Polymer 252 (2022) 124914

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Polymer
journal homepage: www.elsevier.com/locate/polymer

Design of ultrastretchable and super-elastic tailorable hydrophilic

thermoplastic elastomeric materials
Pratiksha Awasthi , Shib Shankar Banerjee *
Department of Materials Science and Engineering. Indian Institute of Technology Delhi, New Delhi, 110016, India

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

Keywords: In this work, new ultrastretchable and super-elastic hydrophilic thermoplastic elastomeric (TPEs) materials were
Thermoplastic polyurethane (TPU) developed for the first time from the thermoplastic polyurethane (TPU) and epichlorohydrin-ethylene oxide-allyl
Epichlorohydrin-ethylene oxide-allyl glycidyl glycidyl ether (GECO) rubber using straightforward melt-blending and dynamic vulcanization approaches, which
ether (GECO)
allows the creation of tailorable hydrophilic TPE materials. The resulting materials can absorb up to ~80% water
Thermoplastic elastomers
Palierne model
within 4 h. The absorbed water convert itself into hexagonal ice crystals in the TPE matrix which was directly
Strain at break evident from differential scanning calorimetry and cryo-transmittance electron microscopy. The phase compo­
nents of developed TPE were found to be interactive which was analysed from the torque and loss tangent values.
Interaction was further enhanced after dynamic vulcanization which was predicted from the rheological Palierne
model. Interestingly, interfacial tension between the TPU and GECO was significantly reduced after dynamic
vulcanization which suggested stronger inter-domain interaction between the phase components. It was revealed
that the resulting TPE possess droplet-matrix phase morphological structure which was supported from the
theoretical Kerner model prediction. Surprisingly, resulting materials showed extraordinary elastomeric prop­
erties than that of TPEs reported earlier, such as very high strain at break (~800–1000%) and lowest tension set
(~2–6%) which enables the creation of ultrastretchable and super-elastic materials.

1. Introduction commodity applications.

Thermoplastic elastomer (TPE) is a special kind of hybrid and
functional material having thermoplastics like processability and at the
same time exhibits rubber like elasticity and flexibility. It comprises of
hard and soft segments; hard segment indicates the thermoplastic phase
and shows semi-crystalline behavior, whereas soft segment resembles to
the elastomeric phase and shows amorphous behavior [1–4]. TPE has an
enormous possibility for industrial revolution due to its unique and
outstanding properties such as superior chemical resistance, high me­
chanical properties, potential to form bonds with various thermoplas­
tics, thermoplastics like processability, and recyclability as well as
unique rubber like elasticity [5–11]. Along with these properties it
provides wider processing window and excellent price-performance
ratio [12–16]. All these combined features make TPEs, fundamentally
interesting class of specialty polymeric materials and enhance their
market value, and recently they have overcome the elastomers and
thermoplastics market. Commercial value of TPE has increased mani­
folds nowadays, because of its importance in engineering and
Thermoplastic vulcanizates (TPVs) are a category of superior per­
formance TPEs developed by dynamic vulcanization of an elastomer
phase in presence of the molten thermoplastics. Degree of crosslinking is
controlled by limiting the incorporation of vulcanizing agents [17–22]
and the crosslink density has notable influence on the final properties
and performance of a material. TPVs exhibit superior chemical and
mechanical properties compared to the TPE because of the excessive
crosslink density of the elastomer segment and the smaller domain size
of the elastomer domain. Among several classes, TPEs from the
rubber-thermoplastics blend have gained maximum popularity because
properties can certainly be tailored by varying the proportion of
different components and incorporation of compatibilizers, vulcanizing
agents, etc. Several environmental factors such as presence of ozone, UV
rays and moisture also effect the properties and performances of the
TPEs [23–25].
Nowadays, hydrophilic polymers are in high research demand
because of its wide application in various areas such as drug delivery,
body implants, membranes, adsorbents, smart materials mechanical

* Corresponding author.
E-mail address: ssbanerjee@mse.iitd.ac.in (S.S. Banerjee).

https://doi.org/10.1016/j.polymer.2022.124914
Received 28 January 2022; Received in revised form 1 April 2022; Accepted 29 April 2022
Available online 13 May 2022
0032-3861/© 2022 Elsevier Ltd. All rights reserved.
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

actuators, etc. [26–30]. Hydrophilic polymers swell by absorbing water 2. Experimental section
up to a certain extent of their weight. The phenomenon of interaction
between polymer and water is very compelling. The absorbed water in 2.1. Materials
hydrophilic polymers could be categorized into three different types:
nonfreezing bound water (non-crystallizable), freezing-bound water The hydrophilic grade of thermoplastic polyurethane (TPU) (HP 93A
(crystallizable) and freely present water [31]. Initially, when the poly­ 100) in granular form (density 1.13 g/cm3) was obtained from Lubrizol
mer absorbs water, it gets uniformly distributed throughout the struc­ Corp. USA and epichlorohydrin− ethylene oxide− allyl glycidyl ether
ture and are tightly bounded with the polar group of polymer, these (GECO) (Hydrin T3000LL) elastomer (density 1.28 g/cm3, Mooney
strong interactions restrict the mobility of a water molecule and hence Viscosity, ML1+4 at 100 ◦ C = 57) was obtained through Zeon Chemicals,
are called non-freezing bound water. After a certain characteristic USA. It is a terpolymer having 23.7–25.7% chlorine content and
threshold, further added water forms weak link with the polar group of 4.5–5.5% allyl glycidyl ether (AGE) content. The chemical structure of
polymer chain and labelled as freezing-bound water and have limited the TPU and GECO are given in Fig. 1. Dicumyl Peroxide (DCP) was used
mobility. Additional increase in the level of absorbed water will not form as dynamic vulcanizing agent and procured from Sigma Aldrich. The
any kind of bond with the polymer and remains in the free form and formulation of the mixed compositions are given in Table 1. In Figures,
termed as freely present water. Non-freezable bound water will not form TPU is referred as TP and GECO is referred as G. Among all the tailored
any ice crystal, only freezable bound water and free water will form ice TPE compositions, best TPE composition was selected to develop TPV.
crystals. However, the melting point of both the waters are at different For TPV, 1 phr (parts hundred rubber) DCP was added in mixed
temperatures, ice crystals of freezable-bound water defrost below 0 ◦ C, formulation.
whereas ice crystals of free-water defrost slightly above 0 ◦ C [32]. Water
behavior can be altered depending on the level of physical and chemical 2.2. Preparation of thermoplastic elastomer compositions
interaction between the polymer phase and water [33,34]. While the
effect of absorbed water on properties of some rubbers and thermo­ TPU granules were completely dried in vacuum oven at 80 ◦ C for 12
plastics have been explored [35–39], however, its impact on the prop­ h prior to blending. The blend compositions were prepared in a Haake
erties and structure of thermoplastic elastomeric materials (TPEs and Rheomix (350 ml, Haake OS Lab Mixer) with roller type rotor at 140 ◦ C
TPVs) has not been explored yet. The phenomenon of water absorption for 10 min having a fixed rotor speed of 80 rpm. Initially, TPU was added
effect on structure and properties of thermoplastic elastomeric materials and after 2 min of melting, GECO was incorporated and allowed to mix
is of wide interest from their application point of view. Most of the TPEs for another 8 min under the same conditions. Mixed compositions were
which are being in use currently, does not have hydrophilic properties, quickly removed from the rheomix after complete mixing. For TPV
thereby affecting the product’s credibility as well as reliability in spe­ initially TPU was added, after 2 min GECO was added and after 4 min
cific applications. However, because of the biphasic phase morpholog­ DCP was added and allowed to mix for another 6 min. 2 mm thick sheets
ical structure, water absorption in the TPE matrix is a complex were prepared through compression molding (Labtech Model LP-S-30)
phenomenon. at 150 ◦ C and 100 bar pressure for 5 min.
The intention of the current work is to develop the hydrophilic and
ultrastretchable thermoplastic elastomeric materials using hydrophilic
2.3. Characterization
thermoplastic polyurethane (TPU) and epichlorohydrin − ethylene
oxide− allyl glycidyl ether (GECO) rubber, which facilitates the
2.3.1. Mechanical tests
designing of a tailorable hydrophilic TPE materials. The resulting ma­
Uniaxial tensile testings were performed using universal testing
terials can absorb up to ~80% water within 4 h. The effect of interaction
between phase components was analysed from the torque and dynamic Table 1
loss tangent values. Influence of dynamic vulcanization on interdomain Formulation on mixes.
interaction between phase components was predicted from the rheo­ Sample compositions TPU GECO Comments
logical Palierne model. In addition, effect of compositional ratios and
TPU 100a (Pristine polymers)
dynamic vulcanization on absolute value of complex viscosity and melt-
–
GECO – 100a
elastic properties, like apparent elasticity and first normal stress differ­ 90 TPU/10GECO 90 10 (Variation of TPU-GECO ratios)
ence were reported. To the best of our knowledge, it was observed that 80 TPU/20GECO 80 20
the developed TPE exhibits extraordinary thermoplastic elastomeric 70 TPU/30GECO 70 30
60 TPU/40GECO 60 40
properties.
50 TPU/50GECO 50 50
a
Weight percent.

Fig. 1. Chemical structure of (a) Thermoplastic polyurethane (TPU) and (b) Epichlorohydrin− ethylene oxide− allyl glycidyl ether (GECO) rubber.

2
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

machine (Zwick, Z010) as per the ISO-527-2-5A specifications. Testing done using Modular Compact Rheometer (Anton Paar Model MCR 702,
was conducted having a crosshead speed of 200 mm/min. Young’s Austria) which is having a parallel plate geometry (diameter = 25 mm)
modulus, elongation at break (EAB) and tensile strength (TS) was and a distance of 2 mm between the plates. Frequency sweep master
measured from the tensile studies. In addition, cyclic tensile tests were curve experiments were performed having the frequency range of
also performed on the same tensile testing instrument. For cyclic tensile 0.1–100 rad− 1 at a persistent strain of 5% at five different temperatures
testing, samples were stretched for three cycles having different strain 130 ◦ C, 140 ◦ C, 150 ◦ C, 160 ◦ C and 170 ◦ C, respectively. The principle of
values of 50% (three cycles), 100% (three cycles) and 200% (three cy­ time-temperature superposition (TTS) was applied to constitute the
cles) and finally it was stretched till the failure point. master curve from absolute value of complex viscosity (η*) and dynamic
Tension set was calculated at room temperature by extending the moduli (Eʹ and Eʺ) at the reference temperature of 150 ◦ C (using a
sample up to 100% strain in the tensile direction and was hold on to that horizontal shift factor (aT) values were shifted to reference tempera­
position for 10 min. After relaxation, sample was left still for 24 h and ture). Individual flow curves represent data from set of three specimens
then changes in dimensions were measured and recorded as tension set. of same compositions. The standard deviation (experimental error) for
Hardness testing was done at room temperature as per DIN ISO-7619 calculation of complex viscosity was ~2–3%.
test method. Shore A and Shore D hardness values of samples were
reported. 2.3.6. Hydrophilicity analysis
For water absorption studies, initially dry weight of the samples were
2.3.2. Infrared radiation (IR) spectroscopy in attenuated total reflectance taken (Wd) and then the samples were dipped in a deionized water at
mode (ATR) ambient temperature. The samples were withdrawn from water and
IR spectra in ATR mode of the pure polymers along with the blend weighed (Ws) after dabbing them with a filter paper to exclude excess
compositions were recorded using Thermo Scientific Nicolet (model amount of water. The samples were weighed several times at different
6700) spectrophotometer having resolution of 4 cm− 1 and for each intervals until swelling stability was reached. The percentage of absor­
spectra average of sixteen scans were taken on a smooth film. bed water was calculated by-
Ws − Wd
2.3.3. Dynamic mechanical analysis x 100 (4)
Wd
Pure polymers and their different blend compositions were tested for
their dynamic mechanical properties using TA instruments (Q800). All
2.3.7. Differential scanning calorimetry (DSC)
the specimens (width 10 mm, thickness 2 mm) were tested having a
Differential scanning calorimetry were done for pure polymers and
persistent frequency of 10Hz over a temperature range of − 70 ◦ C to
blends using Thermal analysis TA instruments, Differential Scanning
+70 ◦ C and the heating rate was kept at 3 ◦ C/min.
calorimeter (DSC Q2000) in an inert atmosphere (Nitrogen atmosphere)
at a ramp rate of 10 ◦ C/min. Experiment was done in the temperature
2.3.4. Field emission scanning electron microscope (FESEM)
span of − 70 to 200 ◦ C.
Blend morphology was analysed from SEM (Zeiss EVO 18) having a
working distance (WD) of 6 mm and acceleration voltage was kept 20.0
2.3.8. Cryo-transmission electron microscopy (Cryo-TEM)
kV. A fine coating of gold was deposited for 60 s on the flat specimen
For cryo-TEM, a water dipped sample was cooled up to − 160 ◦ C,
surface. The coating is done to eliminate charging of sample while
specimen was staged on chamber of ultramicrotome (Ultracut Model,
exposure with an electron beam.
Leica Microsystems GmbH, Germany) and to maintain a temperature at
Particle diameter (di) measurement through the photo-micrographs
− 160 ◦ C the chamber was flooded with a dry nitrogen. Approximately
provides the particle size distribution of rubber for individual blend
120–130 nm wide section was sliced using a diamond knife and the
compositions. The number-average diameter and the weight-average
specimen was transferred to a grid. The TEM grid was then transferred
diameter (<dw>) were measured using the following equations:
into a grid holder stand (Gatan 626) and analysis was done at − 170 ◦ C.
∑
ni di
< di >= ∑ (1)
ni 3. Results and discussion
∑
ni d 2 3.1. Torque
< dw >= ∑ i (2)
ni di
Torque generated while mixing of polymers is the complex merger of
Physico-mechanical properties of developed blend compositions are
elongational and shear flow for real mixing environment. The torque vs.
influenced by the inter-particle distance between the elastomeric
time curve for the immaculate and blend compositions are given in Fig. 2
dispersed phases. The concept of ligament’s average thickness between
(a). The curve gave two peaks, unmolten TPU exerted resistance on the
two particles was initially proposed by Wu [40]. Inter-particle decides
rotor and increased the mixing torque which results into first peak later
whether a blend composition will be brittle or tough. For cubic array
on with further mixing viscosity decreased with complete melting of
arrangement of spherical particles, the distance between the particles
TPU. On further addition of GECO, the value of torque again increased
are obtained using the following equation-
and provide the second peak. After certain mixing time, steady-state was
[ ( )1 ]
π 3 observed with moderate decrease in the value of torque and simulta­
ID = d − 1 (3) neous increase in temperature. After certain time uniform value of tor­
6φr
que evinced optimum mixing of the TPU and GECO.
Mixing time and extent of mixing are important parameters for
where, d denotes the size of rubber particle and φr depicts the volume
defining quality mixing as ultimate properties of a blend depends on the
fraction of rubber.
nature of mixing. The high value of melt viscosity of GECO leads to
For determining size distribution of the rubber particles, rubber
highest mixing torque whereas TPU showed lowest torque value (Fig. 2
particles were considered as spherical and diameter of the spherical was
(a)). Moreover, torque further increases with the addition of peroxide
examined using image J analyzer tool.
for TPV development because of the formation of partial crosslinks of the
rubber phase Fig. 2(b).
2.3.5. Rheological measurement
The rheological measurements of individual polymers and the
developed thermoplastic elastomeric materials (TPEs and TPV) were

3
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

Fig. 2. Torque-time of mixing at 140 ◦ C along with rotor speed was 80 rpm (a) individual polymers and their blend compositions (TPU/GECO) (w/w), increase in
torque is observed with increase in GECO content (b) TPE vs TPV (50 TP/50G) (w/w), higher torque is observed after dynamic vulcanization.

3.1.1. Theoretical analysis for mixing torque
To predict the interaction between the phase constituents, theoret­
ical torque for mixing was analysed on a basis of volume fraction of both
thermoplastic phase (φ1) and rubber phase (φ2) by using the given
equation -
Q = Q1 φ1 + Q2 φ2
where, Q1 and Q2 denotes the experimental torque values for the ther­
moplastic phase and elastomeric phase, respectively obtained from
Haake Rheomix. Theoretical values and experimental values of torque
are given in Table 2. From the torque values of all the blend composi­
tions, it was perceived that the experimental torque value was higher
than the theoretical value of torque. The variance in torque value is due
to the interaction between TPU and GECO during melt mixing which
increases the molecular weight and leads to increased melt viscosity.
It was observed that with an increase in the rubber loading, positive
deviation in the torque value increases which indicates that with in­
crease in the rubber content, the interaction between the TPU and GECO
increases. With 50% of GECO content by weight percent in the blend,
maximum positive deviation was observed (~95%) which is almost
double the theoretical torque. Interaction between TPU and GECO was
further evident and predicted from FTIR (discussed in the forthcoming
section).
3.2. FTIR analysis
polymer used in this blend system is GECO, it is a terpolymer having
ethylene oxide (EO), allyl glycidyl ether (AGE) and epichlorohydrin
(CO). The functional groups present in TPU and GECO are given in
Table 4.
A large number of N–H and C=O bonds exist in TPU, and it has been
shown that there is a presence of broad peak at 3332 cm− 1 because of
(5)
N–H stretching in urethane group available in thermoplastic poly­
urethane. It was found that this peak shifted to a lower wave number
(~3318 cm− 1) in the blend and shifted to further lower wave number
with an increase in the content of GECO in the blend as shown in Fig. 4 a-
b. The reason for this shift is perhaps due to the interaction between TPU
and GECO and the formation of possible H-bond between N–H group of
TPU and oxygen molecules present in the backbone chain of GECO. With
the formation of hydrogen bonding the intensity of hydrogen bonded
C=O group also decreases resulting in a shifting of peak to lower
wavenumber, from 1698 cm− 1 to 1684 cm− 1 as depicted in Fig. 4(c).
Based on FTIR analysis, three possible H-bonding interactions between
TPU and GECO are proposed Fig. 5(a-c) [43]:
a) H bonding interaction between N–H group of TPU with oxygen atom
present in ethylene oxide (EO)
b) H bonding interaction between N–H group of TPU with oxygen atom
present in epichlorohydrin (ECO)
c) H bonding interaction between N–H group of TPU with oxygen atom
present in allyl glycidyl ether (AGE)

Infrared spectroscopic analysis is a useful technique widely used to 3.3. Mechanical properties
recognize interaction within the polymer systems [41,42]. It was evident
from mixing torque that significant interaction took place between TPU The tensile stress-strain behavior of prepared immaculate TPU and
and GECO. This has been further verified from FTIR studies. The amine their blend constituents are depicted in Fig. 3(a). Interestingly, tensile
group of TPU has the ability to interact with another polymer. Another stress vs strain graph of the developed materials showed absence of a
yield point prior to failure which is a typical nature of TPE. The curves
for all the blend compositions showed typical trend of thermoplastic
Table 2
Theoretical and experimental values of torque for TPU/GECO at mixing of 7 elastomers. It was noted that the compositions possess slight reduction
min. in strain percentage with enhancement in GECO content from ~1000 to
~800%, but no significant decrease in modulus was observed. In TPU,
Blend Experimental Theoretical Increment/ Increment/
Compositions torque value torque Deviation Deviation orientation of hard and soft segment increases the crystalline phase thus
(w/w) (Nm) value (Nm) of torque of torque results into higher stress values. Moreover, orientation of amorphous
(Nm) percentage phase of polyethylene oxide in TPU also causes ether moieties to gain
90TPU/ 26.6 24.8 1.8 7 high value for strain at break along with higher tensile strength. There is
10GECO an increment in tensile strength and Young’s modulus with an increase
80TPU/ 31.1 25.4 5.7 22 in the TPU content from ~3.8 to ~6.3 MPa. Moreover, for improving the
20GECO
elasticity and modulus of the resulting material dynamic vulcanization
70TPU/ 34.3 27.1 7.2 33
30GECO was performed for 50 TP/50G (w/w) blend composition. For unvul­
60TPU/ 39.2 20.5 18.6 91 canized sample, the strain at break was around 800% however, after
40GECO dynamic vulcanization strain at break was around 900%. This high
50TPU/ 47.3 24.2 23.1 95 elasticity and stretchability of TPV are originating from the reduction of
50GECO
domain size of rubber domain and its crosslink density. The tension set

4
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

Fig. 3. Mechanical properties of pristine polymer and blend compositions (a) stress vs strain plot, indicates that with increasing percentage of TPU there is slight
increase in stress and strain value, (b) stress vs strain plot showing TPV is having high stress-strain value as compared to TPE, (c) cyclic stress-strain curve for TPE and
TPV (50TPU/50GECO w/w).

Fig. 4. (a) FTIR spectra of TPU, GECO and their blend in the range from 4000 to 400 cm− 1, (b) FTIR spectra showing shift in N–H stretching due to interaction
between TPU and GECO in the range from 3800 to 3000 cm− 1 and (c) FTIR spectra showing shift in carbonyl group present in TPU.

value for unvulcanized and dynamically vulcanized samples was 3% and
2%, respectively. Table 3 depicts the mechanical properties of the
developed blend compositions.
Incorporation of GECO significantly reduces the tension set, this in­
dicates that there is improve in tendency to recover its original shape
after prolonged deformation. It can be recorded that hardness increases
with an increase in TPU content. The tension set for all the developed
compositions was lower than 15% and hardness value was in the range
of 50–75 shore A. Surprisingly, lower tension set (~2–10%), along with
high elasticity reflects the super elastic and ultra-stretchable nature of
the developed thermoplastic elastomeric materials.
Cyclic tensile test was performed as cyclic recovery gives details
about permanent residual strain and hysteresis of materials; this is
related to the elasticity of the specimen. In Fig. 3(c), it was observed that

5
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

Fig. 5. Hydrogen bonding interaction between TPU and GECO (a) urethane and oxygen atom of ethylene oxide (b) urethane and oxygen atom of epichlorohydrin (c)
urethane and oxygen atom of allyl glycidyl ether.

Table 3
Mechanical properties of pristine polymers and their blend compositions.
Specimens Young’s Modulus (MPa) Elongation at Break (%) Modulus @ 100% Elongation (MPa) Tension set % Hardness (Shore D) Hardness (Shore A)

100 TP 6.3 ± 2 990 ± 20 3.7 ± 0.5 9 ±1 24 ± 1 72 ± 1

90 TP/10G 5.8 ± 2 950 ± 25 3.5 ± 0.5 8±1 22 ± 1 68 ± 1
80 TP/20G 5.6 ± 1 900 ± 20 2.7 ±1 7±2 19 ± 2 65 ± 1
70 TP/30G 5.2 ± 2 884 ± 20 2.6 ± 0.5 6 ±1 19 ± 1 63 ± 2
60 TP/40G 4.5 ± 1 838 ± 25 1.8 ±1 4 ±2 18 ± 1 62 ± 1
50 TP/50G 3.8 ± 1 (6.2 ± 2)* 798 ± 20 (900 ± 20)* 1.7 ± 0.5 (2.6 ± 1.2)* 3 ± 1 (2 ± 1)* 16 ± 2 (19 ± 2)* 54 ± 1 (63 ± 2)a
a
Values for dynamically vulcanized blends.

the developed system showed very prominent stress induced softening

Table 4
in TPE system which was further reduced in TPV. It was observed that
Functional group present in TPU and GECO.
hysteresis loop is smaller in TPV as compared to TPE this is because of
Wave number (cm− 1) Functional group the presence of partial crosslinks in the dispersed phase of TPV which
(a) TPU 3332 N–H stretching absorption of amide accounts for lower energy loss and certainly smaller hysteresis loop.
2970 CH2 stretching Residual strain of TPV was also lower compared with TPE, as TPV
1728 C=O stretching
showed more elastic nature and viscous component is lower which is
1597–1412 C=C benzene ring bending
(b) GECO 2872 O–H stretching comparable to filled elastomer as well as it is reprocessable.
1458 CH2 bending vibrations
742 C–Cl stretching
3.4. Dynamic mechanical analysis

Fig. 6 (a) represents the plot for tan delta as a function of temperature
of pristine polymers and their blend compositions over a temperature

Fig. 6. DMA plot of pristine polymers and blend compositions (a) tan δ vs temperature plot, (b) storage modulus as a function of temperature.

6
P. Awasthi and S.S. Banerjee
span of − 70 ◦ C to +70 ◦ C. In the prescribed temperature span, for TPU
prime transition was observed at − 30 ◦ C and designated as the glass
transition (Tg) temperature and it also shows second transition at 13 ◦ C
because of the transition phase of hard segment. Similarly, main tran­
sition of GECO was observed at − 25 ◦ C which is due to glassy to rubbery
transition. For blend system there is shift in Tg value and it was observed
that a single Tg of blend compositions is around − 27 ◦ C, which is in
between Tg of pristine polymers. This clearly reveals the interaction
between TPU and GECO.
The storage modulus is an analysis of stored elastic energy, it rep­
resents the presence of elastic segment in the material. Fig. 6 (b)
Fig. 7. SEM micrographs of TPU/GECO blends (a) 50 TP/50G (w/w), (b) 50TPG (P) (w/w), (c) 70 TP/30G (w/w), (d) 80 TP/20G and distribution of size of
rubber particle.
7
Polymer 252 (2022) 124914
indicates that below Tg value, pure TPU exhibits the lowest value for
storage modulus, which indicates that it has lowest capability to store
energy. With increasing GECO content storage modulus increases indi­
cating an increase in elasticity. The increase in storage modulus is
because of strong interfacial interaction within GECO and TPU. After Tg
value there is decrease in storage modulus because with enhancement in
temperature amorphous region becomes mobile and there is sharp
decrease in storage modulus. The shift in trend of storage modulus after
Tg was observed, GECO exhibits lowest storage modulus whereas TPU
exhibits highest storage modulus. Because, TPU is having hard crystal­
line segment, crystalline phase does not possess sharp decrease in
P. Awasthi and S.S. Banerjee
modulus beyond Tg value. Beyond 30 ◦ C rubbery plateau is recorded
after the melting of crystalline phase present in pristine polymers.
3.5. Morphology
Microstructure and interfacial chemistry highly influence the per­
formance of multiphase polymeric systems. The morphology of TPU/
GECO blend of different blend compositions is given in Fig. 7 along with
the rubber particle size distribution.
The significant factors which influence the morphological properties
of blend are blend constituents, viscosity ratio (ratio of viscosity of
dispersed segment to matrix phase), shear rate applied during mixing,
elasticity, incorporation of additives like plasticizers or fillers and
interfacial modification. Torque curve during mixing indicates that
viscosity of GECO was higher than the viscosity of TPU. TPU being less
viscous could form the continuous phase and high viscous GECO would
form the dispersed phase. Interestingly, it was observed that the size of
the dispersed GECO particles in TPU matrix was observed to be uni­
formly distributed in the nanometer range for all the compositions
(260–480 nm). For 50 TP/50G (w/w) composition the number-average
particle diameter, dn of dispersed GECO segment was found ~475 nm
and for 80 TP/20G (w/w), dn was around ~270 nm. It was reported that
average diameter of particles was increasing with increase in weight
percentage of rubber.
In Fig. 7 (b) it is shown that diameter of dispersed rubber particles in
dynamically vulcanized sample is much smaller than their unvulcanized
counterpart. For dynamically vulcanized sample dispersed particles size
was further reduced to ~240 nm. For dynamically vulcanized sample
number-average particle diameter, dn of dispersed segment was reduced
to ~235 nm when compared to unvulcanized counterpart. In dynami­
cally vulcanized samples there is formation of partial crosslinks which
results in increased viscosity of rubber phase. The increased viscosity
exerts high shear stress, this will cause highly extensive breakdown of
dispersed GECO particles in the TPU matrix. This will lead to formation
of reduced particles of rubber, thus providing lower diameter.
3.6. Theoretical analysis of complex modulus
Theoretically existing Kerner model [44] was imposed to analyze the
behavior of TPE’s bi-phasic system. Kerner model is based on the
two-phase blend where one phase forms the matrix and another phase
serves as dispersed component. Plot given in Fig. 8 shows the complex
moduli of the blend compositions at 30 ◦ C and theoretically measured
values for the complex moduli of the blend compositions based on the
Kerner’s model. Kerner’s equation is-
Fig. 8. Theoretical and experimental plot for complex moduli of TPU/GECO
blend compositions as a function of volume fraction of GECO at room tem­
perature (30 ◦ C).
8
Polymer 252 (2022) 124914
E* (1 − φi )Em* + β(α + φi ) Ei*
= γ (6)
Em* (1 + αφi )Em* + αβ(1 − φi )Ei*
where,
2(4 − 5vm )
α=
(7 − 5vm )
E* denotes complex modulus of blend system, Em* & Ei* denotes the
complex modulus of the matrix and the dispersed segment respectively.
v, vm and vi depicts the Poisson ratio of the blend, matrix and dispersed
phase respectively. The Poisson ratio of blend system is a function of
temperature and is calculated using equation (4) [45]-
{0.17 log E* (glass) − log E* (T)}
v (T) = + 0.32 (7)
{log E* (glass) − log E* (rubber)}
Fig. 8, depicts that experimental value of complex modulus for the
TPU/GECO blends, almost coincides with the complex moduli found
from Kerner’s stiff matrix-soft filler model, which suggests that TPU
forms the continuous matrix. The results obtained from theoretical
calculation of Kerner’s model is in accordance with the morphological
studies that also confirms the continuous matrix is formed by TPU.
3.7. Rheological properties
Rheological measurements have been extensively used for analyzing
the structural changes and viscoelastic behavior in polymeric materials.
Time temperature superposition principle (TTS) is a fitting tool to
analyze the viscoelastic characteristics of polymer for wide range of
frequency and temperatures. Fig. 9(a) depicts the master curve of ab­
solute value for complex viscosity vs reduced frequency for pristine
polymers and their blends. For all the specimens it was observed that
there is continuous decrease in complex viscosity with enhancing fre­
quency, which reflects the shear thinning behavior and confirm the
characteristic of the pseudoplastic material. Polymer chains remains
oriented and in entangled form but with increase in shear rate chains get
disentangled and aligned which results into pseudoplastic behavior. It
was observed that GECO showed high shear thinning behavior than TPU
and with enhancing GECO content, complex viscosity for all the com­
positions increased in the intact frequency span.
It was observed from Fig. 9(b) that at lower frequency region (ω < 1),
absolute value of complex viscosity of dynamically vulcanized sample is
high as compared to the unvulcanized counterpart. Dynamic vulcani­
zation leads to partial crosslinking within the chains which results into
more entanglement and hence restricts the flow of material. Interest­
ingly, it was observed that after the crossover point at 0.82 rad s− 1 TPV
shows more shear thinning behavior than TPE. At lower frequency re­
gion, polymeric chains were in the relaxed state, long-range relaxation
was predominant hence complex viscosity was high. However, at high
frequency range small-range relaxation takes place as chains relaxation
got hindered. Length of the chain segment controlling rheological
behavior was smaller compared to the segmental length of the chain
present between two crosslinked points. Therefore, at higher frequency
region more prominent shear thinning was observed for TPV sample.
3.7.1. Interfacial tension between TPU and GECO
Interfacial tension within the TPU matrix phase and dispersed GECO
phase was estimated from the Palierne model [46,47]. Palierne model is
well-established model for determining interfacial tension within the
matrix and dispersed segment based on free energy of interface. Palierne
model is prominently valid for lower frequency range. Palierne and his
co-workers assumed that droplet-size distributive morphology is narrow
and interfacial tension does not depend on variation in interfacial area
and shear. Based on this assumption model was simplified to-
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

Fig. 9. Master curves of absolute value for complex viscosity (η*) vs reduced frequency (ω aT) of (a) Immaculate polymers (TPU and GECO) and their blend
compositions, (b) TPE vs TPV blend composition at reference temperature 150 ◦ C.

1 + 3φ2 H * (ω) / ( 2 ) ( 2 )
G*b (ω) = G*m (ω) (8) C1 = 40γ12 R(G′m + G′i ) + 38 G′ i − G˝2i + 48 G′ m − G˝2m
1 − 2φ2 H * (ω)
+ 89(G′m G′i − G˝m G˝i ) (17)
where G*b (ω) depicts the complex modulus for the TPU/GECO blend and
G*m (ω) denotes the complex modulus of the TPU matrix segment. The C2 = 40γ12 /R(G˝m + G˝i ) + 96G′m G˝m + 76G′i G˝i + 89(G˝m G′i + G′m G˝i )
complex moduli are obtained from frequency sweep experiments as a (18)
function of angular frequency (ω). The volume fraction of the dispersed / ( ) ( )
2 2
GECO segment is represented by φ2 .
2 2
C3 = 4γ12 R(2G′m + 5G′i ) − 16 G′ m − G˝m + 19 G′ i − G˝i
H* (ω) is defined by the following expression- − 3(G′m G′i − G˝m G˝i ) (19)

/ ( ) ( )( )
4γ12 R 2G*m (ω) + 5G*d (ω) + G*d (ω) − G*m (ω) 16G*m (ω) + 19G*d (ω)
H * (ω) = / ( ) ( )( ) (9)
40γ12 R G*m (ω) + G*d (ω) + 2G*d (ω) + 3G*m (ω) 16G*m (ω) + 19G*d (ω)

where G*d (ω) depicts the complex modulus of the dispersed GECO
segment at fixed value of ω. R is the radius of dispersed rubber phase,
obtained from SEM. γ 12 is the interfacial tension within the TPU and
GECO segment.
Here, it was assumed that deformation of dispersed rubber particles
is almost negligible for small amplitude oscillatory shear (SAOS).
Therefore, morphology will not change in SAOS test, according to this
assumption the real (Gʹb) and imaginary (Gʺb) components of complex
modulus, G*b (ω) of the blends in equation (10) is expressed by the
following equations-
G′ b = 1/D[G′ m (B1 B2 + B3 B4 ) − G"m (B4 B1 − B2 B3 )]
G"b = 1/D[G′ m (B1 B4 − B2 B3 ) + G"m (B1 B2 + B3 B4 )]
where B1, B2, B3, B4 and D are given by the following expression:
B1 = C1 − 2φ2 C3
B2 = C1 + 3φ2 C3
B3 = C2 − 2φ2 C4
B4 = C2 + 3φ2 C4
D = (C2 − 2φ2 C4 )2 + (C1 − 2φ2 C3 )2
where the constants C1, C2, C3 and C4 are expressed by the following
equations:
C4 = 4γ12 /R(2G˝m + 5G˝i ) − 32G′m G˝m + 38G′i G˝i − 3(G˝m G′i + G′m G˝i )
(20)
Now the real (Gʹb) and imaginary (Gʺb) components of complex
modulus can be summarized using equation (21) as follows:
G′b , G˝b = f (G′m , G˝m , G′i , G˝i , R, γ12 , φ2 ) (21)
The parameters (G′m ,G˝m ,G′i ,G˝i ,R,φ2 )
was obtained experimentally.
The dynamic modulus of the blends was determined using the equation
(21) once the phases of dynamic modulus (real and imaginary parts),
volume fraction of the dispersed segment, radius of the dispersed phase
and interface tension are known without any fitting parameters. For
(10) TPU/GECO blend compositions, theoretical curves are fitted with the
experimentally obtained data. The corresponding value of γ 12 where best
(11) fitting of dynamic modulus is obtained with experimental data is
considered as interfacial tension parameter. The sensitivity for the Pal­
ierne model predictions to that of interfacial tension of the 50 TP/50G
(12) based TPE and 50 TP/50G based TPV is shown in Fig. 10 and the fitting
results were found in close proximity with experimental results. The
(13) radius of particles, used to predict the interfacial tension in this case is
Rv = 490 nm for 50 TP/50G based TPE and for 50 TP/50G based TPV, Rv
(14) = 240 nm. It was assumed that there is no change of blend morphology
at small oscillatory shear stress during the frequency sweep experiments.
(15) It has to be mentioned that the Palierne model is applicable for narrow
domain size distribution (Dv/Dn ≤ 2). It was revealed that for TPU/GECO
(16) blend γ12 amounted to 1.8 × 10− 3 N/m and for dynamically vulcanized
sample γ12 is 1.0 × 10− 3 N/m. Lower interfacial tension could be
beneficial to transfer to stress between the phases. In earlier works, it
was outlined that domain size of dispersed elastomer particles and

9
P. Awasthi and S.S. Banerjee
Fig. 10. Palierne model prediction (red circles) of absolute value of complex modulus of TPU/GECO blend having 50 wt% GECO (a) unvulcanized blend (b)
dynamically vulcanized blend. (For interpretation of the references to color in this figure legend, the reader is referred to the Web version of this article.)
interfacial tension is directly proportional [15]. Smaller value for
interfacial tension is result of the stronger interaction between the
components of blend which was confirmed by infrared spectroscopy,
DMA tan delta plot and mixing torque curve.
3.7.2. Melt elasticity
The first normal stress difference (N1) and apparent elasticity (G) are
considered the proportion of elastic energy stored in a viscoelastic ma­
terial which has strong influence on the ultimate properties of a poly­
meric material. The normal stress difference calculation and apparent
elasticity are important for TPE as they influence the rheological
behaviour and performance of final material under different frequency
based on viscous and elastic part available within the TPE structure. The
detailed calculation of melt elasticity parameters is provided in SI. The
representative melt elasticity curve (first normal stress difference, N1 vs
reduced frequency ω aT and apparent elasticity € vs reduced frequency ω
aT) is shown in Fig. S1. It was revealed that melt elasticity of TPU
enhanced with incorporation of GECO content within the tested fre­
quency range. High values of N1 and E represents the high elasticity of
polymer melts which might be responsible for improved elastomeric
properties of blend compositions. Apparent elasticity high value reveals
that TPE melt exhibits high elasticity which can be applied in the ap­
plications where high strain value will be required.
3.8. Hydrophilic behavior
3.8.1. Water absorption characteristics
Water absorption in a polymer generally takes place because of two
Fig. 11. Water absorption characteristics of (a) pristine polymers and blend compositions, water uptake decreases with increase in GECO content (b) TPE and TPV of
50 TP/50G (w/w), dynamically vulcanized samples show lower water uptake.
10
Polymer 252 (2022) 124914
reasons, firstly, presence of hydrophilic units in backbone chain (-O-,
-NH- or –N ¼ ) as they possess lone pair electrons for hydrogen bonding
with water. Secondly, presence of hydrophilic side groups (-OH,
-COONa, –NH2, or –C=O [48]. From the chemical structure of TPU it is
evident that backbone chain of TPU consists of -O- and -NH- group and
from the chemical structure of GECO it is evident that backbone chain of
GECO consists -O-, whereas side chain of TPU and GECO consist of –OH
group, which is highly hydrophilic in nature and thus absorbs high
amount of water within few hours [49].
TPU and GECO absorb almost 80% and 5% of water to its dry weight
within 4 h, respectively. Water up taking characteristics of immaculate
and their blend compositions are given in Fig. 11(a–b) It was observed
that with an increase in the GECO content water absorption properties of
a composition decreases. Water uptake of dynamically vulcanized
sample was slightly lower than the unvulcanized sample because partial
crosslinks present in the TPV structure restricts the entry of water.
When polymer matrix cooled below 0 ◦ C some amount of absorbed
water converted into ice crystals. The proportion of non-freezing and
freezing water for different compositions was calculated from endo­
thermic ice defrosting profile of DSC plot. In Fig. 12(a–c) broad peak was
observed, this endothermic peak is because of the defrosting of
freezable-bound water and freely present water [50,51].
Total water content (Wt) in the polymer matrix was measured by the
sum of freezing water content (Wf) and non-freezing water content (Wnf).
Here freezing water denotes the fraction of both freezing bound and
freely present water in the matrix of a polymer.
Wt = Wnf + Wf (22)
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

Fig. 12. DSC plots of heat flow vs temperature showing formation of ice crystal at 0 ◦ C due to absorbed water (a) TPU curve (b) 50 TP/50G (w/w) blend and (c)
GECO plot.

Considering equal value for melting enthalpies of freely present and

Wt Q− 1
freezing bound water, the content of freezing water was calculated from Wg = = (26)
Ws Q
the given below equation-
The volume percentage of the ice-crystals formed within a matrix is
Wf ΔHs
=Q (23) calculated against total volume of the matrix using
Wd ΔH
Vol. of freezable water
where, Wd is dry sample weight, Q is the swelling ratio, ΔHs denotes the Volume % of the ice crystal=
Vol. of dry matrix + Vol. of total absorbed water
enthalpy of water-swollen sample and ΔH depicts the value of enthalpy
× 100
for whole water, which could be considered as -330J/g (the maximum
(27)
chances of error is less than 5% in the calculation of amount of freezable
water content because enthalpies for melting of different ice-crystals are In Table 5, the volume percentage of the entire ice-crystals obtained
not considered [52]). For tetragonal ice crystals enthalpy is lowest, 312 in-situ and the weight % of freezing water is provided.
J/g and in case of hexagonal ice crystals enthalpy value is highest, 334 From Table 5 it was observed that with an increase in percentage of
J/g. Value of ΔHs was calculated from DSC curve by integrating the peak absorbed water there is a steady increase in volume percentage of
areas for ice crystal melting. formed ice crystals. Maximum ice-crystals formed comprise of ~42%
Q, swelling ratio is calculated using the following equation volume percentage. TPU exhibits highest volume % of ice-crystals
because it absorbed the highest amount of water. Through the chemi­
Ws
Q= (24) cally constituent structure of TPU and GECO, one could anticipate the
Wd
intermolecular hydrogen (H) bonding between polar groups of polymers
where, Ws is weight of the swollen sample. The presence of non- and water molecules. Fig. 13 (a), represents the shifting of band of a
freezable water amount can be calculated using resultant bonded structure in an IR spectrum. The ATR spectrum of the
( ) water swollen sample showed concerted broad bands for stretching of
Wnf
= Q Wg −
ΔHs
(25) hydroxyl group at 3372 cm− 1, indicating presence of high water con­
Wd ΔH centration. According to chemical structure of TPU, oxygen molecule is
present in C=O stretching of TPU, high shift in band is observed from
and, 1694 cm− 1 to 1656 cm− 1 (~38 cm− 1) [53]. The shift in band is because
of water penetration into TPU. The high amount of shift could be used as
a definite sign of interaction between H2O molecule and carbonyl group.
Fig. 13(b), depicts the probable hydrogen (H)-bonding between the
Table 5 polymeric chain and H2O molecules. The polymeric backbone chain was
Melting profile of DSC and vol. % of ice crystals in matrix. obtained from predicted reaction between TPU and GECO as shown in
Sample Absorbed water ΔH (J/ Freezable Vol. % of ice Fig. 5. The suggested mechanism of water swollen TPE is given in Fig. 13
compositions (Ws/Wd) (wt%) g) water (Wf/Wt) crystal in (c). When the developed TPE is freezed, the ice-crystals were formed
(%) matrix
because of presence of freezable H2O molecule, as it is weakly-H bonded
100 TPU 87.8 ± 0.5 92.3 47.6 ± 0.5 42.3 ± 0.5 with polymeric chain.
±1
Cryo-TEM is accounted for profiling of frozen-hydrated samples at
80 TPU/20 77.1 ± 0.5 74.5 52.2 ± 0.5 34.8 ± 1
GECO ± 0.5 subzero temperatures. In the present work, solid ice crystals at cryogenic
50TPU/ 58.8 ± 1 67.8 56.8 ± 0.5 33.1 ± 0.5 temperature (− 170 ◦ C) in three different blend compositions 50 TP/50G
50GECO ± 0.5 (w/w), 70 TP/30G (w/w) and 90 TP/10G (w/w) with different water
100 GECO 11.8 ± 0.5 36.8 91.7 ± 1 13.5 ± 0.5 uptake levels ~60 wt%, ~70 wt% and ~80 wt% respectively, were
± 0.25
imaged through cryo-TEM [54]. The cryo-TEM image of the water

11
P. Awasthi and S.S. Banerjee Polymer 252 (2022) 124914

Fig. 13. (a) ATR-FTIR spectra of TPU and GECO blend system at room temperature, (b) hydrogen (H) bonding interaction between polymeric chain and the water
molecules and (c) schematic representation of TPE and water molecule interaction.

Fig. 14. a–c(i) Ice-crystals formation visualization in cryo-TEM profile of water immersed 50 TP/50G (w/w), 70 TP/30G (w/w) and 90 TP/10G (w/w) respectively,
(a–c)(ii) elemental mapping of carbon and oxygen in accordance with (a–c)(i), and (a–c)(iii) SAED image of ice-crystal composite.).

12
P. Awasthi and S.S. Banerjee
immersed samples are given in Fig. 14(a-c). It was noted that, elliptical
and convex designed ice-crystals are invariably present throughout the
matrix. The ice-crystals were formed due to condensation of air hu­
midity at outer surface of the sample. Energy filtered transmission
electron microscopy (EFTEM) technology was simultaneously used to
detect the chemical constitution of the cryo-TEM visualized sample.
Elemental mapping of oxygen and carbon from the EFTEM measure­
ments are provided in Fig. 14 a-c (ii). The green color signifies presence
of carbon in polymeric chain and red color depicts the oxygen atom in
ice crystal (H2O). The existence of oxygen atom in polymeric chain is
recognized by red spots in green spots enriched areas. The oxygen
enriched areas (red) confirm the presence of ice crystals. Selected area
electron diffraction (SAED) pattern of water-swollen specimen yielded a
dot and band pattern, it was matching with the expected pattern for
poly-crystalline ice crystals, Fig. 14 a-c (iii). SAED pattern could be
indexed like (002), (101), (102), (103) and (201) planes, this confirms
the formation of hexagonal ice crystals, according to Ref. [35]. As the
weight percentage of TPU is increasing in blend composition, there is
increase in water uptake level. It was evident that there is an increase in
the formation of ice-crystals with increasing water uptake percentage.
4. Conclusions
In summary, a series of new kind of super-elastic and hydrophilic
thermoplastic elastomeric materials were developed using TPU/GECO
blend system for the first time. A detailed mechanistic study was per­
formed to understand the hydrophilicity and elasticity of the resulting
materials. The developed materials can absorb up to ~80% water within
4 h and the absorbed water converted itself into the hexagonal ice
crystals in the TPE matrix which was directly evident from DSC and
cryo-TEM analysis. Theoretical calculation of torque, dynamic me­
chanical properties and infrared spectroscopy analysis confirmed that
the phase components of the developed TPE was highly interactive in
nature. Interaction was further enhanced after doing dynamic vulcani­
zation of GECO phase. Interaction between the phase components were
corelated with interfacial tension values which were obtained from the
Palierne model. Stronger inter-domain interaction between phase
components were obtained after dynamic vulcanization. Interestingly, it
was found that in comparison to TPEs reported earlier, developed
thermoplastic elastomeric materials showed outstanding elastomeric
properties which was demonstrated by their relatively higher strain at
failure (up to ~800–1000%), and lower tension set (<2–6%) values. The
improved properties were corelated and explained with the interaction,
melt elasticity and interfacial tension between the phase components.
This work provides an effective strategy for the creation of tailorable
hydrophilic and super-elastic thermoplastic elastomeric materials that
can influence the product reliability as well as credibility of TPEs in
certain applications where hydrophilicity and elasticity are the main
concern.
CRediT authorship contribution statement
Pratiksha Awasthi: Conceptualization, Data curation, Formal
analysis, Writing – original draft, Writing – review & editing. Shib
Shankar Banerjee: Conceptualization, Funding acquisition, Data
curation, Formal analysis, Writing – review & editing.
Declaration of competing interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgement
PA acknowledges financial support from the Ministry of Human
13
Polymer 252 (2022) 124914
Resource Development (MHRD), India.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.polymer.2022.124914.
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