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Effect of nanoparticle on the mechanical and gas barrier properties of

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Article  in  Applied Clay Science · September 2017

DOI: 10.1016/j.clay.2017.07.001

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 Applied Clay Science 146 (2017) 468–474

Contents lists available at ScienceDirect

Applied Clay Science

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

Research paper

Effect of nanoparticle on the mechanical and gas barrier properties of MARK

thermoplastic polyurethane
Shruti Pandeya, Karun K. Janaa, Vinod K. Aswalb, Dipak Ranac, Pralay Maitia,⁎
a
School of Materials Science and Technology, Indian Institute of Technology (Banaras Hindu University), Varanasi 221 005, India
b
Solid State Physics Division, Bhabha Atomic Research Centre, Trombay, Mumbai 400 085, India
c
Industrial Membrane Research Institute, Department of Chemical and Biological Engineering, University of Ottawa, 161 Louis Pasteur St., Ottawa, ON KIN 6N5, Canada

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

Keywords: Thermoplastic polyurethane (TPU) nanohybrids have been prepared through melt extrusion using ester type PU
Thermoplastic polyurethane and different concentrations of Indian origin organically modified nanoclay as filler. The level of dispersion of
Nanohybrid nanoclay in TPU is found to be good and considerable intercalation occurs due to strong interaction between
Structure polymer matrix and filler. The interaction is shown through spectroscopic measurement from the shifting of peak
Mechanical properties and gas permeability
position in FTIR and UV–vis. absorption spectra. Nanoclay induces crystallization in polymer while the blob size,
as measured through small angle neutron scattering, decreases in nanohybrid (1.5 nm) as compared to pure TPU
(1.7 nm) obtained after fitting the initial data point to Debye-Bueche model. Mechanical responses are much
superior in nanohybrid as compared to pure TPU and stiffness values continue to increase with nanoclay con-
centration while the toughness reach ata maximum value at an optimum concentration of 4 wt% of nanoclay.
Uniaxial stretching lead to the crystallization of segments and ordering of hard segments as verified through
sharp melting points in stretched TPU vis-à-vis predominant amorphous nature before stretching. Nanohybrid
membranes are prepared to investigate the gas permeation across the membranes and very high gas barrier of
nanohybrid (449 Barrer) is found as opposed to pure TPU barrier of 169 Barrer. Critical assessment of perme-
ability is performed in presence of nanoclay in different concentrations with a plausible mechanism of gas
barrier.

1. Introduction biocompatibility and, therefore, NK75 is used as a filler in biomedical

During past decades, the development of nanohybrids is customized
with different fillers and it has been the basis of production of many
superior products. Polymers with inorganic clay particles with high
aspect ratio with nanoscale dimension have yielded improved chemical
and physical properties including thermal, mechanical, flame-re-
tardant, electrical, biodegradability and barrier properties (Wang and
Pinnavaia, 1998; Shah et al., 2004; Jana et al., 2012; Jana et al., 2013;
Jana et al., 2015a, Jana et al., 2015b). Clays are layered silicate ma-
terials commonly used as reinforcing filler for the preparation of na-
nohybrids due to their easy availability, natural abundance and low
cost (Barick and Tripathy, 2010). Indian origin NK75 is a montmor-
illonite (Mt) clay and has planar octahedral alumina layer sandwiched
between two tetrahedral silicate layers (Nguyen and Baird, 2006). The
structure repeats itself with a characteristic distance. Mt. clay has high
cation exchange capacity (CEC), aspect ratio, surface area, surface re-
activity and adsorptive properties (Salahuddin et al., 2010). Higher
percentage of iron in nanoclay (NK75) helps in improving the
applications as well (Kapusetti et al., 2014). The properties of nano-
hybrids improve when the silicate layers (inorganic phase) exfoliate or
considerable intercalation occurs (Lebaron et al., 1999; Kim et al.,
2003; Song et al., 2005). Improved nanohybrid preparation is very
much reliant on the structural aspects of the polymer in addition to the
compatibility of the clay with the matrix. Isomorphic substitution
within the silicate layers generates negative charges which are counter
balanced by Ca++ and Na+ cations (residing in interlayer gallery) re-
sulting better miscibility between silicate layer and matrix and overall
good dispersion of the silicate layers (Corcione and Maffezzoli, 2009).
There are two fundamental processes to prepare nanohybrids (1) direct
intercalation of polymer chain into layered clay, and (2) intercalation of
monomer onto clay interlayer and consequent heat treatment for
polymerization (Rehab and Salahuddin, 2005; Joulazadeha and
Navarchiana, 2010a,Joulazadeha and Navarchiana, 2010b). The na-
nohybrid with large surface area can be used in a variety of applications
such as food packaging (Qian et al., 2011), biotechnology (Singh et al.,
2011), devices (Mitra et al., 2011) and fuel cell membrane (Jana et al.,

⁎
Corresponding author.
E-mail address: pmaiti.mst@itbhu.ac.in (P. Maiti).

http://dx.doi.org/10.1016/j.clay.2017.07.001
Received 4 March 2017; Received in revised form 3 July 2017; Accepted 3 July 2017
0169-1317/ © 2017 Elsevier B.V. All rights reserved.
S. Pandey et al.
2015a,b). Thermoplastic polyurethane (TPU) is a thermoplastic block
copolymer characterized by a wide range of properties consisting of
blinking soft segments (which is high molar mass polyether or polyester
macro-diol) and hard segments (which is self-possessed of diisocyanate
and chain-extender molecules that are either diol and diamine)
(Koerner et al., 2008; Mishra et al., 2012). TPU bridges the gap between
flexible rubber and rigid plastics and offers exceptional benefits. Unlike
other thermoplastic elastomers, TPU provides numerous physical
properties which makes it extremely flexible material adaptable to
various uses. Polymer nanohybrids obtained from a polyurethane ma-
trix and the adequate nanofillers offer a chance to produce new mate-
rials (Finnigan et al., 2004), where the properties of polyurethanes can
be improved. Polyurethane elastomers have massive challenge in
modern time as TPU possess good properties like high hardness, abra-
sion resistance, excellent mechanical properties and flexibility and it
has a variety of universal applications caused by its distinctive prop-
erties, e.g. biotechnology, adhesives and packaging etc. (Osman et al.,
2003; Choi et al., 2011; Mahanta et al., 2015). This work has been
carried out to study the properties of elastomeric TPU with clay (NK75)
with significantly improved properties as compared to pure polymer
and the effect of varying concentration of fillers in the nanohybrids
properties. Mechanical, morphological, thermal, gas barrier properties
are used to study the structure and the performance of the nanohybrids.
2. Experimental segment
2.1. Materials
Thermoplastic polyurethane (TPU) was obtained from Bayer
Material Science AG: polyester based TPU (Desmopan 385S) having the
shore hardness of 86A. A typical nanoclay (NK75; Indian origin high
iron content Mt., ion-exchanged with dimethyl dihydrogenated tallow
ammonium; CEC = 70 meq/100 g) was used as a filler for nanohybrid
preparation (Kapusetti et al., 2014). Tallow contains ~65% C18, ~ 30%
C16 and ~ 5% C14 alkyl chains.
2.2. Preparation of nanohybrid
Melt extrusion technique was used for the preparation of nanohy-
brid (Dan et al., 2006; Grande and Pessan, 2017). Nanoclay (NK75) was
mixed with TPU in a Haake twin-screw extruder (Hakke Mini Lab) for
10 min excluding the feeding time at 220 °C with the shear rate of
100 rpm. Henceforth, the nanohybrid of TPU will be termed as “NH”
with 4 wt% of nanoclay in the pristine polymer. Nanohybrids con-
taining 2, 6 and 10 wt% of nanoclay were also prepared to understand
the effect of nanoclay loading. Films (~ 120 μm thick) of pristine
polymer (TPU) and extruded nanohybrids (NHs) were prepared using a
compression molding machine (S. D. Scientific Ltd.).
3. Characterization
3.1. TEM
Bright field images of nanohybrid specimens were obtained using
TEM (Technai G2) operated at an accelerating voltage of 100 kV. A thin
layer, around 70 nm thick, from the sample was sectioned at −85 °C
using a Leica ultra-microtome equipped with a sharp diamond knife.
3.2. XRD
The change in d-value of silicate layers of the nanoclay was de-
termined using Bruker AXS D8 Advance wide-angle X-ray dif-
fractometer with Cu-Kα radiation with a graphite monochromator
(λ = 0.154 nm). The samples were scanned at 1°/min in 1 to 10° range
and at 3°/min for 10 to 40° 2θ range. The basal spacing of the nanoclay,
d001 was calculated using Bragg's law.
469
Applied Clay Science 146 (2017) 468–474
3.3. Small-angle neutron scattering
Small angle neutron scattering experiments were performed on the
spectrometer at the Dhruva reactor at Bhabha Atomic Research Centre
in Mumbai, India. The data was collected for the scattering vector (q)
range from 0.17 to 3.6 nm− 1. The scattering from the samples was
modified after background correction. The characteristics length (Λc)
was calculated using the equation:
2π
Λc =
qm (1)
where, qm is the scattering vector q consequent to the peak position of
shoulder in the scattering patterns of the samples. The temperature was
kept constant and stable at 30 °C during each measurement.
3.4. FTIR
Fourier transform infrared (FTIR) spectroscopy was performed on a
Thermo Scientific FTIR (NICOLET-6700) in the ATR mode in the wa-
venumber range of 650–4000 cm− 1. Each spectrum was recorded by
accumulating 100 scans with a peak resolution of 4 cm− 1in reflectance
mode.
3.5. UV–Vis spectroscopy
The UV–visible absorbance spectra of neat polymer and nanohybrid
films were taken using Shimadzu 17,001 in the range of 200–800 nm
wavelengths of light.
3.6. TGA
Thermogravimetric analysis (TGA) was performed on a Mettler-
Toledo TGA under nitrogen atmosphere. Thermal degradation of TPU
and NH specimens were studied with a heating rate of 20°/min in the
measurement range of 40to 600 °C and the sample weight of nearly
5 mg was used for TGA experiments.
3.7. DSC measurement
Differential scanning calorimetry (DSC) measurements were per-
formed on a Mettler832 instrument. The DSC was calibrated with in-
dium and zinc before actual experiment. The heat of fusion and melting
temperature were evaluated from the melting endotherms using a
software and computer attached to the instrument. Weight of the
samples was in the range from 3 to 10 mg range and a10°/min heating
rate was employed for all experiments.
3.8. Mechanical properties
Tensile tests were carried out on a universal testing machine
(Instron 3369). The strain rate was 5 mm/min at room temperature.
Dog bone shaped specimens with gauge length 20 mm, thickness
2.12 mm and width 4 mm were prepared using Haake micro-injector.
3.9. Measurement of gas Permeability
Gas permeability of the specimens (neat TPU and NH) was ex-
amined at a constant pressure using three parallel cells method (Savoji
et al., 2012). A spherical film of 11.044 cm2 area and 0.003 cm thick
sample was placed in the cell and was fixed using aluminum foil, glue
and cello tape. The feed pressure was set at 80 psi while permeate side
was maintained at the atmospheric pressure. The calculation of gas
permeation rate was resolved using soap bubble flow meter (Rana et al.,
2012). Each experiment was performed triplicate for reproducibility
and the averages of those results are reported. The gas permeability was
calculated from the following Eq. (2);
S. Pandey et al. Applied Clay Science 146 (2017) 468–474

Fig. 1. (a) TEM micrograph of TPU/nanoclay nanohybrid,

a. b. (b) Wide-angle XRD patterns of neat nanoclay and its na-
4 nm NH nohybrid, (c) FTIR spectra of the pristine TPU and NH in
Clay the stretching frequency range 3500–1400 cm− 1; and (d)
UV–Vis absorption spectra of pure TPU and its nanohybrid.

Intensity / a.u.
2 nm

2 4 6 8
2θ / deg

0.5
c. d. NH
NH 322 nm
TPU
390 nm
0.4
Reflectance / a.u.

3325 288 nm
Absorbance

0.3

1725 0.2
TPU

3330 3300 0.1

1728
1703
0.0
3400 1800 -1 1500 200 400 600 800
Wavenumber / cm Wavelength / nm

10 ml nature of interactions between polymer and nanoclay (Vaia and

Gas flow rate (GFr) =
t min × 60
where, tmin is the time (sec) of gas flow rate of the permeate gas passing
through the membrane (cm3/s). Gas flux was calculated from the Gfr
per unit area where, gauge pressure was considered as 80–14.69 psi.
Gauge pressure indicates the absolute pressure difference between the
feed side and permeates side (cm Hg). Then, the normalized gas flux
was calculated using the Eq. (3);
Gas flux
Normalized gas flux (NGF) =
Guage pressure
and gas permeability coefficient (GPC) = NGF × membrane thickness,
where, permeability was expressed in barrer (1 bar-
rer = 10− 10 cm3(STP) cm cm− 2 s− 1 cm Hg− 1).
4. Results and discussion
4.1. Dispersion and interactions
Organically modified nanoclay is dispersed in TPU and the disper-
sion is found to be uniform as evident from the bright field TEM image
(Fig. 1a) showing stacks of nanoclay with the correlation length, ξ of
239 ± 10 nm. High resolution image of TEM also indicates the inter-
calated structure of the nanohybrid (supplementary document) (Cai
et al., 2007). The nanostructure analysis through XRD pattern showed a
strong reflection at 2θ ~ 2.2°, corresponding to d001 value of 4 nm for
nanohybrid as opposed to the value of 2 nm of organically modified
nanoclay showing significant level of intercalation of polymer within
the gallery of platelets of nanoclay (Fig. 1b) (Kapusetti et al., 2014).
Further, the higher intensity of the intercalated reflection is presumably
due to ordered pattern of the platelets against the relatively disordered
nature of nanoclay powder. It should be noted that the level of dis-
persion and the extent of intercalation is strongly correlated with the
(2) Giannelis, 1997) and to some extent on the preparation method of
nanohybrid (Wang et al., 2002).
Fig. 1c exhibits FTIR spectra of pure TPU and NH showing the
carbonyl peaks around 1703 and 1728 cm− 1 for pure TPU assigned as
hydrogen-bonded carbonyl group and free carbonyl group (eC = O) of
the urethane linkage (Pattanayak and Jana, 2005). However, a single
stretching frequency at 1725 cm− 1 has been observed in NH and the
shifting of peak position from 1728 → 1725 cm− 1 along with con-
siderable suppression of hydrogen bonded peak is presumably due to
(3) the interaction between polymer and nanoclay in nanohybrid. Simi-
larly, pure TPU shows two eNH stretching frequency at 3330 and
3300 cm− 1 assigned as non-hydrogen bonded and hydrogen bonded
eNH peak, respectively, while a single peak at 3325 cm− 1 is observed
in nanohybrid suggesting interactions between the components as evi-
dent from shifting of peak and suppression of hydrogen bonded peak. A
strong and wide UV–visible absorption band at 288 nm is observed in
pure TPU, accredited as π → π⁎ electronic transition from carbo-
n–oxygen double bond (C]O) (Wang et al., 2013) (Fig. 1d). It is in-
teresting to note that a significant red shift along with greater absorp-
tion has been observed for nanohybrid at 322 nm arising from
enhanced interaction of organic modifier and polymer. Further, a wider
tail appeared for NH at 390 nm, preassembly duo to filler. Therefore,
the interactions, as evident from FTIR and UV–vis studies, between
polymer and nanofiller are responsible for good dispersion and superior
intercalation as observed in TEM micrograph and XRD patterns. How-
ever, slight shift of peak position occurs in FTIR (1728–1725 cm− 1) led
to inference that there are interaction but that is not very strong rather
some sort of interaction do exist. That is the reason behind moderately
good dispersion in TEM arising from weak interaction.

470
S. Pandey et al. Applied Clay Science 146 (2017) 468–474

a. b. 4.8 c. TPU

Intensity / a.u.
NH Clay 3.2
4 NH NH
TPU
20.9 TPU
3.2
ΔΤ = 22.5 nm
Intensity / a.u.

20.1 2.4 c 2.8

I(q) / a.u.
I(q) / a.u.
10 15 20 25 30 35 40
2θ / deg ξ = 1.58
1.6
2.4
Δc = 14.9 nm

ξ = 1.70
2.0
0.8

1.6
10 15 20 25 30 35 40 0.25 0.5 0.75 1 -1 2.5 0.15 0.20 0.25 0.30 0.35
2θ / deg q / nm -1
q / nm
Fig. 2. (a) XRD patterns of the pure TPU and NH (the inset figure show the XRD pattern of pure nanoclay), (b) Small-angle neutron scattering plot I(q) vs. q (wavevector) of indicated TPU
and nanohybrid, and (c) Debye-Bueche fitting for TPU and NH considering the value at lower q range.

4.2. Structure of nanohybrid degrades at around 336 °C (Strankowskil et al., 2012) (temperature
corresponding to 5% mass loss) while nanohybrid degradation takes
The structural alteration has been verified through wide angle X-ray place at 320 °C. The slight faster degradation of nanohybrid is pre-
scattering. Fig. 2a shows broad reflections at 20.1° due to amorphous sumably due to nanoclay while two stage degradation is noticed in both
hallow of pure TPU (Koerner et al., 2008). This reflection has been the cases for the degradation of hard segment (lower temperature) and
shifted to 20.9° in presence of filler in addition to other smaller humps soft segment (relatively high temperature).
indicating a crystalline phase in the nanohybrid. Fig. 2b represents the
small angle neutron scattering (SANS) patterns of pristine TPU and its
nanohybrid on a log-log scale. A distinctive shoulder is clear at wave- 4.4. Mechanical responses
vector, q ~ 0.65 nm− 1 for pure TPU, corresponding to characteristic
length, Ʌc of 14.96 nm which has been shifted to q ~ 0.53 nm− 1 in Filler present in polymer matrix is expected to enhance the me-
nanohybrid, corresponding to Ʌc of 22.41 nm. These peaks are in- chanical responses of polymer and the stress-strain curves of the sam-
dicative of a stacked lamellar pattern inside the crystallites. Further, the ples under tensile condition are presented in Fig. 4a showing much
initial data points are fitted with Debye-Bueche model to calculate the higher elongation at break for nanohybrid as compared to neat TPU.
correlation length to understand the blob sizes which are found to be Further, continuous increase of stress with increasing elongation sug-
1.70 and 1.58 nm for TPU and NH, respectively (Fig. 2c). These ag- gests possible strain induced crystallization. The variation of mechan-
gregates are formed due to self-assembly of greater hydrogen bonded ical properties with respect to varying filler concentrations in different
clusters (Patel et al., 2015) and lower size in nanohybrid indicate that nanohybrids is shown in Fig. 4b. The modulus was calculated from the
smaller aggregation size is enough for nanohybrid to form self-assembly linear regime while the area under stress-strain curves is considered for
because of stronger interactions between filler and TPU as opposed to toughness calculation. The nanohybrids show improvement in elastic
only hydrogen bonded interaction exist in pure TPU. This result is in moduli consistently with increasing nanoclay concentration due to re-
agreement with the literature reported values of different variety of inforcing effect of the filler while toughness increases up to 4 wt% of
polyurethanes (Mishra et al., 2010). nanoclay followed by a decreasing trend raising an optimum con-
centration of 4 wt% of filler concentration both in terms of stiffness and
4.3. Thermal properties including stability toughness. Halpin–Tsai model (Ashton et al., 1969; Halpin, 1969;
Halpin and Kardos, 1976) is widely used to estimate the reinforcement
Fig. 3a shows the DSC thermograms obtained by heating the sample effect of filler particle in nanohybrids, following the equation (Fornes
from room temperature to 300 °C. A prominent glass transition tem- and Paul, 2003; Joulazadeha and Navarchiana, 2010a,b):
perature, Tg of TPU is found at 128 °C. The glass transition temperature
of the nanohybrid has increased considerably to 148 °C and higher Tg of Ec 1 + ξηVf
=
nanohybrid is attributed to the interactions between the organic and Em 1 − ηVf (4)
inorganic phases. The thermal stability of the TPU and NH has been
investigated by using thermogravimetric analyzer (TGA) and the mass where, ξ is a shape parameter dependent upon filler geometry, or-
loss as a function of temperature has been shown in Fig. 3b. Pure TPU ientation and loading direction, and η is given by:

Fig. 3. (a) DSC thermograms of TPU and nanohybrid, and

a. b. NH (b) TGA thermograms of neat TPU and NH.
NH 1.0
TPU
TPU
Heat flow / a.u.

0.8
Weight fraction

o
148 C
0.6

0.4
o
128 C
0.2

0.0

200 300 400 500

100 150 200 0
T / ∞C Temp / C

471
S. Pandey et al. Applied Clay Science 146 (2017) 468–474

a. NH b. NH
c. 2.0

Modulus / MPa
20 20 NH
TPU
1.8 ξ=9.0
16
15
287 1.6
σ / MPa

Ec/Em
12
10

-3
Toughness / MJ m
120 1.4
288
5 80 1.2

40 1.0
0 0.00 0.02 0.04 0.06 0.08
0 300 600 900 1200 0 2 4 6 8 10 Vf
ε/% wt. of filler / %

Fig. 4. (a) Stress-strain curves of injected specimens at a rate of 5 mm/min for pristine TPU and TPU nanohybrid (NH) showing the dramatic increase in elongation at break for NH, (b)
Variations of tensile modulus and toughness of nanohybrids as a function of nanofiller concentration, and (c) Young's modulus vs. loading of nanoclay (volume fraction) in nanohybrids,
fitted with Halpin-Tsai model.

Ef
−1 exhibit any melting peak in the DSC thermograms (Fig. 3a). The effect
Em
η= Ef of uniaxial stretching has been shown through schematic in Fig. 5c
+ξ (5)
Em where amorphous soft segments get crystallized after stretching while
disordered hard segment transform in to an ordered state under the
where, Ef, Em represent Young's modulus of the filler and matrix,
influence of stretching. Uniaxial stretching usually converts the coiled
respectively. The model is based on micromechanics contributed by
state of polymer chain into uncoiled configuration and the thermo-
Herman and Hill (Hill, 1964; Hermans, 1967). Halpin-Tsai fit for TPU/
dynamically unfavorable low entropic condition is overcome through
nanoclay nanohybrids has been shown in Fig. 4c considering
its crystallization to minimize the overall Gibbs energy. Relatively
Em = 8.6 MPa and Ef = 200 GPa. The modulus predictions for nano-
lower heats of fusion for hard segment is presumably due to their poor
clay volume fraction range from 2 to 10% which is within the range for
ability to crystallize in presence of aromatic diisocyanate used to pre-
practical applications. As expected, Halpin-Tsai equation predicts well
pare TPU.
the development of modulus with increasing volume fraction of nano-
filler with the value of ξ = 3 which fits the data point in a best possible
manner. The value of ξ depends on the geometry and packing of the 4.6. Effect of nanoclay on gas permeation
particles as well as on the direction of the load relative to the or-
ientation of the nanoparticles. Increasing the aspect ratio results in Incorporation of filler particles in the polymer matrix increases the
higher reinforcement for a given filler modulus and volume fraction. gas barrier properties in nanohybrids (Adame and Beall, 2009; Sheng
For oriented lamellar shape filler particles, ξ is equal to 2 (w/t), where et al., 2011; Tan and Thomas, 2017). The influence of nanoclay content
w and t are the width and thickness of the particles, respectively. on the barrier performance to nitrogen has been studied by in-
vestigating nitrogen permeability through TPU and its nanohybrid
4.5. Effect of uniaxial stretching on structure films. Nitrogen permeability results from testing of the neat TPU and its
nanohybrid films of different filler concentrations are shown in Fig. 6a.
The samples are stretched uniaxially using UTM at a particular rate. All the nanohybrid films showed better nitrogen barrier than pure TPU
Interestingly, sharp reflections appear in XRD patterns both in TPU and film and the gas permeability decreases with increasing filler con-
NH at 2θ ~ 21.5 and 21.7° for TPU and NH, respectively (Fig. 5a). The centration while this effect is more pronounced in lower concentration
shifting of reflection position for nanohybrid indicates greater crystal- arising from the uniform distribution of nanoplatelets. The efficiency of
lization vis-à-vis amorphous hallow at 2θ ~ 20.1° before stretching. barrier effect is reduced for high concentration presumably due to ag-
Further, the appearance of new peak in DSC thermograms also con- glomeration of nanoclay at higher concentration because of effective
solidates the crystallization after stretching. Moreover, the higher heat blockade is less as compared to increased concentration. The schematic
of fusion for stretched nanohybrid (22.4 J·g− 1) as opposed to stretched representation of gas permeation has been shown in Fig. 6b where the
TPU (7.0 J·g− 1) confirms the crystallization of both the soft segment path becomes tortuous in presence of two-dimensional platelets redu-
(peak around 55 °C) and hard segment (small peak around 189 °C). This cing the gas permeation to significant level. Geometrical influences like
is to mention that unstretched samples (both pure TPU and NH) do not shape and state of exfoliation/intercalation of platelets and their

a. NH
b. c.
NH
TPU 21.7
TPU
Heat flow / a.u.
Intensity / a.u.

ΔH = 1.5

21.5
175.8

ΔH = 22.4

55.9 ΔH = 2.6

ΔH = 7.0
179.5

55.8

10 15 20 25 30 50 100 150 200

2θ / deg T / ∞C
Fig. 5. (a) XRD patterns of TPU and its nanohybrid after stretching, (b) DSC thermograms of TPU and its nanohybrid showing the melting peak of soft and hard segments with respective
heat of fusion values, and (c) schematic representation of chain configuration before and after stretching. Disorder hard segment along with amorphous soft segment is predicted against
the order hard segment and crystallized soft segment after uniaxial stretching.

472
S. Pandey et al.
Fig. 6. (a) Experimental (points and dashed line) and predicted (solid line following the Eq. (6)) gas permeability of nitrogen vs. nanoclay content of TPU-nanohybrid specimens at room
temperature. (1 Barrer = 1 × 10− 10 [cm3 (STP) cm/cm2 s cm Hg]), (b) Schematic path of representative for neat TPU and nanohybrid (in case of TPU, nitrogen gas can permeate across
the film thickness while gas has to follow a tortuous path in presence of two-dimensional platelets).
orientation in the polymer matrix is also reflected by the degree of
tortuosity created by the filler particles. The permeability of the na-
nohybrids (Ps) is related to the permeability of the pure polymer (Pp)
and the volume fraction of the sheets (Фs), length (L) and width (w) of
the sheets (nanoclay particles) as shown in Eq. (6) following Bhar-
adwaj's model (Sridhar, 2006). S is considered as filler order parameter
and is found to be the value of 0.3 using best fitting of the Bharadwaj's
equation to the experimental data points. The Eq. (6) reduces to the
expression in the form of Eq. (7)considering the value of S = 1. Thus,
the deviation of the order parameter from unity in this case is due to the
retardation in the diffusion mechanism of the gas molecules through the
matrix because of the tortuous path being created by the orientation of
nanoclay platelets.
Ps (1 − Фs)
= lization has been observed as revealed through sharp melting points
Pp 1+
L
2w
2
Фs 3 ( )(S + )1
2 (6)
Ps (1 − Фs)
= L
Pp 1 + 2w Фs
where, L and W are the length and thickness of the filler platelets
and Фs is the volume fraction of the filler (nanoclay). Volume fractions
of the nanoclay platelets in NH are calculated from the weight fraction
using the density of fillers used. Aspect ratio (L/2w) is likely to be
changed due to considerable agglomeration of nanoclay platelets at
higher concentration and, hence, slight distortion of permeability oc-
curs from the prediction by Bharadwaj. However, theoretical prediction
of permeability happens to a great extent in this case and more im-
portantly, permeability can be reduced using the nanoclay.
Now, it is pertinent to compare the results of literature reported
data against our work to improve the properties and structure property
relationship of TPU nanoclay nanohybrid. Most of the works are related
to the dispersion using different types of nanoclay and subsequent
improvement in mechanical properties mentioning the interaction be-
hind the enhancement (Dan et al., 2006; Cai et al., 2007). This work
emphasizes on the significant improvement in gas barrier properties
using small amount nanoclay as compared to minimal increment re-
ported by Sheng et al., 2011. Further, structural development during
stretching is the unique feather suggesting crystallization of soft seg-
mented zone and overall crystallite size determination through small
angle neutron studies.
5. Conclusions
Thermoplastic polyurethane nanohybrids have been prepared
through melt extrusion using Indian based organically modified nano-
clay. The dispersion level of nanoclay in TPU matrix is found to be good
as observed through TEM bright field image. Intercalated nanostructure
is noticed as the gallery spacing of nanoclay increases from 2 to 4 nm
due to insertion of polymer chain into the gallery arising from specific
Applied Clay Science 146 (2017) 468–474
interactions. The interactions are visualized through spectroscopic
measurement and considerable shifting of peak position both in FTIR
and UV–vis. suggest strong interaction between TPU and nanoclay.
Crystallinity develops in nanohybrid in presence of nanoclay as op-
posed to predominant amorphous nature of TPU. Greater assembly of
tens of nanometer is observed through small angle neutron scattering of
varying size of 22.5 and 14.9 nm for TPU and nanohybrid, respectively,
with blob size of ~ 1.7 nm, arising from the Debye-Bueche fitting of the
data points at lower wavevector region. Nanohybrids show remarkable
improvement in mechanical strength and toughness increase up to 4 wt
% of nanoclay followed by decreasing tendency while Young's moduli
gradually increase with the nanofiller concentration. Gas barrier
property of nanohybrid has significantly been improved in nanohybrid
as compared to the matrix without nanoclay. Strain induced crystal-
both for soft and hard segment vis-à-vis the absence of any melting
point before stretching leading to propose a model of ordering of hard
segment and crystallization of soft segment under uniaxial stretching.
(7) The permeability of gas decreases in nanohybrids with increasing na-
noclay loading because of delayed diffusion in tortuous path created by
the dispersed nanoclay platelets. Gas permeation in nanohybrid has
been critically evaluated using different models.
Acknowledgement
The authors are thankful to Dr. D. K. Avasthi and Dr. Pawan K.
Kulriya of University Accelerator Centre (IUAC), New Delhi, India for
supporting in XRD measurement. Authors also acknowledge the Council
for Scientific and Industrial Research, New Delhi (Grant No. 02(0074)/
12/EMR-II).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.clay.2017.07.001.
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