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Carbohydrate Polymers
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a r t i c l e i n f o a b s t r a c t
Article history: 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 Amylose and highly branched amylopectin are two important con-
stituents of starch. The content of amylose and amylopectin are one
Green nanocomposites attain much attention today due to their factor which affects the final performance of starch based polymers.
versatile applications. One of the key threat that our world faces Despite of its great advantages like biodegradability, low cost and
nowadays is problems due to plastic wastes and scientists all over ease to chemical reactions it also faces many draw backs due to
the world constantly work on developing green composites as a its hygroscopic nature, poor mechanical, thermal and barrier prop-
substitute for synthetic plastics while conserving biodegradability. erties, (Karimi, Dufresne, Md. Tahir, Karimi, & Abdulkhani, 2014).
(Dean & Yu, 2005). Starch exists in a crystalline nature, so it plasticized to improve
The awareness of global issues due to plastic wastes increased the final properties and flexibility. Many plasticizers have been
the importance of starch based thermoplastics which are fully used for plasticizing starch like citric acid (Priya, Gupta, Pathania, &
biodegradable and green in nature (Wang, Cai, Yu, & Xia, Singha, 2014), sorbitol (Arun, Kumar, & Sreekala, 2012), glycerol etc.
2009).Some of the important applications of starch polymer include (Bootklad & Kaewtatip, 2013; Versino & García, 2014). To advance
production of paper and board, textiles and adhesives. Linear 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-
∗ Corresponding author at: International and Inter University Centre for
lactic acid (Ke & Sun, 2003) and reinforcing with naturally available
Nanoscienece and Nanotechnology, PD Hills P.O, Mahatma Gandhi University, Kot-
tayam, Kerala, 686560, India.
macro to nano fillers have been extensively reported.
E-mail addresses: sabuchathukulam@yahoo.co.uk, sabuthomas@mgu.ac.in,
sabupolymer@yahoo.com (S. Thomas).
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) 176–188 177
Cellulose is one of the naturally available polymers which the leaf. For the fabrication of thermoplastic starch (TPS), potato
consist of repeating units of ˇ – Dglucopyranosegroup. It is semi starch (supplied by Lobha chem India Pvt. Ltd. Mumbai) and glyc-
crystalline in nature with crystalline part and amorphous part erol (98% Purity chemical formula (HOCH2 )2 CHOH supplied by
like lignin, pectin, hemicellulose etc. Apart from nanocrystals and Merck India Pvt. Ltd) were used. For nanofiber synthesis sodium
whiskers nanofibers contain both crystalline and amorphous region hydroxide, oxalic acid, hydrogen peroxide was supplied by (MERCK
and high aspect ratio (L/D)which provide an extensive network India Pvt. Ltd).
of nanofibers which result in superior properties (Dhar, Bhardwaj,
Kumar, & Katiyar, 2014). 2.1.2. Isolation of cellulose nanofibrils from pineapple leaf (PALF)
One of the major advantages of reinforcing cellulose material Procedure for the isolation of cellulose nanofiber were adapted
in starch matrix is the presence of similar polysaccharide structure from previously reported work (Cherian et al., 2011). Firstly, PALF
which could benefit better matrix/filler interaction. Several stud- fibers were dried and chopped into small pieces. The finely chopped
ies have been reported the effect of cellulose as a reinforcing filler fibers were alkali treated using 2% NaOH solution in an autoclave
in the starch matrix; these include work on jute (Das et al., 2011), under a pressure of 138 kPa for almost 1 h. After that, the pressure
hemp (Gironès et al., 2012), sisal (Gironès et al., 2012), oil palm fiber released instantly and the alkali treated fibers were then soaked
(Salehudin, Salleh, Mamat, & Muhamad, 2014), cotton (Savadekar with distilled water several times until it relieved of any alkali con-
& Mhaske, 2012), bamboo (Liu, Zhong, Chang, Li, & Wu, 2010), dates tent. The steam exploded fiber then bleached using a mixture of
palm fiber (Ibrahim, Farag, Megahed, & Mehanny, 2014). Yang et al. equal parts of NaOH/glacial acetic acid (27 g/L and 78.5 g/L respec-
scrutinized the effect of nanocellulose reinforced starch as a sur- tively) and hydrogen peroxide. The bleaching was done for 30 min
face sizing agent for cellulosic paper and found that there was an and repeatedly six times until the colour of fibers completely turns
enhancement in the tear strength and printing quality of the paper to white colour. It was then soaked and washed with distilled water
(Yang, Tang, Wang, Kong, & Zhang, 2014). several times and dried in an air circulating oven for 10 h. The fibers
Plasticizer glycerol is an extremely small organic molecule with were then subjected to mild acid hydrolysis using 11% H2 C2 O4 in an
three hydroxyl functionalities. it can enter into the starch molecules auto clave set at 138 kPa for 15 min, centrifuged and homogenized
and thereby reduce the intermolecular interaction between starch
molecules leading to an increase in the flexibility. Pineapple leaf
2.1.3. Preparation of thermoplastic potato starch (TPS)/cellulose
considered as a waste material after the harvesting of pineapples.
nanofiber (CNF) composites
It consist of 80% cellulose, which is being wasted in the normal case
Thermoplastic starch composites were prepared by solvent cast-
after harvesting (Faruk, Bledzki, Fink, & Sain, 2012). So, utilization
ing technique. Calculated weight percentage (on dry starch basis)
of waste material into an eco-friendly biodegradable composite for
of cellulose nanofibers were dispersed in distilled water and bath
packaging application is one way to reduce the problems due to
sonicated for almost 30 min. Pre-weighed potato starch was mixed
synthetic plastic materials. So, the endeavour of this work is to
well with 30% glycerol (on dry starch basis) using mechanical stir-
make use of pineapple waste fibers as potential nano scale rein-
rer by adding 100 ml distilled water. The suspension of cellulose
forcement on a green agro based polymer matrix, starch which
nanofiber was added to starch-glycerol water mixture and mixed
was extracted from the potato plantation waste. Potato starch rein-
in a mechanical stirrer (700 rpm) for 30 min at a temperature of
forced with cellulose nanofiber has been reported earlier by Moran
90 ◦ C. After the solution became viscous, it was poured on to lev-
et al. (Morán, Vázquez, & Cyras, 2013), in which starch derivatives
elled Borosil glass Petri dishes and kept at 50 ◦ C for 12 h until
were used as a matrix for biocomposite. Although there are many
it completely dry. Solution cast films of TPS cellulose nanofiber
studies on the nanofibers from various resources on thermoplas-
composites were made at 1,2,3,4 wt.% nanofiber concentrations (as
tic starch, systematic and in-depth literature survey indicates that
per dry weight of matrix). The films of thickness approximately
there are no systematic investigations on nano scale pineapple leaf
80 m were obtained by this technique. Schematic representation
fiber reinforced potato starch nanocomposites. It is important to
of preparation of nanocomposite shown in Fig. 1.
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 2.2. Characterization techniques of cellulose nanofibers and
potential reinforcement for polymers. The matrix we have chosen nanocomposites
is thermoplastic starch derived from agro-waste potato, which is a
major waste after extracting food grade potato starch. Very specif- 2.2.1. Fourier transform infrared spectroscopy (FTIR-ATR)
ically, we have extracted nano cellulose from pineapple leaf fiber FTIR spectra recorded using a Shimadzu IR-470 IR spectrometer.
by a standard protocol of acid washing as reported in literature. Raw fibers and final product (acid treated fiber) were dried in an
Nanocomposites of starch/nanoscale pineapple fibers have been air circulating oven at 50 ◦ C. The spectrum of each sample analysed
fabricated by solution casting technique. Morphology, viscoelas- at a range of 400–4500 cm−1 with a resolution of 2 cm−1 . Total of 4
tic properties and transport behaviour have been carefully studied. scans per each sample were taken.
Morphology-property correlation has been established. Finally, the
amount of starch macromolecular chains confined at the nanoscale 2.2.2. X-ray diffraction (XRD)
cellulose surface has been carefully estimated and this has been Crystallinity of fibers and composites are determined by XRD
correlated with interfacial, transport properties. 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
2. Materials and methods were recorded over scattering 2angles from 5 to 55◦ (step
size = 0.02◦ , scanning rate = 2 s/step) using a Ni-filtered Cu K radi-
2.1. Experimental ation ( = 1.5406 Å) an operating voltage of 45 kV, and a filament
current of 40 mA.
2.1.1. Materials The crystallinity of fiber samples was determined by following
Post harvested pineapple leaves were collected from neighbour- empirical Segals equation (Segal, Creely, Martin, & Conrad, 1959).
ing fields around Kottayam District Kerala, India. The leaves were Crystallinity index (CrI) of each sample were calculated by refer-
washed thoroughly to remove dust and other impurities stick into ring to diffraction intensity of crystalline (I200 ) and amorphous
178 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
regions (Iam ). Where I200 represents both crystalline and amor- grid and coated with a carbon film. Before image the grid was dried
phous regions of the material whereas Iam represents only the in sodium vapor lamp for 4 h.
amorphous regions.
2.2.5. Dynamic mechanical analysis
I200 − Iam
CrI = × 100 (1) Dynamic mechanical analysis was performed on TA Q800 ther-
I200
mal analyser (Q800 DMA, TA Instruments, New Castle, Delaware,
United States) using a thin film clamp. The viscoelastic proper-
2.2.3. Scanning electron microscopy of nanofibers and ties were measured at a frequency of 1 Hz, strain amplitude of 5
nanocomposites micrometres in a temperature range −120 ◦ C to 70 ◦ C. The heating
Scanning electron microscopy (JEOL JSM-820 model) was used rate was 2 ◦ C/min.
to examine the surface morphology of fibers after each treatment
and fracture surface of TPS-CNF nanocomposites. The samples were 2.2.6. Transport properties
then coated with gold using a vacuum sputter coater to avoid char- The kinetics of water absorption of the specimens was studied
ring during SEM. The accelerating voltage was 15 kV. To understand using circular specimens of 2 cm diameter which were prepared
the fracture behaviour specimens were first frozen in liquid nitro- by cutting the samples using circular sharp edged die. Thickness of
gen and then immediately fractured. the samples were measured using a screw gauge at several points.
The microtopographies of acid treated CNF samples were These specimens were weighed and dipped in 30 ml of distilled
observed by FESEM. The FESEM micrographs were taken on a Zeiss water kept in diffusion bottles. Samples were weighed after regu-
Supra 35 VP. For the FESEM, about 30 mg of the well sonicated lar intervals and the surface of specimens were wiped with tissue
samples were dispersed in 50 ml of acetone. (Ultrasonic Processor paper to remove adhering solvents. The process was continued until
UP400S, Hielscher). The suspension was applied to a glass substrate equilibrium swelling attained.
from which the acetone quickly evaporated. The dried glass support
with its CNF particles on the surface was then coated with gold and
3. Results and discussions
used for FESEM observations.
3.1. Cellulose nanofiber characterizations
2.2.4. High-resolution transmission electron microscopy (HR
TEM) The FTIR spectra of raw pineapple leaf and nanofibers are
The morphology of the nanofibrils were analysed by TEM shown in Fig. 2a. The two spectra have a characteristic band at
(JEM-2100HRTEM). The nanofiber suspension was subjected to 3300 cm−1 due to the hydroxyl groups. This indicates the occur-
ultrasonic treatment for 30 min to disperse the nanofibers. A drop rence of hydrophilic OH group in the fiber, which is a prime reason
of dilute solution was drop cast on the surface of the clean copper behind the hygroscopic nature of cellulose. The band at 2901 cm−1
P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188 179
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 and wheat straw (Kaushik, Singh, & Verma, 2010) respectively were
was absent in the spectra of untreated pineapple leaf because of the previously reported.
presence of impurities which upon chemical treatment increases its Morphological investigation of pineapple leaf after various
intensity. (Alemdar & Sain, 2008). The peak at 1062 cm−1 assigned chemical treatments is shown in Fig. 3(a–d). From the SEM images,
to the carbonyl stretching and CH stretching vibrations of cellu- it is evident that after successive chemical treatment the smooth-
lose. The newly emerged peak observed in the 1317–1320 cm−1 ness of fibers increases and fiber diameter decreases.
region corresponds to the C O groups of the aromatic ring in cel- The rough surface of untreated PALF fiber shown in Fig. 3a.
lulose (Gañán, Cruz, Garbizu, Arbelaiz, & Mondragon, 2004). The Following alkali treatment (Fig. 3b), the fiber surface becomes
intensity of the OH functionality indicates the cellulose content smoother which be a sign of the fractional elimination of hemicel-
increased by successive chemical treatment. When native cellulose lulose, lignin, pectin, wax and other impurities adhering in PALF.
from PALF converted to PALF CNF through steam explosion, bleach- Wax and pectin act as a shielding coating surrounding natural
ing and acid hydrolysis, the characteristic peak at 3300 cm−1 still fiber. Moreover, it is important to note that the fiber diameter
exist. Intensity of peak increase with chemical treatment because reduces after each treatment which shows the removal of non-
the non-cellulosic matrix of native cellulose was removed success- cellulose components. Lignin forms a connecting link bond with
fully without losing the cellulose structure and also due the purity the cellulose ester and acts as a binder in the fiber components,
of prepared nanofibers. Peak at 2890 cm−1 corresponds to the thus preserving the bundle form after alkali treatment. To eval-
asymmetric vibrations of CH2 group present in the cellulose. The uate the decrease in fiber diameter after each treatment, fiber
intensity of this peak increases with the chemical treatment corre- diameter calculated using imageJ software and found that, a sub-
sponds to cellulose structure. The peak at 1655 cm−1 is due to the stantial decrease in fiber diameter 7.80 m, 4.68 m, 0.67 m for
bending mode vibration of the absorbed water with some contri- alkali, bleached, and acid treated fiber respectively. Later, aggre-
butions from carboxylate groups (C.S., George, & Narayanankutty, gated nanofibers obtained from acid treatment defibrillated via
2016). These results indicate that the cellulose component retained high shear homogenization and used as reinforcement filler. The
during the chemical treatment carried out on PALF. effect of the subsequent mechanical treatment (steam explosion
Cellulose crystallinity is one of the important factors governing and bleaching) was clear from the assessment of micrographs in
the performance of nanocomposites. Fig. 2b shows the diffrac- Fig. 3(b and c) and observed that the PALF fiber bundles separate
togram of PALF after various chemical treatments and found that into individual fibers. Fig. 3d, FESEM image (1 m magnification) of
the crystallinity increases with the chemical treatments. Pineapple acid treated PALF fiber shows the presence of long individual fibers
leaf consists of approximately 10.5% lignin, 80.5% Hemicellulose, which confirms the formation of cellulose nanofibers.
73.4% cellulose (Costa et al., 2013). Higher crystallinity of cellulose To confirm the nanofibers morphology, PALF nanofibrils pre-
is due to the presence of strong inter and intramolecular interac- pared by the steam explosion were examined by high resolution
tion. The XRD profiles have two major peaks corresponds to 2 = 16◦ transmission electron microscopy (HRTEM). The size, shape and the
and 22.7◦ which is typically of cellulose 1 structure. The sharp peak distributions were quantified from the TEM data (Fig. 3e). Cellulose
at 22.7◦ of acid treated fiber is due to higher crystallinity of cellu- fibers tend to agglomerate and to form network due to hydrogen
lose. The crystallinity of nanofiber will increase their firmness and bonding interactions. It is observed that large aggregates consist-
stiffness, and it results in superior reinforcement in composites. ing of cellulose fibrils resembling a mesh like structure with an
The peak strength at 2 = 22.7◦ related to [002] lattice plane approximate width of 30 nm exist in the system. The size was esti-
increases after each chemical treatment which is almost similar to mated using imagej software. The TEM images very clearly show
earlier reported work of Wan et al. (Wan et al., 2009). It further rises tendency of strong network formation of long nano fibers leading
stridently with chemical treatment during isolation. From the XRD to an entanglement network structure in which polymer chains are
profiles, we can assume that the hydrolysis take place selectively to immobilized.
the amorphous regions where the crystalline region is more or less
stable to chemical attack. Crystallinity of cellulose after each treat-
3.2. Nanocomposites characterization
ment calculated by Segals equation which shows the crystallinity
increases from 42.01% for untreated fibers to 67.03% for chemically
3.2.1. Morphology: scanning electron microscopy and
treated fibers and to 75.38% for cellulose nanofibrils, which can
crystallinity of nanocomposites
be compared to formerly reported data for nanofibers from vari-
Fig. 4a shows XRD profiles of starch nanocomposites films. A
ous origin. The crystallinity of 54.10%, 69.34%, 79.87% for cassava
diffraction pattern of B-type structure was obtained for tuber ori-
bagasse (Versino & García, 2014), wood fibers (Chen et al., 2011)
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- and gradually crystallizes into several single helical structures. TPS
tion of starch structure, the granular swelling and melting occurs are not completely amorphous since they can present two crys-
and the TPS crystallinity decreases in relation to the native starch. talline structures such as residual crystallinity, which occurs due
So, when the plasticization is complete, the characteristic XRD pro- to the incomplete disruption of starch granules during casting or
file of native starch must change and amorphous halo cantered on even by the reorganization of starch molecular chains in their native
19◦ emerged, typical of semi-crystalline thermoplastic starches. arrangements, mainly the short chains of amylopectin into dou-
By the thermal processing of starch by high temperature and ble helices (Montero, Rico, Rodríguez-Llamazares, Barral, & Bouza,
shear force, linear amylose chain dissociates out from the granules 2017) and processing-induced crystallinity, occurs during the pro-
P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188 181
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 starch. Figs. 4(c–g) show SEM picture of nanocomposites with 0, 1,
has vanished during the processing due to the granular melting of 2, 3, 4 wt.% CNF. Fig. 4c shows the fractured surface of TPS, a smooth
starch particles by mechanical and heat treatment during process- surface without any deformation, which confirms effective blend-
ing which was evident from the SEM analysis. By closely observing ing of plasticizer glycerol with starch matrix. By incorporation of
the XRD pattern, we can see that a peak is gradually evolved at nanofibers to the thermoplastic starch matrix the surface becomes
16.80 which is denoted by a line. This characterizes the branched uneven and more structured. The cellulosic nanofibers emerge as
amylopectin recrystallization (B- type crystallization). This phe- embedded in the thermoplastic starch matrix in Fig. 4(d–g) seem
nomenon is due to the process called retrogradation of the samples to be uniformly distributed.
upon storage as well as recrystallization induced by lipids and other From the SEM micrographs, it is seen that the cellulose
complex forming agents like glycerol that favours the retrograda- nanofibers homogenously dispersed in starch matrix. Due to sim-
tion of branched amylopectin chains. Characteristic peak for the ilar polysaccharide structure a homogenous morphology could be
cellulose is not so prominent in the diffractogram which is due to seen where cellulose is bound to starch matrix as seen in SEM
the amorphous nature of thermoplastic starch and similar func- micrographs.
tionality of starch and cellulose. Magnitude of peak at 2 = 27.80
increases upon increase in nanofibers content probably due to the
3.2.2. Viscoelastic properties, polymer chain dynamics and
recrystallization of amylopectin chain (dotted line shown in Fig. 4a).
evaluation of constrained region
This diffraction peak is not because of neat TPS or CNF, and it can
Dynamic Mechanical Analysis (DMA) used to follow the relax-
be most probably from amylopectin. Because CNFs are well defined
ation of polymer chains. The effect of temperature on the
objects, in which crystallinity should not be changed when it dis-
viscoelastic properties of starch CNF nanocomposites was studied
persed in the matrix and this specific crystallinity occurs, or at least
using DMA analysis. Evaluation of storage modulus, loss modulus
is detectable, only in the presence of high CNF content. It is most
and tan ␦ is a useful tool to study the molecular chain dynamics
probably ascribed to an interfacial effect. This interfacial crystal-
of polymer nanocomposites. Generally, an increase in nanofiller
lization seems to be favoured when the starch matrix plasticized
reinforcement results in the enhancement of storage modulus as
with the glycerol (Angellier, Molina-Boisseau, Dole, & Dufresne,
there is a decrease chain mobility of the polymer chains leading to
2006; Dufresne, 2000; Zainuddin, Ahmad, Kargarzadeh, Abdullah,
a decrease in the intensity of the tan ␦ peak.
& Dufresne, 2013).
In the present study, glycerol used as the plasticizer in the
To estimate the surface morphology of starch nanocomposites,
nanocomposites. The significance of glycerol on the viscoelastic
films were cryo fractured and observed through SEM. Fig. 4b shows
characteristics of starch composites was earlier studied by Garcia
the SEM image of native potato starch granules. It has a spheri-
et al. (Garcia, Ribba, Dufresne, Aranguren, & Goyanes, 2009) who
cal morphology which destroys after processing into thermoplastic
reported starch glycerol system as a heterogeneous system con-
182 P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188
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)
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 3.2.2.6. CNF-TPS interface adhesion (ˇ). As said earlier, CNF tended
(Fig. 5c). to locate glycerol rich starch phase as well as to the interphase
between two phases, glycerol rich starch phase and glycerol lean
3.2.2.5. Adhesion factor (A). The adhesion factor (A) between the starch phase. So, a measure of interface adhesion is important for
polymer matrix and reinforcing filler was calculated from Dynamic the evaluation of the interaction of CNF on to the starch/glycerol
Mechanical Analysis where loss factor of composites expressed in matrix. DMA is based upon a fact that energy dissipation is not only
volume fraction and damping factor of filler which is expressed by due to the matrix alone but also on the matrix/filler interaction and
the formula suggested by Wei et al. (Wei, 2006) interface.
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 rate of diffusion of water or any solvent is lower than that of poly-
√
the solvent against the square root of time ( t). Fig. 6a shows mer chain relaxation, the value of n will be equal to 0.5. In case, the
the sorption curves of water in glycerol plasticized potato starch- rate of relaxation of polymer chain is lower than diffusion of sol-
CNF nanocomposites by varying the CNF content. It is found that vent molecules through the system, the value will be 1 and called
the absorption of solvent water increases considerably in the first non-Fickian mode of transport, while the value comes between
because of higher hygroscopic character of starch and cellulose and 0.5–1 indicated anomalous behaviour. When the solvent penetra-
later the rate of uptake decreases and gradually level off reaching tion is much below the polymer chain relaxation, it is possible to
saturation. This is probably because of the decrease in concentra- record the n values below 0.5. This situation is named ‘Less Fickian
tion gradient of the penetrant, water. By the DMA analysis it was or pseudofickian (Abraham, Maria, George, Kalarikkal, & Thomas,
clear that there is a formation of constrained region among the 2015).
polymer chains that restricts the segmental mobility of polymer For this system, value of n comes around 0.4 which suggest a
chains due to strong matrix filler interaction which lead to less deviation from normal Fickian mode and hence can be classified as
flexibility and thereby low sorption behaviour. Since CNF creates Less fickian or pseudo fickian. K value gives an idea regarding the
a circuitous path for the diffusion of water molecules, after succes- solvent/matrix interaction.
sive addition of CNF, the equilibrium uptake decreases. At 1 wt.% The diffusion coefficient (D) which indicates the rate of solvent
CNF, the amount of CNF is unable to form a far-reaching network diffusion into the system which can be correlated with the polymer
structure and hence we can see the sorption curve of TPS reinforced chain segmental motion. The diffusion coefficient can be calculated
with 1 wt% CNF shows same absorption that of unreinforced one. using the formula of Fickian law (Schurtenberger, 1996).
Transport mechanism of solvent through polymeric system can The diffusivity of solvent i.e., water is strongly influenced by the
be analysed by fitting dynamic swelling data in the equation microstructure of the matrix as well as reinforcing phase, such as
the pores that may form during the drying process.
logQt/Q ∞ = logk + nlogt (16)
2
where, Qt is the mole percent solvent uptake upon each time inter- h
D= (17)
vals and k is a constant which is depends upon the solvent/matrix 4Q∞
interaction and value n gives an idea of the sorption mechanism.
The values of n and k are obtained from linear portion of plots Where
Qt versus the square root of time. The value of n depends on the h = Thickness of sample
nanocomposites characteristics which are to be considered. If the 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.
At high level of reinforcement, the diffusion coefficient tends to 3.2.3.2. Mathematical modelling. Mathematical diffusion mod-
decrease because of drop of matrix free volume by the addition of elling employed to analyse the diffusion characteristics of
nonreinforcements. At the higher concentration of CNF loading it penetrant molecules through polymeric system by comparing
shows a sort of aggregation. experimental results and theoretical models. In this study, we pro-
Permittivity and diffusivity of the composites lowers with suc- pose two models to study the mode of transport and diffusion
cessive nanofiber concentration which is due to the formation of a phenomena. These models depend on the migration of solvent
web like structure between starch and cellulose nanofibers. But at molecules from initial point to the other end of the sample. To fit
the higher concentration of nanofiber the values level off or increase the models with the experimental data, composites with 3 wt.% CNF
which may due to the formation of aggregates of nanofibers. were fitted with two models (Peppas sahlin and Korsmeyar pep-
Sorption coefficient of nanocomposites is calculated using the pas). The composition is chosen since these composite shows the
equation shown below. best results. Fig. 6c shows the model fit curve with experimental
Where, M∞ is the initial weight and M0 is the final weight of data which is indicated with dotted line. As per the graph shows
sample. the data is best fit with Kormeyar peppas model.
M∞ 3.2.3.2.1. Peppas–Sahlin model. According to this model, poly-
S= (18) mer matrixes contain two types of processes, diffusion of polymer
M0
and matrix relaxation (Peppas & Sahlin, 1989).
The permeability coefficient (P) of a composite gives an
Mt
overview of permeability of the composite towards the solvent and = kf t m + kr t 2m (22)
can be obtained by equation M∞
Where, Mt and M∞ are the fraction of solvent released at time t, kf
P = DXS (19) and kr are fickian contribution coefficient and relaxation coefficient
Where, D = Diffusion Coefficient contribution respectively.
S = Sorption Coefficient 3.2.3.2.2. Korsmeyer–Peppas model. Korsmeyar −Peppas
The difference in D and P for the successive CNF loadings in water model based on the fact that, the fractional diffusion and diffusion
at room temperature is shown below. From Fig. 6b, it was clear that time are exponently related (Eq. (23)) (Korsmeyer, Gurny, Doelker,
TPS reinforced with 3 wt.% CNF samples show minimum diffusivity Buri, & Peppas, 1983). In the equation, Mt and M␣ are the fraction
and permeability in water, whereas both are maximum for the neat of solvent released at time t, n and k are constant which diffusion
sample. The inside image shows the restriction of water molecules rate are and characteristics value of polymer solvent interaction.
in the CNF reinforced thermoplastic starch matrix that causes the Mt
minimal diffusivity and permittivity of composites with 3 wt.% of = kt n (23)
M∞
cellulose nanofiber. At higher filler loading D and P tends to level
To evaluate the diffusion mechanism, one of the data was plot-
off which accounts for the formation of aggregated of nanofibers.
ted and mathematically fitted with two principles that mentioned
above and observed that, data fitted well with Korsmeyer–Peppas
3.2.3.1. Swelling coefficient. The swelling coefficient is an indicator
model than peppas-sahlin model with an R value 0.9789. Thus,
of the capacity with which the samples swell in the solvent here in
the diffusion of polymer chains were exponentially related to the
water.
diffusion time.
(W2 − W1)
Swelling coefficient = (20)
W1 4. Conclusions
Where,
W1 = Dry weight of sample Starch-based nanocomposites reinforced with 1–4 wt% PALF
W2 = Swollen weight of sample nanofibers were prepared by solution casting process. The mor-
phological and structural analysis confirmed the formation of
(W2 − W1)
Swelling Index = × 100 (21) nanofibers from Pineapple leaf. Dynamic Mechanical Analysis
W1
of prepared composites was analysed thoroughly and from the
By looking to Table 3, we can see that both the swelling inference we conclude there is better interaction of CNF on to
coefficient and swelling index were found to be declining with suc- the thermoplastic starch matrix. Evaluation of constrained region
cessive filler reinforcement; because, nonreinforcement creates an shows that CNF had a tendency towards glycerol rich starch phase
obstruction in the path of solvent molecule through starch matrix since the composite exhibit two relaxation phenomena as evident
and therefore, nanocomposite swelling was reduced in the pres- by tan delta curve. Modelling by Cole Cole plot shows an imperfect
ence of fillers within the plasticized starch system. semicircle that further confirms the formation of heterogeneous
The decreased water sensitivity of cellulose filled starch system. Diffusion kinetics shows the pseudofickian behaviour of
nanocomposites happens, at least partially, from another phe- composites, Diffusion coefficient and permittivity decreases with
nomenon which include a restriction in the chains mobility, an successive CNF reinforcement which is probably because of the
improvement in the crystallinity and also due to effect of plasticiza- formation of a network structure that created a convoluted path
tion effect of glycerol which was evident from the DMA analysis. to a solvent molecule (water) to diffuse into the starch matrix and
P. Balakrishnan et al. / Carbohydrate Polymers 169 (2017) 176–188 187
the composites follow Korsmeyar Peppas model. Nanocomposites melt processing. Composites Science and Technology, 72, 858–863. http://dx.doi.
reinforced with 3 wt.% of CNF shows better dispersion in all cases org/10.1016/j.compscitech.2012.02.019
Gupta, A. P., & Alam, A. (2014). Study of flexural, tensile impact properties and
with low diffusivity and permittivity, high reinforcing efficiency, morphology of potato starch/polypropylene blends. International Journal of
low Ef and high entanglement of nanofibers. Advanced Research, 2(11), 599–604.
Ibrahim, H., Farag, M., Megahed, H., & Mehanny, S. (2014). Characteristics of
starch-based biodegradable composites reinforced with date palm and flax
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Acknowledgements 2013.08.051
Idicula, M., Malhotra, S. K., Joseph, K., & Thomas, S. (2005). Dynamic mechanical
The authors are grateful to Department of Science and Technol- analysis of randomly oriented intimately mixed short banana/sisal hybrid fibre
reinforced polyester composites. Composites Science and Technology, 65(7–8),
ogy (DST) for awarding INSPIRE fellowship to Preetha Balakrishnan,
1077–1087. http://dx.doi.org/10.1016/j.compscitech.2004.10.023
Financial support under DST-FIST New Delhi to Sree Sankara Col- Jyoti, J., Singh, B. P., Arya, A. K., & Dhakate, S. R. (2016). Dynamic mechanical
lege Kalady and DST Nanomission for instrumental facilities to properties of multiwall carbon nanotube reinforced ABS composites and their
correlation with entanglement density, adhesion, reinforcement and C factor.
Centre.
RSC Advances, 6, 3997–4006. http://dx.doi.org/10.1039/c5ra25561a
Karimi, S., Dufresne, A., Md. Tahir, P., Karimi, A., & Abdulkhani, A. (2014).
Biodegradable starch-based composites: Effect of micro and
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