Carbohydrate Polymers 169 (2017) 176–188

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Carbohydrate Polymers
journal homepage: www.elsevier.com/locate/carbpol

Morphology, transport characteristics and viscoelastic polymer chain

confinement in nanocomposites based on thermoplastic potato starch
and cellulose nanofibers from pineapple leaf
Preetha Balakrishnan a , Sreekala M.S. b , Matjaž Kunaver c , Miroslav Huskić c ,
Sabu Thomas a,d,∗
a
International and Inter University Centre for Nanoscienece and Nanotechnology, PD Hills P.O, Mahatma Gandhi University, Kottayam, Kerala, 686560,
India
b
Post Graduate Department of Chemistry, Sree Sankara College Kalady, Ernakulum, Kerala, 683574 India
c
National Institute of Chemistry, Polymer Chemistry and Technology Dpt., Hajdrihova, 19SI-1000 Ljubljana, Slovenia
d
School of Chemical Sciences, Mahatma Gandhi University, PD Hills P.O, Kottayam, Kerala, 686560, India

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

Article history: Eco-friendly “green” nano composites were fabricated from potato starch and cellulose nanofibers from
Received 23 January 2017 pineapple leaf. Nanocomposites of starch/cellulose nanofibers were prepared by solution mixing followed
Received in revised form 10 March 2017 by casting. The investigation of the viscoelastic properties confirms starch macromolecular chain con-
Accepted 8 April 2017
finement around the nano scale cellulose surface, superior dispersion and very good interaction between
Available online 10 April 2017
thermoplastic starch and cellulose nanofibers. The degree of chain confinement was quantified. The chain
confinement was associated with the immobilization of the starch macromolecular chains in the network
Keywords:
formed by the nano-scale cellulose fibers as a result of hydrogen boding interactions. From the results,
Thermoplastic starch
Nanofiber
it was assumed that the starch glycerol system exhibits a heterogenous nature and cellulose nanofibers
Transport tend to move towards glycerol rich starch phase. Barrier properties also improved with the addition of
Isolation morphology nanofiller up to 3 wt.% but further addition depreciated properties due to possible fiber agglomeration.
Polymer chain confinement The kinetics of diffusion was investigated and typical kinetic parameters were determined and found
that the nanocomposites follow pseudo fickian behaviour. The outcome of the work confirms that the
prepared nanocomposites films can be used as a swap for packaging applications.
© 2017 Elsevier Ltd. All rights reserved.

1. Introduction
Green nanocomposites attain much attention today due to their
versatile applications. One of the key threat that our world faces
nowadays is problems due to plastic wastes and scientists all over
the world constantly work on developing green composites as a
substitute for synthetic plastics while conserving biodegradability.
(Dean & Yu, 2005).
The awareness of global issues due to plastic wastes increased
the importance of starch based thermoplastics which are fully
biodegradable and green in nature (Wang, Cai, Yu, & Xia,
2009).Some of the important applications of starch polymer include
production of paper and board, textiles and adhesives. Linear
∗ Corresponding author at: International and Inter University Centre for
Nanoscienece and Nanotechnology, PD Hills P.O, Mahatma Gandhi University, Kot-
tayam, Kerala, 686560, India.
E-mail addresses: sabuchathukulam@yahoo.co.uk, sabuthomas@mgu.ac.in,
sabupolymer@yahoo.com (S. Thomas).
Amylose and highly branched amylopectin are two important con-
stituents of starch. The content of amylose and amylopectin are one
factor which affects the final performance of starch based polymers.
Despite of its great advantages like biodegradability, low cost and
ease to chemical reactions it also faces many draw backs due to
its hygroscopic nature, poor mechanical, thermal and barrier prop-
erties, (Karimi, Dufresne, Md. Tahir, Karimi, & Abdulkhani, 2014).
Starch exists in a crystalline nature, so it plasticized to improve
the final properties and flexibility. Many plasticizers have been
used for plasticizing starch like citric acid (Priya, Gupta, Pathania, &
Singha, 2014), sorbitol (Arun, Kumar, & Sreekala, 2012), glycerol etc.
(Bootklad & Kaewtatip, 2013; Versino & García, 2014). To advance
the properties of thermoplastic starch, various methods like blend-
ing with other polymers like polyvinyl alcohol (Priya et al., 2014),
poly caprolactone (Avella et al., 2000), polyethylene (Oromiehie,
Lari, & Rabiee, 2013), polypropylene (Gupta & Alam, 2014), poly-
lactic acid (Ke & Sun, 2003) and reinforcing with naturally available
macro to nano fillers have been extensively reported.

http://dx.doi.org/10.1016/j.carbpol.2017.04.017
0144-8617/© 2017 Elsevier Ltd. All rights reserved.
 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
Cellulose is one of the naturally available polymers which
consist of repeating units of ˇ – Dglucopyranosegroup. It is semi
crystalline in nature with crystalline part and amorphous part
like lignin, pectin, hemicellulose etc. Apart from nanocrystals and
whiskers nanofibers contain both crystalline and amorphous region
and high aspect ratio (L/D)which provide an extensive network
of nanofibers which result in superior properties (Dhar, Bhardwaj,
Kumar, & Katiyar, 2014).
One of the major advantages of reinforcing cellulose material
in starch matrix is the presence of similar polysaccharide structure
which could benefit better matrix/filler interaction. Several stud-
ies have been reported the effect of cellulose as a reinforcing filler
in the starch matrix; these include work on jute (Das et al., 2011),
hemp (Gironès et al., 2012), sisal (Gironès et al., 2012), oil palm fiber
(Salehudin, Salleh, Mamat, & Muhamad, 2014), cotton (Savadekar
& Mhaske, 2012), bamboo (Liu, Zhong, Chang, Li, & Wu, 2010), dates
palm fiber (Ibrahim, Farag, Megahed, & Mehanny, 2014). Yang et al.
scrutinized the effect of nanocellulose reinforced starch as a sur-
face sizing agent for cellulosic paper and found that there was an
enhancement in the tear strength and printing quality of the paper
(Yang, Tang, Wang, Kong, & Zhang, 2014).
Plasticizer glycerol is an extremely small organic molecule with
three hydroxyl functionalities. it can enter into the starch molecules
and thereby reduce the intermolecular interaction between starch
molecules leading to an increase in the flexibility. Pineapple leaf
considered as a waste material after the harvesting of pineapples.
It consist of 80% cellulose, which is being wasted in the normal case
after harvesting (Faruk, Bledzki, Fink, & Sain, 2012). So, utilization
of waste material into an eco-friendly biodegradable composite for
packaging application is one way to reduce the problems due to
synthetic plastic materials. So, the endeavour of this work is to
make use of pineapple waste fibers as potential nano scale rein-
forcement on a green agro based polymer matrix, starch which
was extracted from the potato plantation waste. Potato starch rein-
forced with cellulose nanofiber has been reported earlier by Moran
et al. (Morán, Vázquez, & Cyras, 2013), in which starch derivatives
were used as a matrix for biocomposite. Although there are many
studies on the nanofibers from various resources on thermoplas-
tic starch, systematic and in-depth literature survey indicates that
there are no systematic investigations on nano scale pineapple leaf
fiber reinforced potato starch nanocomposites. It is important to
mention that large quantity of pineapple fibers is being wasted in
tropical countries where it is a very important farming activity.
Therefore, there is every need to make use of this agro-waste as
potential reinforcement for polymers. The matrix we have chosen
is thermoplastic starch derived from agro-waste potato, which is a
major waste after extracting food grade potato starch. Very specif-
ically, we have extracted nano cellulose from pineapple leaf fiber
by a standard protocol of acid washing as reported in literature.
Nanocomposites of starch/nanoscale pineapple fibers have been
fabricated by solution casting technique. Morphology, viscoelas-
tic properties and transport behaviour have been carefully studied.
Morphology-property correlation has been established. Finally, the
amount of starch macromolecular chains confined at the nanoscale
cellulose surface has been carefully estimated and this has been
correlated with interfacial, transport properties.
2. Materials and methods
2.1. Experimental
2.1.1. Materials
Post harvested pineapple leaves were collected from neighbour-
ing fields around Kottayam District Kerala, India. The leaves were
washed thoroughly to remove dust and other impurities stick into
177
the leaf. For the fabrication of thermoplastic starch (TPS), potato
starch (supplied by Lobha chem India Pvt. Ltd. Mumbai) and glyc-
erol (98% Purity chemical formula (HOCH2 )2 CHOH supplied by
Merck India Pvt. Ltd) were used. For nanofiber synthesis sodium
hydroxide, oxalic acid, hydrogen peroxide was supplied by (MERCK
India Pvt. Ltd).
2.1.2. Isolation of cellulose nanofibrils from pineapple leaf (PALF)
Procedure for the isolation of cellulose nanofiber were adapted
from previously reported work (Cherian et al., 2011). Firstly, PALF
fibers were dried and chopped into small pieces. The finely chopped
fibers were alkali treated using 2% NaOH solution in an autoclave
under a pressure of 138 kPa for almost 1 h. After that, the pressure
released instantly and the alkali treated fibers were then soaked
with distilled water several times until it relieved of any alkali con-
tent. The steam exploded fiber then bleached using a mixture of
equal parts of NaOH/glacial acetic acid (27 g/L and 78.5 g/L respec-
tively) and hydrogen peroxide. The bleaching was done for 30 min
and repeatedly six times until the colour of fibers completely turns
to white colour. It was then soaked and washed with distilled water
several times and dried in an air circulating oven for 10 h. The fibers
were then subjected to mild acid hydrolysis using 11% H2 C2 O4 in an
auto clave set at 138 kPa for 15 min, centrifuged and homogenized
2.1.3. Preparation of thermoplastic potato starch (TPS)/cellulose
nanofiber (CNF) composites
Thermoplastic starch composites were prepared by solvent cast-
ing technique. Calculated weight percentage (on dry starch basis)
of cellulose nanofibers were dispersed in distilled water and bath
sonicated for almost 30 min. Pre-weighed potato starch was mixed
well with 30% glycerol (on dry starch basis) using mechanical stir-
rer by adding 100 ml distilled water. The suspension of cellulose
nanofiber was added to starch-glycerol water mixture and mixed
in a mechanical stirrer (700 rpm) for 30 min at a temperature of
90 ◦ C. After the solution became viscous, it was poured on to lev-
elled Borosil glass Petri dishes and kept at 50 ◦ C for 12 h until
it completely dry. Solution cast films of TPS cellulose nanofiber
composites were made at 1,2,3,4 wt.% nanofiber concentrations (as
per dry weight of matrix). The films of thickness approximately
80 ␮m were obtained by this technique. Schematic representation
of preparation of nanocomposite shown in Fig. 1.
2.2. Characterization techniques of cellulose nanofibers and
nanocomposites
2.2.1. Fourier transform infrared spectroscopy (FTIR-ATR)
FTIR spectra recorded using a Shimadzu IR-470 IR spectrometer.
Raw fibers and final product (acid treated fiber) were dried in an
air circulating oven at 50 ◦ C. The spectrum of each sample analysed
at a range of 400–4500 cm−1 with a resolution of 2 cm−1 . Total of 4
scans per each sample were taken.
2.2.2. X-ray diffraction (XRD)
Crystallinity of fibers and composites are determined by XRD
measurement on a Bruker powder diffractometer. Prior to the
experiments the fibers (after each succesive treatment) and TPS-
CNF nancomposites dried in an oven. Radial scans of intensity
were recorded over scattering 2␪angles from 5 to 55◦ (step
size = 0.02◦ , scanning rate = 2 s/step) using a Ni-filtered Cu K radi-
ation (␪ = 1.5406 Å) an operating voltage of 45 kV, and a filament
current of 40 mA.
The crystallinity of fiber samples was determined by following
empirical Segals equation (Segal, Creely, Martin, & Conrad, 1959).
Crystallinity index (CrI) of each sample were calculated by refer-
ring to diffraction intensity of crystalline (I200 ) and amorphous
178 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
Fig. 1. Schematic representation of preparation of starch – CNF nanocomposites.
regions (Iam ). Where I200 represents both crystalline and amor-
phous regions of the material whereas Iam represents only the
amorphous regions.
I200 − Iam
CrI = × 100
I200
2.2.3. Scanning electron microscopy of nanofibers and
nanocomposites
Scanning electron microscopy (JEOL JSM-820 model) was used
to examine the surface morphology of fibers after each treatment
and fracture surface of TPS-CNF nanocomposites. The samples were
then coated with gold using a vacuum sputter coater to avoid char-
ring during SEM. The accelerating voltage was 15 kV. To understand
the fracture behaviour specimens were first frozen in liquid nitro-
gen and then immediately fractured.
The microtopographies of acid treated CNF samples were
observed by FESEM. The FESEM micrographs were taken on a Zeiss
Supra 35 VP. For the FESEM, about 30 mg of the well sonicated
samples were dispersed in 50 ml of acetone. (Ultrasonic Processor
UP400S, Hielscher). The suspension was applied to a glass substrate
from which the acetone quickly evaporated. The dried glass support
with its CNF particles on the surface was then coated with gold and
used for FESEM observations.
2.2.4. High-resolution transmission electron microscopy (HR
TEM)
The morphology of the nanofibrils were analysed by TEM
(JEM-2100HRTEM). The nanofiber suspension was subjected to
ultrasonic treatment for 30 min to disperse the nanofibers. A drop
of dilute solution was drop cast on the surface of the clean copper
grid and coated with a carbon film. Before image the grid was dried
in sodium vapor lamp for 4 h.
2.2.5. Dynamic mechanical analysis
(1) Dynamic mechanical analysis was performed on TA Q800 ther-
mal analyser (Q800 DMA, TA Instruments, New Castle, Delaware,
United States) using a thin film clamp. The viscoelastic proper-
ties were measured at a frequency of 1 Hz, strain amplitude of 5
micrometres in a temperature range −120 ◦ C to 70 ◦ C. The heating
rate was 2 ◦ C/min.
2.2.6. Transport properties
The kinetics of water absorption of the specimens was studied
using circular specimens of 2 cm diameter which were prepared
by cutting the samples using circular sharp edged die. Thickness of
the samples were measured using a screw gauge at several points.
These specimens were weighed and dipped in 30 ml of distilled
water kept in diffusion bottles. Samples were weighed after regu-
lar intervals and the surface of specimens were wiped with tissue
paper to remove adhering solvents. The process was continued until
equilibrium swelling attained.
3. Results and discussions
3.1. Cellulose nanofiber characterizations
The FTIR spectra of raw pineapple leaf and nanofibers are
shown in Fig. 2a. The two spectra have a characteristic band at
3300 cm−1 due to the hydroxyl groups. This indicates the occur-
rence of hydrophilic OH group in the fiber, which is a prime reason
behind the hygroscopic nature of cellulose. The band at 2901 cm−1
 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
Fig. 2. (2a) FTIR spectrum of raw PALF and Cellulose nanofiber. (2b) XRD profiles PALF after each treatment.
indicates the existence of polysaccharide functionality. This peak
was absent in the spectra of untreated pineapple leaf because of the
presence of impurities which upon chemical treatment increases its
intensity. (Alemdar & Sain, 2008). The peak at 1062 cm−1 assigned
to the carbonyl stretching and CH stretching vibrations of cellu-
lose. The newly emerged peak observed in the 1317–1320 cm−1
region corresponds to the C O groups of the aromatic ring in cel-
lulose (Gañán, Cruz, Garbizu, Arbelaiz, & Mondragon, 2004). The
intensity of the OH functionality indicates the cellulose content
increased by successive chemical treatment. When native cellulose
from PALF converted to PALF CNF through steam explosion, bleach-
ing and acid hydrolysis, the characteristic peak at 3300 cm−1 still
exist. Intensity of peak increase with chemical treatment because
the non-cellulosic matrix of native cellulose was removed success-
fully without losing the cellulose structure and also due the purity
of prepared nanofibers. Peak at 2890 cm−1 corresponds to the
asymmetric vibrations of CH2 group present in the cellulose. The
intensity of this peak increases with the chemical treatment corre-
sponds to cellulose structure. The peak at 1655 cm−1 is due to the
bending mode vibration of the absorbed water with some contri-
butions from carboxylate groups (C.S., George, & Narayanankutty,
2016). These results indicate that the cellulose component retained
during the chemical treatment carried out on PALF.
Cellulose crystallinity is one of the important factors governing
the performance of nanocomposites. Fig. 2b shows the diffrac-
togram of PALF after various chemical treatments and found that
the crystallinity increases with the chemical treatments. Pineapple
leaf consists of approximately 10.5% lignin, 80.5% Hemicellulose,
73.4% cellulose (Costa et al., 2013). Higher crystallinity of cellulose
is due to the presence of strong inter and intramolecular interac-
tion. The XRD profiles have two major peaks corresponds to 2␪ = 16◦
and 22.7◦ which is typically of cellulose 1 structure. The sharp peak
at 22.7◦ of acid treated fiber is due to higher crystallinity of cellu-
lose. The crystallinity of nanofiber will increase their firmness and
stiffness, and it results in superior reinforcement in composites.
The peak strength at 2␪ = 22.7◦ related to [002] lattice plane
increases after each chemical treatment which is almost similar to
earlier reported work of Wan et al. (Wan et al., 2009). It further rises
stridently with chemical treatment during isolation. From the XRD
profiles, we can assume that the hydrolysis take place selectively to
the amorphous regions where the crystalline region is more or less
stable to chemical attack. Crystallinity of cellulose after each treat-
ment calculated by Segals equation which shows the crystallinity
increases from 42.01% for untreated fibers to 67.03% for chemically
treated fibers and to 75.38% for cellulose nanofibrils, which can
be compared to formerly reported data for nanofibers from vari-
ous origin. The crystallinity of 54.10%, 69.34%, 79.87% for cassava
bagasse (Versino & García, 2014), wood fibers (Chen et al., 2011)
179
and wheat straw (Kaushik, Singh, & Verma, 2010) respectively were
previously reported.
Morphological investigation of pineapple leaf after various
chemical treatments is shown in Fig. 3(a–d). From the SEM images,
it is evident that after successive chemical treatment the smooth-
ness of fibers increases and fiber diameter decreases.
The rough surface of untreated PALF fiber shown in Fig. 3a.
Following alkali treatment (Fig. 3b), the fiber surface becomes
smoother which be a sign of the fractional elimination of hemicel-
lulose, lignin, pectin, wax and other impurities adhering in PALF.
Wax and pectin act as a shielding coating surrounding natural
fiber. Moreover, it is important to note that the fiber diameter
reduces after each treatment which shows the removal of non-
cellulose components. Lignin forms a connecting link bond with
the cellulose ester and acts as a binder in the fiber components,
thus preserving the bundle form after alkali treatment. To eval-
uate the decrease in fiber diameter after each treatment, fiber
diameter calculated using imageJ software and found that, a sub-
stantial decrease in fiber diameter 7.80 ␮m, 4.68 ␮m, 0.67 ␮m for
alkali, bleached, and acid treated fiber respectively. Later, aggre-
gated nanofibers obtained from acid treatment defibrillated via
high shear homogenization and used as reinforcement filler. The
effect of the subsequent mechanical treatment (steam explosion
and bleaching) was clear from the assessment of micrographs in
Fig. 3(b and c) and observed that the PALF fiber bundles separate
into individual fibers. Fig. 3d, FESEM image (1 ␮m magnification) of
acid treated PALF fiber shows the presence of long individual fibers
which confirms the formation of cellulose nanofibers.
To confirm the nanofibers morphology, PALF nanofibrils pre-
pared by the steam explosion were examined by high resolution
transmission electron microscopy (HRTEM). The size, shape and the
distributions were quantified from the TEM data (Fig. 3e). Cellulose
fibers tend to agglomerate and to form network due to hydrogen
bonding interactions. It is observed that large aggregates consist-
ing of cellulose fibrils resembling a mesh like structure with an
approximate width of 30 nm exist in the system. The size was esti-
mated using imagej software. The TEM images very clearly show
tendency of strong network formation of long nano fibers leading
to an entanglement network structure in which polymer chains are
immobilized.
3.2. Nanocomposites characterization
3.2.1. Morphology: scanning electron microscopy and
crystallinity of nanocomposites
Fig. 4a shows XRD profiles of starch nanocomposites films. A
diffraction pattern of B-type structure was obtained for tuber ori-
gin like potato starch, with a peak at 5.8◦ and a peak at 17.3◦
180 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188

Fig. 3. SEM images of PALF after each treatment. (a) Raw PALF (b) steam exploded(c)after bleaching(d)FESEM images of PALF nanofibers after homogenization (e) HRTEM
image of Cellulose nanofiber.

(Teixeira et al., 2009). The plasticization process leads to a disrup-
tion of starch structure, the granular swelling and melting occurs
and the TPS crystallinity decreases in relation to the native starch.
So, when the plasticization is complete, the characteristic XRD pro-
file of native starch must change and amorphous halo cantered on
19◦ emerged, typical of semi-crystalline thermoplastic starches.
By the thermal processing of starch by high temperature and
shear force, linear amylose chain dissociates out from the granules
and gradually crystallizes into several single helical structures. TPS
are not completely amorphous since they can present two crys-
talline structures such as residual crystallinity, which occurs due
to the incomplete disruption of starch granules during casting or
even by the reorganization of starch molecular chains in their native
arrangements, mainly the short chains of amylopectin into dou-
ble helices (Montero, Rico, Rodríguez-Llamazares, Barral, & Bouza,
2017) and processing-induced crystallinity, occurs during the pro-
 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
Fig. 4. (a) XRD profile of Thermoplastic starch nanocomposites with different filler loading, and 4 (b–g) SEM images: (4b) potato starch granules (4c) TPS (4d) TPS + 1 wt.%
CNF(4e) TPS + 2 wt.% CNF (4f) TPS + 3 wt.% CNF (4 g) TPS + 4 wt.% CNF.
cessing. The crystalline structure of native potato starch granules
has vanished during the processing due to the granular melting of
starch particles by mechanical and heat treatment during process-
ing which was evident from the SEM analysis. By closely observing
the XRD pattern, we can see that a peak is gradually evolved at
16.80 which is denoted by a line. This characterizes the branched
amylopectin recrystallization (B- type crystallization). This phe-
nomenon is due to the process called retrogradation of the samples
upon storage as well as recrystallization induced by lipids and other
complex forming agents like glycerol that favours the retrograda-
tion of branched amylopectin chains. Characteristic peak for the
cellulose is not so prominent in the diffractogram which is due to
the amorphous nature of thermoplastic starch and similar func-
tionality of starch and cellulose. Magnitude of peak at 2␪ = 27.80
increases upon increase in nanofibers content probably due to the
recrystallization of amylopectin chain (dotted line shown in Fig. 4a).
This diffraction peak is not because of neat TPS or CNF, and it can
be most probably from amylopectin. Because CNFs are well defined
objects, in which crystallinity should not be changed when it dis-
persed in the matrix and this specific crystallinity occurs, or at least
is detectable, only in the presence of high CNF content. It is most
probably ascribed to an interfacial effect. This interfacial crystal-
lization seems to be favoured when the starch matrix plasticized
with the glycerol (Angellier, Molina-Boisseau, Dole, & Dufresne,
2006; Dufresne, 2000; Zainuddin, Ahmad, Kargarzadeh, Abdullah,
& Dufresne, 2013).
To estimate the surface morphology of starch nanocomposites,
films were cryo fractured and observed through SEM. Fig. 4b shows
the SEM image of native potato starch granules. It has a spheri-
cal morphology which destroys after processing into thermoplastic
181
starch. Figs. 4(c–g) show SEM picture of nanocomposites with 0, 1,
2, 3, 4 wt.% CNF. Fig. 4c shows the fractured surface of TPS, a smooth
surface without any deformation, which confirms effective blend-
ing of plasticizer glycerol with starch matrix. By incorporation of
nanofibers to the thermoplastic starch matrix the surface becomes
uneven and more structured. The cellulosic nanofibers emerge as
embedded in the thermoplastic starch matrix in Fig. 4(d–g) seem
to be uniformly distributed.
From the SEM micrographs, it is seen that the cellulose
nanofibers homogenously dispersed in starch matrix. Due to sim-
ilar polysaccharide structure a homogenous morphology could be
seen where cellulose is bound to starch matrix as seen in SEM
micrographs.
3.2.2. Viscoelastic properties, polymer chain dynamics and
evaluation of constrained region
Dynamic Mechanical Analysis (DMA) used to follow the relax-
ation of polymer chains. The effect of temperature on the
viscoelastic properties of starch CNF nanocomposites was studied
using DMA analysis. Evaluation of storage modulus, loss modulus
and tan ␦ is a useful tool to study the molecular chain dynamics
of polymer nanocomposites. Generally, an increase in nanofiller
reinforcement results in the enhancement of storage modulus as
there is a decrease chain mobility of the polymer chains leading to
a decrease in the intensity of the tan ␦ peak.
In the present study, glycerol used as the plasticizer in the
nanocomposites. The significance of glycerol on the viscoelastic
characteristics of starch composites was earlier studied by Garcia
et al. (Garcia, Ribba, Dufresne, Aranguren, & Goyanes, 2009) who
reported starch glycerol system as a heterogeneous system con-
182 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
Table 1
DMA data (Effectiveness of dispersion, Degree of entanglement and reinforcing effi-
ciency) of TPS and different wt.% of CNF-TPS nanocomposites.
Wt.% of filler Effectiveness of Degree of Reinforcing
Dispersion Entanglement Efficiency
(Ef .) (␸) (r)
1 0.693 0.131 30.95
2 0.580 0.151 35.73
3 0.265 0.237 47.01
4 0.357 0.242 36.62
sisting of two phases: one rich in glycerol and other rich in starch
phase. In the proposed microstructure, the domains of glycerol rich
phase are dispersed in a continuous starch rich phase especially
amylopectin chains. Accordingly, two relaxations were observed
in tan ␦vs temperature plots which were denoted as ␣1 and ␣ 2 .
Storage modulus is allied to the amount of energy stored for each
cycle and is directly proportional to the amount of reinforcing filler
since the reinforcing material creates a restriction to the mobility
of the polymer chains and there by increases the storage modulus
values. The value of storage modulus of neat TPS matrix is very
low compared to reinforced samples which then confirms lower
energy needed per cycle. At low temperature region (<0 ◦ C), there
is a significant change in the storage modulus with the addition of
nanocellulose, however, as the temperature approaches to higher
region the effect is not so predominant (Fig. 5a).
The increase in storage modulus with increase in nonreinforce-
ment is directly correlated to the dispersion of cellulose nanofibers
on to the thermoplastic starch matrix which was confirmed by
the SEM analysis and transportation experiments. The SEM image
reveals an enhanced dispersion of CNF in the thermoplastic starch
matrix in which CNF is covered with thermoplastic starch. As
explained earlier, the network of nano cellulose immobilizes poly-
mer chains giving rise to a high degree of modulus. Additionally,
the diffusion and transport analysis also indicated a similar trend
and this will be discussed in the coming section.
3.2.2.1. Effectiveness of dispersion Ef . Using the storage modulus
values, we can predict different parameters like effective dis-
persion, degree of entanglement and reinforcing efficiency. The
effectiveness of CNF addition on to the starch matrix can be esti-
mated using the following equation.
E1 g/E1 r Nanocomposites
Ef =
E1 g/E1 r Matrix
Where Ef . indicates the effectiveness of the dispersion, Eg and Er are
storage modulus at glassy and rubbery regions of the nanocom-
posite and the neat starch which were taken at −90 ◦ C and 0 ◦ C
respectively.
The factor Ef is a relative measure of decrease in storage modu-
lus of nanocomposite with increase in temperature. The lower the
value of Ef , the higher will be the effectiveness of filler dispersion in
polymer matrix. Values of Ef Vs filler loading were given in Table 1.
The decrease in Ef value with increase in CNF loading is due to
the effective dispersion of CNF on to the starch matrix. However,
nanocomposite with higher wt.% of CNF shows slight increase in Ef
value (but lower than neat matrix) which may due to the agglom-
eration of nanocellulose at higher filler loading (Pothan, Oommen,
& Thomas, 2003).
3.2.2.2. Degree of entanglement␸. The entangled nanofiber net-
work can immobilize the starch polymer chains giving rise to high
degree of reinforcement. So, degree of entanglement of CNF over
the thermoplastic starch matrix is important to understand the fine
dispersion of fillers over the surface of thermoplastic starch. The
degree of entanglement was estimated using the following equa-
tion (Oommen, Groeninckx, & Thomas, 2000).
 = E1 /6RT (3)
Where E1 is the storage modulus at rubbery region (0 ◦ C), R is uni-
versal gas constant and T is temperature at Kelvin scale
The degree of entanglement with increase in filler loading is
shown in Table 1. We can find that degree of entanglement becomes
more effective with increase in the filler loading.
3.2.2.3. Reinforcing efficiency (r). The reinforcing ability of cellulose
nanofibers on thermoplastic starch matrix can be obtained using
well known Einstein equation. (Einstein, 1956)
Ec = Em (1 + rVf ) (4)
Where, Ec and Em are storage modulus of composites and matrix
at rubbery region which here taken as 0 ◦ C. Vf is the volume frac-
tion of filler (obtained by density equation) and r is the reinforcing
efficiency of filler to the matrix. From the above equation
r = [(Ec/Em) − 1]/Vf (5)
Reinforcing efficiency of CNF on thermoplastic starch matrix are
given in the Table 1. From the values, it is obvious that the reinforce-
ment efficiency increases with increase in filler content upto 3 wt.%
CNF after that reinforcing efficiency found to be decreased due to a
tendency to get agglomeration at higher filler loading.
By carefully analyzing Table 1, one can deduce the following
conclusions: (1). The effectiveness of filler dispersion is maximum
at 3 wt.% of nano cellulose loading followed by decrease because
of nanocellulose agglomeration. (2.) Interestingly, the degree of
entanglement as shown by the data in Table 1 clearly indicates that
the values level off at 4 wt.% of nano cellulose where agglomeration
starts. (3.) The reinforcing reaches a maximum value at 3 wt.% of
nano cellulose followed by a decrease at 4 wt.% of loading. Degree of
entanglement increases almost double when the nanofiber content
increases from 2 wt.% to 3 wt.% which accounts for the better dis-
persion of nanofiller into matrix phase (lower Ef value) and because
of strong network formation of cellulose nanofibers by hydrogen
bonding interaction. In summary, all the three parameters such
as Effectiveness of Dispersion (Ef .), Degree of Entanglement, (␸)
and Reinforcing Efficiency (r) very well substantiate the fact that
beyond 3 wt.% of loading nano cellulose, strong aggregation takes
place and the degree of reinforcement is maximum at 3 wt.% load-
(2)
ing.
As discussed earlier, starch –glycerol is partially miscible sys-
tem i.e., heterogeneities exist in the system as reported by several
authors, (Müller, Yamashita, & Laurindo, 2008; Teixeira et al., 2009).
This could be understood from the two different relaxations, ␣ 1 and
␣ 2 (-50 ◦ Cand 12.5 ◦ C) as seen from the tan delta –temperature plot
given in Fig. 5b. The two relaxations are associated with a starch
rich phase, which shows a high temperature relaxation (12.5 ◦ C, ␣
◦
2 ) and glycerol rich phase (–50 C, ␣ 1 ) as show in Fig. 5b. In fact, ␣2
is associated with the relaxation of the amylopectin chains of the
starch. Up on the addition of nano cellulose into the system, nano
cellulose localizes predominantly at the glycerol rich starch phase
and at the interface between glycerol rich starch phase and glyc-
erol lean starch phase on account of the proximity of large hydroxyl
groups in the glycerol rich starch phase. However, a small fraction
of nano cellulose localizes at the glycerol lean starch phase too. The
interaction between the nanocellulose and starch/glycerol chains at
the interface leads to the immobilization of the glycerol rich phase
leading to a constrained region in the glycerol rich phase. The for-
mation of the constrained region is responsible for the dramatic
decrease in the tan delta peak height of the glycerol rich phase. The
amount of constrained region has been quantified from the height
 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188 183

Fig. 5. DMA data of starch cellulose system (a) variation of storage modulus with temperature of pure TPS and different wt.% of TPS with CNF loading at the frequency of
1 Hz. (b) Variation of tan delta with temperature of pure TPS and different wt.% of CNF TPS nanocomposites at frequency of 1 Hz. (c) Schematic representation of formation
of constrained region around starch polymer due to nanofiber reinforcement (d) Cole–Cole plots for Pure TPS and different wt.% of CNF-TPS nanocomposites.

of Tan ␦ peak peak height which has been discussed below. One For linear viscoelastic region
can notice another very interesting phenomenon in Fig. 5b, where
W = ␲tan␦/(␲tan␦ + 1) (6)
the relaxation of the glycerol rich starch phase progressively shifts
towards low temperature region as you increase the amount of Where, W = Energy loss factor and
nano cellulose up to 3 wt.%. This could be explained as follows: The tan ␦ = Dissipation factor
well dispersed nano cellulose chains are able to make specific inter- For Dynamic viscoelastic region,
action with glycerol chains as a result the amount of glycerol in the
glycerol lean starch phase progressively migrates to the glycerol W = [(1 − C)W0 ]/(1 − C0 ) (7)
rich starch phase as we increase the nano cellulose content. The Where, C = Volume of constrained region
progressive migration of the glycerol is responsible for the very W0 and C0 are energy loss factor and volume fraction of con-
regular and progressive decrease of Tg of the glycerol rich starch strained region
phase. The Tg shifts from −53.61 ◦ C to −59.73 ◦ C as the cellulose Finally, constrained volume has been calculated by rearranging
content is increased from 1 to 3. However, at 4 wt.% loading, this the equation
does not take place since the cellulose chains form aggregates. This
is explained in a cartoon shown in Fig. 5c. C = 1 − [(1 − C0 )W/W0 ] (8)

We have estimated the volume of the constrained region in

3.2.2.4. Estimation of constrained region (C). To estimate the con-
strained region and assess the interaction of cellulose nanofibers
with matrix, the decrease in peak height in the tan delta plot
(Fig. 5b) has been made use of.
both phases, glycerol rich phase and starch rich phase, since some
small amount of nano cellulose is dispersed in the starch phase
(Table 2). The volume of constrained region in both phases is found
to be increased with the increase in the nano filler content which
is a direct implication of formation of strong interaction between
the filler and polymer creating a constrained region around the
184 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188

Table 2
Variation of DMA parameters of two phases: Glycerol rich starch phase as well as Glycerol poor starch phase.

Sample Glycerol rich starch phase (␣1 ) Glycerol lean starch phase (␣2 )

Constrained Volume Adhesion factor CNF-TPS Constrained Volume Adhesion factor CNF-TPS
A interface A interface
adhesion adhesion
(␤) (␤)

TPS 0 0 0 0 0 0
TPS + 1 wt.% CNF 0.029 −0.064 5.59 0.0045 −0.0173 0.7785
TPS + 2 wt.% CNF 0.094 −0.184 8.61 0.0213 −0.0165 1.8874
TPS + 3 wt.% CNF 0.147 −0.272 8.63 0.1079 −0.1946 5.8812
TPS + 4 wt.% CNF 0.163 −0.302 7.15 0.2112 −0.3392 8.1467

filler surface restricting polymer mobility as shown in the cartoon
(Fig. 5c).
3.2.2.5. Adhesion factor (A). The adhesion factor (A) between the
polymer matrix and reinforcing filler was calculated from Dynamic
Mechanical Analysis where loss factor of composites expressed in
volume fraction and damping factor of filler which is expressed by
the formula suggested by Wei et al. (Wei, 2006)
3.2.2.6. CNF-TPS interface adhesion (ˇ). As said earlier, CNF tended
to locate glycerol rich starch phase as well as to the interphase
between two phases, glycerol rich starch phase and glycerol lean
starch phase. So, a measure of interface adhesion is important for
the evaluation of the interaction of CNF on to the starch/glycerol
matrix. DMA is based upon a fact that energy dissipation is not only
due to the matrix alone but also on the matrix/filler interaction and
interface.

(Tanıcomposites/tanımatrix) = 1 − ˇVf (13)

Tan␦composite = Vfiller tan␦filler + Vinterface tan␦interface
+ Vmatrix tan␦matrix
Where, Tan ␦ (composites,filler,interface,matrix) are the damping fac-
tor of composites, filler interface and matrix respectively. V
(filler,interface,matrix) are the volume fraction of filler, interface and
matrix respectively.
Due to rigidity, the damping factor of filler considered to be very
low and volume fraction of interface is even very low, compared to
filler and matrix counterparts, (Vfiller tan ␦ filler = 0) therefore both
these contributions could be neglected. So, Tan ␦ composite = V interface
tan ␦ interface + V matrix tan ␦ matrix
We all know that
(Vfiller + Vmatrix = 1)
then equation becomes:
tan ı composite
= (1 − Vf )(1 + A)
tan ı matrix
The adhesion factor, ‘A’, can be expressed in terms of the relative
damping of the composite and the polymer and the volume fraction
of the filler at a given temperature.
The equation can be rearranged by considering the ration of
damping factor of composite to that of neat matrix without rein-
forcing filler and the volume fraction of fillers.
A = 1/(1 − Vf )[tanıcomposite /tanımatrix ] − 1
At high concentration of nanofibers reinforcement, there will
be reduction in tan delta values followed by a decrease in Adhe-
sion factor A. Lower the value of A greater the interaction between
filler and matrix. The negative value of Adhesion factor is due to
the filler anisotropy as well as well as development of interface
region of composite. Table 2 represents the Adhesion factor and
constrained volume of two relaxation regions obtained from tan
delta graph. From the table, it is evident that the value of A decreases
with increase in nonreinforcement which is due effective reinforce-
ment of filler on to the matrix. There is an increment in the adhesion
factor, from 2 to 3 wt% of CNF in the glycerol lean phase, probably
due to the fine dispersion of CNF over the starch matrix, (as evi-
dent from the other parameters). But the value is still higher than
corresponding glycerol rich phase suggests the tendency of CNFs
towards the glycerol rich starch phase.
Where, Tan ␦ composites and tan ␦ matrix are the damping factor
(9) of composites and matrix respectively, Vf is the volume fraction of
filler and ␤ is a parameter of correct volume fraction of filler after
the formation of immobilized interface layer due to matrix/filler
interaction.
From the above equation, we can estimate the value of ␤ as:
␤ = [1 − (Tanıcomposites/tanımatrix)]/Vf (14)
3.2.2.7. Cole–Cole analysis. Cole–Cole analysis is important to find
out the structure/property changes by the addition of nanosized
fillers to the polymer matrix. The Cole–Cole method is a dielec-
tric relaxation data, obtained by plotting storage modulus against
loss modulus, where each point corresponds to 1 Hz frequency.
(10) The dynamic mechanical properties examined as function of tem-
perature and frequency represented on the Cole–Cole complex
plane. Structural and dynamic changes of polymeric system after
the addition of fillers were studied by Cole–Cole method. Usually
(11) homogenous polymeric system exhibits a semicircle while a het-
erogeneous system like starch exhibit distorted semicircle (Idicula,
Malhotra, Joseph, & Thomas, 2005; Jyoti, Singh, Arya, & Dhakate,
2016). The Cole–Cole plot of composites containing varying filler
concentration is shown in Fig. 5d.
3.2.3. Transport properties
Films with lower air permeability and transport property are
best suited for packaging applications. Transport of solvent through
(12)
polymeric membranes depends on several factors like matrix free
volume, dispersion of fillers, cross link density, nature of matrix and
reinforcing fillers, matrix and filler interaction etc. (Lomelí-Ramírez
et al., 2014).
Since starch and cellulose have similar polysaccharide structure
the reinforcing filler CNF tries to occupy into the starch matrix and
decreases the free volume and thereby decreases the diffusion of
solvent through the system. Diffusion of water through nanocom-
posite films with different CNF concentration was determined.
Mole% uptake of water through nanocomposite film determined
using the formula
 
Mass of solvent absorbed/Molar mass of solvent
Qt mol% = × 100
Mass of polymer
(15)
 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
Fig. 6. Transport properties of starch cellulose nanofiber composite films (a) Sorption curves of water through potato starch-CNF nanocomposites at different CNF loading
(b) Variation in Diffusivity & Permittivity of composites with different CNF loadings (c) Model fitting curve of thermoplastic starch nanocomposites.
A graph was plotted with mole percentage uptake (%Qt ) for
√
the solvent against the square root of time ( t). Fig. 6a shows
the sorption curves of water in glycerol plasticized potato starch-
CNF nanocomposites by varying the CNF content. It is found that
the absorption of solvent water increases considerably in the first
because of higher hygroscopic character of starch and cellulose and
later the rate of uptake decreases and gradually level off reaching
saturation. This is probably because of the decrease in concentra-
tion gradient of the penetrant, water. By the DMA analysis it was
clear that there is a formation of constrained region among the
polymer chains that restricts the segmental mobility of polymer
chains due to strong matrix filler interaction which lead to less
flexibility and thereby low sorption behaviour. Since CNF creates
a circuitous path for the diffusion of water molecules, after succes-
sive addition of CNF, the equilibrium uptake decreases. At 1 wt.%
CNF, the amount of CNF is unable to form a far-reaching network
structure and hence we can see the sorption curve of TPS reinforced
with 1 wt% CNF shows same absorption that of unreinforced one.
Transport mechanism of solvent through polymeric system can
be analysed by fitting dynamic swelling data in the equation
logQt/Q ∞ = logk + nlogt
where, Qt is the mole percent solvent uptake upon each time inter-
vals and k is a constant which is depends upon the solvent/matrix
interaction and value n gives an idea of the sorption mechanism.
The values of n and k are obtained from linear portion of plots
Qt versus the square root of time. The value of n depends on the
nanocomposites characteristics which are to be considered. If the
185
rate of diffusion of water or any solvent is lower than that of poly-
mer chain relaxation, the value of n will be equal to 0.5. In case, the
rate of relaxation of polymer chain is lower than diffusion of sol-
vent molecules through the system, the value will be 1 and called
non-Fickian mode of transport, while the value comes between
0.5–1 indicated anomalous behaviour. When the solvent penetra-
tion is much below the polymer chain relaxation, it is possible to
record the n values below 0.5. This situation is named ‘Less Fickian
or pseudofickian (Abraham, Maria, George, Kalarikkal, & Thomas,
2015).
For this system, value of n comes around 0.4 which suggest a
deviation from normal Fickian mode and hence can be classified as
Less fickian or pseudo fickian. K value gives an idea regarding the
solvent/matrix interaction.
The diffusion coefficient (D) which indicates the rate of solvent
diffusion into the system which can be correlated with the polymer
chain segmental motion. The diffusion coefficient can be calculated
using the formula of Fickian law (Schurtenberger, 1996).
The diffusivity of solvent i.e., water is strongly influenced by the
microstructure of the matrix as well as reinforcing phase, such as
the pores that may form during the drying process.
(16)
 2
h
D= (17)
4Q∞
Where
h = Thickness of sample
y = slope of linear portion of sorption curve
186 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188

Table 3
Transport parameters of starch-CNF nanocomposites.

Sample Diffusion Sorption Coefficient permeability Swelling Coefficient Swelling Index

Coefficient coefficient (%)
(*105 cm−1 S−1 ) (*105 cm−1 S−1 )

TPS 5.36 5.36 9.64 0.94 94.05

TPS + 1wt%CNF 4.74 3.99 7.74 0.74 74.05
TPS + 2wt%CNF 3.99 2.77 4.75 0.71 71.58
TPS + 3wt%CNF 2.77 0.33 0.52 0.59 59.41
TPS + 4wt%CNF 2.71 0.07 0.09 0.26 26.09

At high level of reinforcement, the diffusion coefficient tends to
decrease because of drop of matrix free volume by the addition of
nonreinforcements. At the higher concentration of CNF loading it
shows a sort of aggregation.
Permittivity and diffusivity of the composites lowers with suc-
cessive nanofiber concentration which is due to the formation of a
web like structure between starch and cellulose nanofibers. But at
the higher concentration of nanofiber the values level off or increase
which may due to the formation of aggregates of nanofibers.
Sorption coefficient of nanocomposites is calculated using the
equation shown below.
Where, M∞ is the initial weight and M0 is the final weight of
sample.
M∞
S=
M0
The permeability coefficient (P) of a composite gives an
overview of permeability of the composite towards the solvent and
can be obtained by equation
P = DXS
Where, D = Diffusion Coefficient
S = Sorption Coefficient
The difference in D and P for the successive CNF loadings in water
at room temperature is shown below. From Fig. 6b, it was clear that
TPS reinforced with 3 wt.% CNF samples show minimum diffusivity
and permeability in water, whereas both are maximum for the neat
sample. The inside image shows the restriction of water molecules
in the CNF reinforced thermoplastic starch matrix that causes the
minimal diffusivity and permittivity of composites with 3 wt.% of
cellulose nanofiber. At higher filler loading D and P tends to level
off which accounts for the formation of aggregated of nanofibers.
3.2.3.1. Swelling coefficient. The swelling coefficient is an indicator
of the capacity with which the samples swell in the solvent here in
water.
 
(W2 − W1)
Swelling coefficient =
W1
Where,
W1 = Dry weight of sample
W2 = Swollen weight of sample
 
(W2 − W1)
Swelling Index = × 100
W1
By looking to Table 3, we can see that both the swelling
coefficient and swelling index were found to be declining with suc-
cessive filler reinforcement; because, nonreinforcement creates an
obstruction in the path of solvent molecule through starch matrix
and therefore, nanocomposite swelling was reduced in the pres-
ence of fillers within the plasticized starch system.
The decreased water sensitivity of cellulose filled starch
nanocomposites happens, at least partially, from another phe-
nomenon which include a restriction in the chains mobility, an
improvement in the crystallinity and also due to effect of plasticiza-
tion effect of glycerol which was evident from the DMA analysis.
3.2.3.2. Mathematical modelling. Mathematical diffusion mod-
elling employed to analyse the diffusion characteristics of
penetrant molecules through polymeric system by comparing
experimental results and theoretical models. In this study, we pro-
pose two models to study the mode of transport and diffusion
phenomena. These models depend on the migration of solvent
molecules from initial point to the other end of the sample. To fit
the models with the experimental data, composites with 3 wt.% CNF
were fitted with two models (Peppas sahlin and Korsmeyar pep-
pas). The composition is chosen since these composite shows the
best results. Fig. 6c shows the model fit curve with experimental
data which is indicated with dotted line. As per the graph shows
the data is best fit with Kormeyar peppas model.
3.2.3.2.1. Peppas–Sahlin model. According to this model, poly-
(18) mer matrixes contain two types of processes, diffusion of polymer
and matrix relaxation (Peppas & Sahlin, 1989).
Mt
= kf t m + kr t 2m (22)
M∞
Where, Mt and M∞ are the fraction of solvent released at time t, kf
(19) and kr are fickian contribution coefficient and relaxation coefficient
contribution respectively.
3.2.3.2.2. Korsmeyer–Peppas model. Korsmeyar −Peppas
model based on the fact that, the fractional diffusion and diffusion
time are exponently related (Eq. (23)) (Korsmeyer, Gurny, Doelker,
Buri, & Peppas, 1983). In the equation, Mt and M␣ are the fraction
of solvent released at time t, n and k are constant which diffusion
rate are and characteristics value of polymer solvent interaction.
Mt
= kt n (23)
M∞
To evaluate the diffusion mechanism, one of the data was plot-
ted and mathematically fitted with two principles that mentioned
above and observed that, data fitted well with Korsmeyer–Peppas
model than peppas-sahlin model with an R value 0.9789. Thus,
the diffusion of polymer chains were exponentially related to the
diffusion time.
(20)
4. Conclusions
Starch-based nanocomposites reinforced with 1–4 wt% PALF
nanofibers were prepared by solution casting process. The mor-
phological and structural analysis confirmed the formation of
(21) nanofibers from Pineapple leaf. Dynamic Mechanical Analysis
of prepared composites was analysed thoroughly and from the
inference we conclude there is better interaction of CNF on to
the thermoplastic starch matrix. Evaluation of constrained region
shows that CNF had a tendency towards glycerol rich starch phase
since the composite exhibit two relaxation phenomena as evident
by tan delta curve. Modelling by Cole Cole plot shows an imperfect
semicircle that further confirms the formation of heterogeneous
system. Diffusion kinetics shows the pseudofickian behaviour of
composites, Diffusion coefficient and permittivity decreases with
successive CNF reinforcement which is probably because of the
formation of a network structure that created a convoluted path
to a solvent molecule (water) to diffuse into the starch matrix and
 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
the composites follow Korsmeyar Peppas model. Nanocomposites
reinforced with 3 wt.% of CNF shows better dispersion in all cases
with low diffusivity and permittivity, high reinforcing efficiency,
low Ef and high entanglement of nanofibers.
Acknowledgements
The authors are grateful to Department of Science and Technol-
ogy (DST) for awarding INSPIRE fellowship to Preetha Balakrishnan,
Financial support under DST-FIST New Delhi to Sree Sankara Col-
lege Kalady and DST Nanomission for instrumental facilities to
Centre.
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