolaminted films, is controlled by the diffusion
amphiphilic characteristics, combined with SO hydrophobicity process through hydrophobic nanolayers. The study of the sorption
resulted in a material with improved water resistance, even at high isotherms indicates that water content of films plays a determinant
water activity. In contrast to bi-layer films, nanolaminated films do role in the permeation process. At low aw, water content of
not present fractures or delamination of the lipid layer. nanolaminated films is much lower than starch films, while at high
GAB model parameters calculated for the different film samples aw the moisture content has similar values. Deposited oil nano-
are presented in Table 2. Monolayer water content of Starch/ELO/ layers form a barrier against water molecule transport due to their
SO films (3.325%) was substantially lower than that presented by hydrophobic characteristic.
starch films (11.352%). Starch/ELO films showed a value slightly
higher than Starch/ELO/SO. The deposition of lipid nanolayers 4. Conclusion
reduces the number of active sites of the film surface available for
water molecule interaction. The C values are related to the Nanolaminated films were formed by coating a starch films
with lipid nanolayers. The nanolayer formation was proved by SEM
images and surface properties. Images indicated that nanolayers
Table 3 were strongly attached to the starch surface and present a wavy
Water vapour permeability of starch films and nanolaminated films under different aspect. Sorption isotherms evidenced a decrease in water
driven forces. adsorption of nanolaminated films in all the range of water
awext  awint |Daw| Pm  1010 g/m s Pa Pc  1010 g/m s Pa Thickness (mm) activities. Permeation phenomenon was controlled by the water
Starch diffusion through the lipid nanolayers in starch/ELO/SO films.
0.329–0.536 0.207 3.73  0.19 7.14 83  7 Then, the incorporation of lipid nanolayers improved the water
0.536–0.762 0.226 4.59  0.18 8.02 85  6 vapour resistance and decreased by nearly half the water vapour
0.762-1 0.238 6.93  0.25 18.8 85  4 permeability of starch films.
Starch/ELO
0.329–0.536 0.207 1.80  0.11 2.44 82  3 Acknowledgements
0.536–0.762 0.226 2.14  0.09 3.11 85  6
0.762–1 0.238 3.48  0.26 7.03 86  7 The financial support provided by Consejo de Investigación de
la Universidad Nacional de Salta (CIUNSa) and by Agencia Nacional
Starch/ELO/SO
0.329–0.536 0.207 2.22  0.21 3.32 88  3 de Promoción Científica y Tecnológica (ANPCyT) are gratefully
0.536–0.762 0.226 2.82  0.12 4.82 83  8 acknowledged. The authors thank technical assistance of LASEM
0.762–1 0.238 4.47  0.34 9.01 84  9 (Laboratorio de Microscopia Electrónica de Barrido, ANPCyT,
CONICET, UNSA).
46 A.M. Slavutsky, M.A. Bertuzzi / Food Packaging and Shelf Life 7 (2016) 41–46

References Perdomo, J., Cova, A., Sandoval, A. J., García, L., Laredo, E., & Müller, A. J. (2009). Glass
transition temperatures and water sorption isotherms of cassava starch.
Andrade, C. T., & Sima, R. A. (2005). Surface modification of maize starch films by Carbohydrate Polymers, 76(2), 305–313.
low-pressure glow 1-butene plasma. Carbohydrate Polymers, 61, 407–413. Pérez-Gago, M. B., & Krochta, J. M. (2005). Emulsion and bi-layer edible films. In J. H.
ASTM. (2010). Standards American Society for testing and materials. E96. Standard Han (Ed.), Innovations in food packaging (pp. 384–402).New York: Elsevier
test methods for water vapour transmission of materials. Philadelphia. Academic.
Averous, M. O. L. (2001). Poly(lactic acid): plasticization and properties of Phan The, D., Debeaufort, F., Luu, D., & Voilley, A. (2008). Moisture barrier, wetting
biodegradable multiphase systems. Polymer, 42, 6209–6219. and mechanical properties of shellac/agar or shellac/cassava starch bilayer
Bakkali, F., Averbeck, S., Averbeck, D., & Idaomar, M. (2008). Biological effects of bio-membrane for food applications. Journal of Membrane Science, 325(1),
essential oils—a review. Food and Chemical Toxicology, 46(2), 446–475. 277–283.
Bertuzzi, M. A., Castro Vidaurre, E. F., Armada, M., & Gottifredi, J. C. (2007). Water Rhim, J. W., & Shellhammer, T. H. (2005). Lipid-based edible films and coatings. In J.
vapor permeability of edible starch based films. Journal of Food Engineering, 80 H. Han (Ed.), Innovations in Food Packaging (pp. 362–383).London,U.K: Academic
(3), 972–978. Press.
Bodirlau, R., Teaca, C. A., & Spiridon, J. (2013). Influence of natural fillers on the Rubner, M. F. (2003). pH-controlled fabrication of polyelectrolyte multilayers:
properties of starch-based biocomposite films. Composites: Part B, 44, 575–583. assembly and applications. In G. Decher, & J. B. Schlenoff (Eds.), Multilayer thin
Carneiro-da-Cunha, M. G., Cerqueira, M. A., Souza, B. W. S., Carvalho, S., Quintas, M. films: sequential assembly of nanocomposite materials (pp. 133–154).New York:
A. C., Teixeira, J. A., et al. (2010). Physical and thermal properties of a chitosan/ Weinheim & Wiley-VCH.
alginate nanolayered PET film. Carbohydrate Polymers, 82, 153–159. Rudra, J. S., Dave, K., & Hayne, D. T. (2006). Antimicrobial polypeptide multilayer
Chen, Y., Liu, C., Chang, P. R., Cao, X., & Anderson, D. P. (2009). Bionanocomposites nanocoatings. Journal of Biomaterial Science Polymer Edition, 17(11), 1301–1315.
based on pea starch and cellulose nanowhiskers hydrolyzed from pea hull fibre: Sánchez-González, L., Chiralt, A., González-Martínez, C., & Cháfer, M. (2011). Effect
Effect of hydrolysis time. Carbohydrate Polymers, 76(4), 607–615. of essential oils on properties of film forming emulsions and films based on
De S. Medeiros, B. G., Pinheiro, A. C., Carneiro-da-Cunha, M. G., & Vicente, A. A. hydroxypropylmethylcellulose and chitosan. Journal of Food Engineering, 105(2),
(2012). Development and characterization of a nanomultilayer coating of pectin 246–253.
and chitosan—evaluation of its gas barrier properties and application on Slavutsky, A. M., & Bertuzzi, M. A. (2012). A phenomenological and thermodynamic
“Tommy Atkins” mangoes. Journal of Food Engineering, 110(3), 457–464. study of the water permeation process in corn starch/MMT films. Carbohydrate
Debeaufort, F., Quezada-Gallo, J. A., Delporte, B., & Voilley, A. (2000). Lipid Polymers, 90(1), 551–557.
hydrophobicity and physical state effects on the properties of bilayer edible Slavutsky, A. M., & Bertuzzi, M. A. (2014). Water barrier properties of starch films
films. Journal of Membrane Science, 180, 47–55. reinforced with cellulose nanocrystals obtained from sugarcane bagasse.
Donhowe, I. G., & Fennema, O. (1992). The effect of relative humidity gradient on Carbohydrate Polymers, 110, 53–61.
water vapour permeance of lipid and lipid-hydrocolloid bilayer films. Journal Slavutsky, A. M., & Bertuzzi, M. A. (2015). Formulation and characterization of
American Oil Chemistry Society, 69, 1081–1087. nanolaminated starch based film. LWT—Food Science and Technology, 61(2),
Fu, J., Ji, J., Yuan, W., & Shen, J. (2005). Construction of anti-adhesive and 407–413.
antibacterial multilayer assembly of heparin and chitosan. Biomaterials, 26, Slavutsky, A. M., Armada, M., & Bertuzzi, M. A. (2012). Water barrier properties of
6684–6692. starch–clay nanocomposite films. Brazilian Journal of Food Technology, 15(3),
Gennadios, A., Weller, C. L., & Gooding, C. H. (1994). Measurement errors in water 208–218.
vapour permeability of highly permeable, hydrophilic edible films. Journal of Slavutsky, A. M., Bertuzzi, M. A., Armada, M., García, M. G., & Ochoa, N. A. (2014).
Food Engineering, 21(4), 395–409. Preparation and characterization of montmorillonite/brea gum
Kampeerapappun, P., Aht-ong, D., Pentrakoon, D., & Srikulkit, K. (2007). Preparation nanocomposites films. Food Hydrocolloids, 35, 270–278.
of cassava starch/montmorillonite composite film. Carbohydrate Polymers, 67, Spiess, W. E. L., & Wolf, W. F. (1983). The results of the COST 90 project on water
155–163. activity. Physical properties of foods. London: Applied Science Publishers.
Kwok, D. Y., & Neumann, A. W. (1999). Contact angle measurement and contact Svagan, A. J., Hedenqvist, M. S., & Berglund, L. (2009). Reduced water vapour
angle interpretation. Advantage in Colloid and Interface Science, 81, 167–249. sorption in cellulose nanocomposites with starch matrix. Composites Science
Liu, H., Chaudhary, D., Yusa, S., & Tadé, M. O. (2011). Glycerol/starch/Na+ and Technology, 69(3–4), 500–506.
-montmorillonite nanocomposites: a XRD, FTIR, DSC and 1H NMR study. Vargas, M., Albors, A., & Chiralt, A. (2011). Application of chitosan-sunflower oil
Carbohydrate Polymers, 83(4), 1591–1597. edible films to pork meat hamburgers. Procedia Food Science, 1(11), 39–43.
Mayachiew, P., Devahastin, S., Mackey, B. M., & Niranjan, K. (2010). Effects of drying Vieira, M. G. A., Da Silva, M. A., Dos Santos, L. O., & Beppu, M. M. (2011). Natural-
methods and conditions on antimicrobial activity of edible chitosan films based plasticizers and biopolymer films: a review. European Polymer Journal, 47
enriched with galangal extract. Food Research International, 43, 125–132. (3), 254–263.
Morillon, V., Debeaufort, F., Blond, G., Capelle, M., & Voilley, A. (2002). Factors Zahedi, Y., Ghanbarzadeh, B., & Sedaghat, N. (2010). Physical properties of edible
affecting the moisture permeability of lipid-based edible films: a review. Critical emulsified films based on pistachio globulin protein and fatty acids. Journal of
Reviews in Food Science and Nutrition, 42(1), 67–89. Food Engineering, 100, 102–108.
Parra, D. F., Tadini, C. C., Ponce, P., & Luga, A. B. (2004). Mechanical properties and
water vapour transmission in some blends of cassava starch edible films.
Carbohydrate Polymers, 58, 475–481.