Composites Communications 4 (2017) 59

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Composites Communications
journal homepage: www.elsevier.com/locate/coco

Novel sandwiched structures in starch/cellulose nanowhiskers (CNWs) MARK

composite lms

Dongyan Liua, Yu Dongb, Debes Bhattacharyyac, Guoxin Suia,
a
Institute of Metal Research, Chinese Academy of Science, 72 Wenhua Road, Shenhe District, Shenyang City, Liaoning Province, 110016 China
b
Department of Mechanical Engineering, School of Civil and Mechanical Engineering, Curtin University, Perth, WA 6845, Australia
c
Centre for Advanced Composite Materials, University of Auckland, 20 Symonds Street, Auckland 1101, New Zealand

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

Keywords: Novel sandwiched structures of cellulose nanowhiskers (CNWs) were found for the rst time at the cross section
Starch of fractured starch/CNWs composite lms. CNWs were obtained by hydrolysing bleached ax yarns through
Cellulose nanowhiskers (CNWs) heating in a concentrated sulfuric acid (60 wt. %) aqueous solution at 55 C for 60 min. Starch and starch/CNWs
Sandwiched structures composite lms were prepared by casting starch and mixtures of starch/CNWs homogenous aqueous
Solvent casting
suspensions, which was followed by drying at atmosphere. The CNWs layers are sandwiched within starch
matrices in a parallel direction to nanocomposite lm surfaces. The layer thickness increases with an increase in
the content of CNWs. The discovery of novel sandwiched structures demonstrates that both the interaction and
evaporation rate of the solvent can aect the dispersion and thus play important roles in the nanoparticle
dispersion. Such nanocomposite lms in the presence of self-assembled multi-layer structures may further
improve mechanical and gas barrier properties as a promising material candidate for food packaging
applications.

1. Introduction to a high elastic modulus [810]. The extent of reinforcements relies on

Starch, one of the most abundant natural polysaccharides, has been
well recognised as a potential bio-polymer for environmental sustain-
ability. It is inexpensive, biodegradable and edible with good form-
ability of lms [1]. Starch has been utilised in the packaging and
coating of food products owing to its edibility and low oxygen
permeability. However, its extensive application is limited due to its
water sensitivity. Starch lms are brittle and dicult to handle. Hence
a plasticiser is required to increase the exibility, elongation and
toughness of lms. Unfortunately, plasticisers generally decrease
mechanical strength and gas barrier properties, resulting from the
decrease in lm cohesion [2]. The addition of reinforcing llers, such as
layer silicates [3], carbon nanotubes [4,5], carbon black [6] and metal
or non-metal oxide nanoparticles [7], to biopolymers has proven to be
eective in enhancing their thermal, mechanical and barrier properties.
Cellulose is the most abundant natural bioresource in the world.
Cellulosic bres have been used as reinforcements due to their high
modulus, renewable sources, low density, biodegradability and low
cost. CNWs possess high crystallinity because their amorphous phases
can be mostly removed by acids during a hydrolysis process. Such
reinforcements have large specic areas, and high aspect ratios leading
the ller dispersion into polymer matrices as well as their interfacial
adhesion between llers and polymer matrices [11]. Hence, CNWs are
ideal llers for starch matrices due to their similar chemical structures,
which provide good compatibility between cellulose and starch through
hydrogen bonding. Dissolving starch in a solvent (usually warm water),
and then casting, dipping or spraying on a specic surface is still the
main method to produce edible starch lms or coating [12]. Nanocel-
lulose shows positive eects on the properties of starch matrices due to
uniform nanocellulose dispersion and good interfacial bonding between
cellulose and starch [1315]. It is conventionally recognised that the
strong interface bonding between nanoparticles and matrices is attrib-
uted to good nanoparticle dispersion. Dufresne got the well-dispersed
nanollers in starch/microbril composite lms at high cellulose
concentration of 20 and 50 wt.% [16]. In this study, novel layer
structured CNWs closely connected within starch matrices was obtained
for the rst time by evaporating water from starch/CNWs solution at
room temperature. Very recently, Chen et al. [17] demonstrated that
nanoparticle dispersion was dependent on the strength of nanoparticle/
polymeric molecule interaction by large-scaled molecular dynamics
simulations [17]. From the experiment viewpoint, this paper oers
strong support, for Chen's simulation work [17] in relation to layer

Corresponding author.
E-mail address: gxsui@imr.ac.cn (G. Sui).

http://dx.doi.org/10.1016/j.coco.2017.03.001
Received 27 September 2016; Received in revised form 1 March 2017; Accepted 9 March 2017
2452-2139/ 2017 Elsevier Ltd. All rights reserved.
D. Liu et al.
structures formed in starch/CNWs lms by using solvent casting. The
formation of layered structures is crucial to tailor the dispersion of
nanoparticles into polymer matrices, which could be achieved by
controlling the interfacial strength and solvent evaporation rates. Our
pioneering study sheds light on the further investigation of the
interactions between components in starch/CNWs composites in order
to understand the fundamental mechanism of such interactions.
2. Materials and methods
2.1. Materials
Normal maize starch (average granule size: ~20 m) was purchased
from Penford NZ Ltd., New Zealand, which consists of 25% amylase and
75% amylopectin. Raw ax yarns were supplied by Jayashree Textiles,
Kolkata, India. Sodium hydroxide and sulphuric acid with the concen-
tration in range from 9597% were supplied from Ajax Finechem Pty
Ltd., Taren Point, Australia and, ECP Ltd., New Zealand, respectively.
2.2. Preparation of nanocellulose and composite lms
The extraction of nanocellulose was similar to the process reported
in the previous literature [18]. Briey, the ax yarn was mixed with a
concentrated sulfuric acid aqueous solution at 60 wt.% and stirred
vigorously at 55 C for 1 h, which was followed by the centrifugation
and neutralisation to remove free acid. Subsequently, freeze drying was
utilized to obtain loose cellulose whiskers.
The simple solution casting process was used for the preparation of
starch/CNWs composite lms. Starch, glycerol, and nanocellulose
aqueous suspension were mixed together in order to obtain homo-
geneously dispersed composite lms. The plasticiser and ller contents
were xed at 35 wt.% for glycerol, 5, 10, 15, and 20 wt.% for CNWs,
based on dry starch matrices. The mixture was then heated above the
gelatinisation temperature for 30 min with aid of agitated stirring. After
the mixture was cooled down, it was cast on a polystyrene Petri dish,
prior to drying at room temperature until it was easily peeled o.
2.3. Characterisation
The structure of hydrolysed ax cellulose was investigated using a
transmission electron microscope (TEM Philips CM 12, Holland). A
droplet of the diluted suspension was stained by allowing the grids to
oat in a 2.0 wt% uranyl acetate solution for 1 min before observation.
The fracture surfaces of starch and starch/nanocomposite lms were
examined by a eld-emission scanning electron microscope (FE-SEM,
Philips XL30s FEG). Fourier transform infrared spectroscopy (FTIR,
ATR-FTIR, Nicolet 8700, USA) was employed to evaluate chemical
structures of starch and composite lms.
3. Results and discussion
3.1. Morphology
TEM micrograph of CNWs is shown in Fig. 1. The rod-like CNWs
with diameters of 1030 nm and lengths of 300500 nm were obtained
by the acid hydrolysis of bleached ax yarns. The incorporation of
sulphate groups along cellulose surfaces could result in a negative
charge of the surfaces. This anionic stabilisation via attraction/repul-
sion forces of electrical double layers might be the reason for CNWs to
form a stable and uniform aqueous suspension. The formation of
starch/CNWs mixture was then obtained by heating the mixtures above
85C. However, CNWs could be rearranged with the water evaporation
under room temperature during the lm formation.
All composite lms appear to be smooth, uniform and transparent.
Fig. 2 shows fracture surfaces of pure starch, starch/CNWs composites
and pure cellulose lms. Compared to pure starch shown in Fig. 2(a),
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Composites Communications 4 (2017) 59
Fig. 1. TEM micrograph of CNWs via the hydrolysis of bleached ax yarns.
starch/CNWs composites possess the formation of clear CNWs layers.
CNWs layers become thin and discontinuous at the low concentration,
as evidenced by single layer and double close layers for 5 and 10%,
respectively. The distance between CNWs layers is around 1 m. The
thickness of CNWs layer signicantly increases with increasing the
cellulose contents up to 15 and 20%. The whiskers can be clearly
detected under the high magnication for starch composites reinforced
with 15 wt% CNWs. However, the distance between the layers is
independent on the cellulose concentration. Fracture surfaces of pure
CNWs lms demonstrate layered CNWs structures of CNWs that are
closely connected. These results signify totally dierent morphology
from previously reported research. Sain et al. reported that 10 wt.%
cellulose nanobers shown as white spots uniformly distributed in
potato starch lms [19]. Aggregates of cellulosic crystals were present
at the fractural surface of pea starch-based nanocomposite lms when
the crystals content reaches 15 and 20 wt.% [13]. Cao et al. also
obtained the homogeneously embedded ax cellulose nanocrystals in
the plasticised starch at the concentrations of 1030 wt.% cellulose
nanocrystals via drying the composites in a vent oven at 50 C [20].
These morphologies have been recognized as the strong interactions
between the cellulose and starch matrix. From our experimental results,
the formation of the above mentioned layered CNWs results from minor
interactions between CNWs and slow water evaporation rate. The
determination of associated factors to control the CNWs dispersion in
starch matrices are currently under way in our research group and will
be reported in the near future.
The chemical structure of CNWs in composites was evaluated by
FTIR analysis. Fig. 3 shows FTIR spectra of pure starch, starch/CNWs
composite lm, as well as pure CNWs. The wide peak at around
3258 cm-1 and sharp peak at around 997 cm -1 were attributed to the
stretching vibrations of the hydrogen bonding of OH groups and CO
stretching vibrations in starch. All samples show similar spectra in
Fig. 3(1), resulting from similar structures of starch and cellulose. Pure
starch presents single peak at 3258 cm-1 from OH-stretching. This peak
moves to the higher wave number with an increase in CNWs content
from 3262 to 3279 cm-1 for 5 and 20 wt%, respectively. A small peak at
the left shoulder appears when the CNWs content is higher than 15 wt
%, clearly shown as the characteristic peak for CNWs. From Fig. 3 (2),
the spectra have no apparent peak shifting for pure starch and starch/
CNWs composites at lower wave numbers. A decrease in the peak
intensity of starch at 1074.6 cm-1 and an increase in the peak intensity
of cellulose at 1105.5 cm-1 become manifested, which suggests that the
D. Liu et al.
Fig. 2. SEM morphologies of fracture surface of (a) pure starch, and starch composite lms containing (b) 5, (c) 10, (d) 15, (e) 20 wt.% CNWs, (f) pure nanocellulose lm; Insets in (d) and
(f) are selected areas of interest at high magnications, respectively.
interaction between starch and CNWs are not as strong as uniformly
dispersed cellulose in matrices [20].
The dispersion of CNWs in starch matrices is illustrated in Fig. 4.
The unique structures of starch/CNWs composite lms by using
solution casting are ascribed to the slow water evaporation rate when
lms are formed, as illustrated in Fig. 4. This process is close to
equilibrium states. The uniform CNWs dispersion in starch matrices for
the rapid water evaporation case was observed, in which CNWs are
believed to have sucient time for their self-organisation to form a web
[5]. However, uniform mixtures are usually kept under vigorous
stirring before the fast evaporation of water molecules. Uniform CNW
dispersion in starch matrices generally lies in the strong hydrogen
bonding between cellulose and starch. Our nding indicates the CNWs
dispersion in starch matrices can be dominated by the combined eect
of interactions between nanoparticles and matrices and water evapora-
7
Composites Communications 4 (2017) 59
tion rate during the process of lm formation [17].
4. Conclusions
Novel sandwiched CNW layers within starch matrices were ob-
served for the rst time at the cross section of fractured starch/CNWs
composite lms. The thickness of such layers increases with an increase
in the CNWs content. Our results demonstrate that CNWs dispersion in
starch matrices are associated with the good interaction between
nanoparticles and matrices as well as water evaporation rate during
the lm fabrication. Such layered structures in composite lms can
oer great potential to food packaging applications with enhancements
of mechanical and gas barrier properties.
D. Liu et al. Composites Communications 4 (2017) 59

Fig. 3. FTIR spectra of (a) pure starch, and starch composites containing (b) 5, (c) 10, (d) 15, (e) 20 wt.% CNWs, and (f) pure (CNWs).

Fig. 4. Illustrations of typical layered structures with increasing the CNWs content in starch matrices (a), (b), and (c) (o denotes the cross section of CNWs), as well as corresponding
SEM micrographs of fractured surfaces for starch/CNWs composite lms with the CNWs contents of (d) 5, (e) 15 and (f) 20 wt%.

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