Article

Journal of Thermoplastic Composite

Materials
Comparing of melt 1–21
ª The Author(s) 2015
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mixing methods on DOI: 10.1177/0892705715614068

jtc.sagepub.com

the physical properties

of thermoplastic
polyurethane/organoclay
nanocomposite films
Nevra Ercan, Ali Durmus and Ahmet Kaşgöz

Abstract
In this study, microstructural features and physical properties of thermoplastic poly-
urethane (TPU)/organoclay nanocomposites films prepared via melt blending (MB) and
solution mixing (SM) methods were investigated in detail. Amount of organoclay into the
composition varied in the range of 2 and 8 wt%. Microstructural properties of samples
were characterized by X-ray diffraction, scanning electron microscopy (SEM), and
transmission electron microscopy (TEM) methods. It was found that the organoclay
layers exhibited better dispersion, exfoliated, and semi-exfoliated structure in the MB
samples than the SM counterparts. Viscoelastic properties of samples were also studied
by measuring the rheological behaviors of bulk samples in an oscillatory rheometer in the
melt state and measuring of the time-dependent nonlinear creep behaviors of film
samples in a dynamic mechanical analyzer in the solid state. Gas and water vapor per-
meability (WVP) values of nanocomposite films were measured. Based on the melt
rheology measurements, it was found that the MB samples showed characteristic solid-
like behavior and higher improvement in storage modulus at low-frequency region.
Creep behaviors of samples were also quantified with the four-element Burger model. It
was found that the introducing of organoclay into the composition via MB method
yielded more improvement in the creep resistance, gas, and WVP values of films than the
SM counterparts, possibly due to the better dispersion of organoclay layers into the TPU

Department of Chemical Engineering, Engineering Faculty, Istanbul University, Avcilar, Istanbul, Turkey

Corresponding author:
Nevra Ercan, Department of Chemical Engineering, Engineering Faculty, Istanbul University, Avcilar, Istanbul
34320, Turkey.
Email: [email protected]

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2 Journal of Thermoplastic Composite Materials

structure. Based on the improvement in permeability and mechanical properties of the

samples and also SEM and TEM observations, the average aspect ratio value (Af) of
organoclay stacks was estimated in the range of 15–20 for the MB samples.

Keywords
Polyurethane, nanocomposite, rheology, creep, gas permeability

Introduction
Reinforcing of polymers by introducing of organic or inorganic nanofillers has been
attracted considerable attention in a last few decades since the relatively low amount of
nanosize fillers can effectively enhance the thermal, mechanical, and barrier properties
of composites by using of relatively lower nanofiller amounts compared to polymer
composites including conventional macro-size fillers. Natural or organically modified
clay (organoclay) is one of the most abundant and widely used nanofillers to prepare
polymer nanocomposites showing superior physical properties. Physical properties of
polymer/clay nanocomposites (PCNs) depend on several compositional parameters such
as amount of filler, structural features of components, dispersion quality of clay layers
into the polymer structure and orientation issues, interfacial interactions, and so on.1–6 It
is generally accepted that the better dispersion of clay layers yields more enhancement in
the physical properties of PCNs.7
Clay or organoclay filled polymer nanocomposites can be prepared by in situ poly-
merization, melt processing (or blending, MB) and solution mixing (SM) methods. The
MB is the most widely used and convenient method to prepare thermoplastic nano-
composites compared to other methods because it is simple, industrially favorable, low
cost, and environmentally friendly. It is also known that the processing method strongly
affects the distribution and dispersion of clay layers, interfacial interactions, and
resulting structural and physical properties of PCNs.8–12 Müller et al. investigated the
effects of preparation method on the structure and mechanical properties of thermo-
plastic starch/Naþ-montmorillonite nanocomposite films prepared by SM and MB
methods.13 They reported that the introducing of relatively higher amounts of clay
(above 10 wt%) yielded aggregated structure in the melt-processed samples. Berti et al.
compared the dispersion of clay layers into poly(butylene terephtlate) structure prepared
by in situ ring-opening polymerization and melt-processing methods.14 They found that
the in situ polymerization lead to higher degree of dispersion and resulted in better
thermomechanical properties. In another study, Furlan et al. studied on the effects of
melt-processing conditions on the mechanical, thermal, and morphological properties of
polypropylene (PP)/montmorillonite nanocomposites at clay content of 5 wt% by using
of different screw configurations consisting of low, medium, and high shear intensity.15
They reported that the higher property enhancement was obtained by the medium shear
intensity screw profile. Numerous attempts such as chemical modification of clay surfaces,
using various types of additives and compatibilizers with different functional groups to
improve the interfacial interactions between polymer matrix and fillers, applying different

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Ercan et al. 3

processing routes, reactive blending, or extrusion, using supercritical conditions, and so on,
have also been extensively studied to obtain exfoliated PCN structures.16–21
Thermoplastic polyurethane (TPU) is one of the most versatile elastomers, consisting
of alternatingly arranged hard and soft segments and exhibiting different physical
properties depending on the its segmental structure. Some studies have been reported on
the preparation and characterization of physical properties of TPU/organoclay nano-
composites.22–26 In recent years, many of TPU/clay nanocomposites works have focused
on the subjects related to the formation of foam structures and surface coating films
which exhibit enhanced thermal stability and flame retardant properties, and/or utili-
zation of bio-based raw materials.27–34 Meng et al. prepared TPU/octadecyl ammonium
chloride modified montmorillonite (OMMT-C18) nanocomposites by using maleic
anhydride-grafted polypropylene (MAPP) as pre-intercalation agent.35 In the first step,
MAPP was blended with the OMMT-C18 at different ratios in in the melt state. Then,
this mixture was melt mixed with the TPU. They suggested that the pre-intercalation of
lower molecular weight MAPP into clay layers was an effective processing strategy for
exfoliation of clay layers into the TPU matrix.
In this study, TPU/organoclay nanocomposite films including various amount of
organoclay were prepared by MB and SM methods. Effects of preparing methods on the
morphological and physical properties of nanocomposite films were quantified, in detail.

Experimental
Materials
TPU used in the study was a polyester-based polyurethane (Desmopan1 3380A, shore
hardness: 80A, d: 1.16 g cm3) kindly donated by Bayer (Turkey). The clay was a
commercial organoclay (Cloisite1 30B) supplied from the Southern Clay (USA). The
Cloisite 30B is a methyl, tallow, bis-2-hydroxyethyl, quaternary ammonium (MT2E-
tOH) salt modified montmorillonite. Organic content of the Cloisite 30B was declared as
30% by the manufacturer. The TPU and organoclay were dried at 80 C in a vacuum oven
overnight before processing. An analytical grade tetrahydrofuran (THF; Sigma-Aldrich,
St Louis, Missouri, USA) was also used as solvent.

Sample preparation
The TPU/organoclay nanocomposites were prepared by MB and solution casting methods.
Sample compositions are given in Table 1. MB was carried out in a lab-scale corotating
twin screw extruder (Rondol Micro Lab., UK; D: 10 mm, L/D: 20) with a screw speed of
50 r min1. Extruder screws were configured with the segments including 3-D of 4  60
followed by 2-D of 4  90 kneading units. A temperature profile of 110–150–160–175–
175 C was applied throughout the barrel from the feeding zone to die. A slit die and cast
film haul-off unit were used to prepare film samples for the subsequent microstructural
analysis and physical tests. The TPU was also processed under the same conditions.
In SM process, a 10 wt% of TPU solution was first prepared in THF. Then the proper
amount of organoclay, suspended in the same solvent under the sonication for 15 min,

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4 Journal of Thermoplastic Composite Materials

Table 1. Sample compositions and intergallery distances between organoclay layers.

wt%

Samples TPU Organoclay d001 (nm)

TPU 100
Organoclay 100 1.85
MB 2 98 2 –
MB 5 95 5 –
MB 8 92 8 –
SM 2 98 2 –
SM 5 95 5 3.32
SM 8 92 8 3.60

TPU: thermoplastic polyurethane; SM: solution mixed; MB: melt blended.

was added into the TPU solution and stirred with a magnetic stirrer for 30 min. This
mixture was also sonicated for 30 min then casted onto Teflon1 petri dishes. The TPU/
organoclay mixture was dried to constant weight and subsequently under vacuum at
50 C for 24 h to ensure for removing of solvent.

Characterization of sample microstructure by XRD, SEM, and TEM analysis

X-ray diffraction (XRD) analysis of the film samples were performed with a Rigaku D/Max-
2200/PC model (Japan) wide angle x-ray diffractometer with a copper K, running at 40 kV
and 40 mA, scanning from 2 to 35 with the step of 0.1 at room temperature. Intergallery
distance between clay layers in nanocomposites was calculated by the Bragg’s equation:
 ¼ 2d Sin ; ð1Þ
where d is the intergallery distance between the layers of clay,  is the wavelength of
X-ray (0.154 nm), and  is the diffraction angle.
Morphological features of nanocomposite films were investigated by a field emission
scanning electron microscope (model Quanta 450 FEG, FEI Co., USA) operated at 20
kV. Cryofractured surfaces of the samples were directly imaged in the microscope after a
proper sample preparation of sputter-coated with gold.
Microstructural properties of the samples were also studied with a transmission
electron microscope (model Tecnai G2 Sphera, FEI Co., USA). Ultrathin test specimens
(thickness about 150 nm) were prepared by cryoultramicrotomy method using liquid
nitrogen and diamond knife. Test specimens were placed onto a TEM grid then dried and
imaged in the instrument.

Rheological measurements
Viscoelastic behaviors of the TPU and nanocomposite samples were analyzed by a
dynamic oscillatory rheometer in the melt state. A controlled stress rheometer (AR-G2;

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Ercan et al. 5

TA Instruments, New Castle, Delaware, USA) equipped with 25-mm diameter parallel
plate geometry was employed for the rheology tests. Melt rheology tests were performed
at 170 C with a gap distance of 1 mm under inert atmosphere by employing nitrogen gas.
First, strain sweep test was carried out in the strain range of 0.1–50% with the angular
frequency of 1 rad s1 to detect the linear viscoelastic limits of samples. The storage (G0 )
and loss modulus (G00 ) values of samples were monitored as a function of shear strain
(%). In frequency sweep test, a small amplitude oscillatory shear was applied to the
samples and the G0 and G00 were measured as a function of angular frequency (!) in the
frequency range of 0.1–100 rad s1 at a strain value in the linear viscoelastic region
(strain magnitude of 1%).

Dynamic mechanical analysis

Short-term creep behaviors of samples were tested in a dynamic mechanical analyzer
(DMA ExStar 6100, SII Nanotechnology, Japan). The dynamic mechanical analysis
(DMA) tests were performed in uniaxial tension mode at 25 C with the frequency of
1.0 Hz. The creep and recoverable strains (ε) were recorded as a function of time. A
constant stress (2 MPa) was applied to the samples for 60 min then the creep recovery
was followed for 60 min after removing the stress. Nonlinear, time-dependent creep
behaviors of samples were modeled with the four-element Burger model. Creep curves
of the samples were converted to stress–strain (SS) curves and the elastic modulus (E) of
test specimens which is analogous to the Young’s modulus in conventional tensile test
was determined.

Permeability measurements
Gas permeability tests of samples were performed according to the ASTM D 1434-82
standard,36 by using the manometric method with a permeability testing apparatus
(model GDP-C, Brugger Feinmechanik GmbH, Germany) at 25 C. Oxygen (O2),
nitrogen (N2), and carbon dioxide (CO2) gases used in gas permeation measurements.
Film thicknesses, measured with a digital micrometer, was about 100–120 μm and the
deviation was less than 5% in each test specimen. For each composition, three different
films were tested and the average p values were reported.
The water vapor transmission rate of the samples was carried out in a water vapor
transmission rate tester (Labthink Perme W3/30, China) under the conditions of 90%
relative humidity and 38 C, according to the ASTM E96-95 standard.37 Thickness
deviation of the test specimens was within the range of 5%.

Results and discussion

Sample microstructure by XRD, SEM, and TEM analysis
The XRD patterns of MB and SM TPU/organoclay nanocomposite samples were given
in Figure 1(a) and (b), respectively. Characteristic diffraction peak of d001 plane of
organoclay (Cloisite 30B) was found to be 2 ¼ 4.77 which corresponds to intergallery

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6 Journal of Thermoplastic Composite Materials

Figure 1. XRD patterns of the (a) MB and (b) SM samples.

SM: solution mixed; MB: melt blended; XRD: X-ray diffraction.

distance between the organoclay layers 1.85 nm as reported in the producer data sheet. In
Figure 1(a), it is seen that the diffraction peak belongs to the d001 plane of organoclay
was almost disappeared or shifted to undetectable diffraction angles below the 2 ¼ 2
for the MB samples including various amount of organoclay into the composition.
Similarly, no diffraction peak was observed for the SM-2 sample. On the other hand, the
diffraction peak of d001 plane of organoclay was clearly seen in the XRD patterns of
SM-5 and SM-8 samples. But, it is seen that the peak position was significantly shifted to
lower diffraction angles for the SM-5 and SM-8 samples which indicated the formation
of intercalated nanocomposite structure. Basal spacing of organoclay layers were
determined to be 3.32 (2 ¼ 2.66 ) and 3.60 nm (2 ¼ 2.45 ) for the SM-5 and SM-8
samples, respectively. Based on the XRD result, it could be suggested that the TPU
chains can easily diffuse to intergallery spaces of organoclay layers by the MB method

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Ercan et al. 7

Figure 2. SEM images of the (a) MB-8 and (b) SM-8 samples.
SM: solution mixed; MB: melt blended; SEM: scanning electron microscopy.

without a compatibilizer. This could be attributed to contributions of interactions

between the hydroxyl (–OH) groups of intercalant molecule of Cloisite 30B and polar
segments of polyurethane and the effect of intensive shear forces on the organoclay
particles to provide peeling apart of clay stacks during melt processing. But, the SM
method yielded less sufficient dispersion for the clay layers at specifically relatively
higher organoclay contents possibly due to short mixing time and re-agglomeration of
particles during solvent evaporation as previously reported.38
Figure 2(a) and (b) shows the scanning electron microscopic (SEM) images of
cryofractured cross sections of MB-8 and SM-8 films, respectively. Sharp edges of
organoclay stacks, uniformly dispersed and embedded into the polymer matrix, are
clearly seen in these figures. Lateral sizes of stacks were found to be less than 1 μm.
Although no diffraction peak was observed for the MB-8 sample in XRD analysis, it
could be suggested that the MB-8 might exhibit both intercalated and partially exfoliated
structures by considering the SEM images of sample. Furthermore, no big holes or voids
were observed in the fractured cross-section of samples which implied the presence of
fairly strong interfacial interaction between the organoclay stacks and TPU.
Figure 3(a) and (b) shows the TEM images of MB-8 and SM-8 samples, respectively.
As seen in Figure 3(a), the MB-8 sample consists of both well-dispersed and partially
exfoliated clay layers and some few-layer stacks. On the other hand, the SM-8 sample
exhibits some large and possibly intercalated tactoids. Microstructural observations
based on the TEM images of samples are very consistent with the results obtained from
the XRD analysis and SEM study.

Rheological behavior of samples

Characterization of rheological behavior and viscoelastic properties of polymer com-
posites and blends in the melt state provides critical information to both understand the
processability and structure–property relationships of such materials. Moreover,

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8 Journal of Thermoplastic Composite Materials

Figure 3. TEM images of the (a) MB-8 and (b) SM-8 samples.
TEM: transmission electron microscopy; SM: solution mixed; MB: melt blended.

rheological measurements in the melt state can probe the behavior of relatively large
amount of material that is also useful from the macroscopic point of view.
Figure 4(a) and (b) demonstrates the dependence of G0 of MB and SM series of
samples on the shear strain, respectively. The storage modulus of samples exhibits a
linear region, called Newtonian plateau or plateau modulus, at low strains and nonlinear
region at high strain amplitudes. It is also clearly seen that the plateau modulus (G0 plt) of
the composites increases with the increasing amount of organoclay for both the series of
samples. This result typically implies the reinforcement effect of fillers on the storage
modulus of TPU. It was found that the extruded TPU (E-TPU) showed quite lower
storage modulus value (220 Pa) than the SM one (S-TPU) (1250 Pa) at Newtonian
region. This might be attributed to the fact that the molecular weight of TPU decreased
possibly due to the thermomechanical effects during melt processing. It can be clearly
seen in the Figure 3 that the SM samples exhibit higher G0 plt values than the MB
counterparts at a particular amount of organoclay loading. For instance, the G0 plt value of
SM-8 sample was about 8000 Pa while the value was about 1750 Pa for the MB-8. But, as
concluded in the previous part based on the XRD results, the MB-8 sample showed better
organoclay dispersion than the SM-8. It can be concluded that the reinforcing effect of
organoclay was suppressed by the random chains scissions and resulted loss in some
physical properties of TPU during melt processing even though the MB method yielded
better filler dispersion.
Dependence of G0 and G00 of samples on the angular frequency (!) are given in
Figure 5. Figure 5(a) and (b) shows the rheological behaviors of MB samples while the
Figure 5(c) and (d) illustrates those of SM ones. It is clearly seen that introducing
organoclay affects on both storage and loss modulus of samples and this effect is more
evident at low-frequency region, especially in the storage modulus curves. The mag-
nitude of the G0 increases and slope of the G0 decreases at low-frequency region with the
increasing organoclay amount into the composition. It is well known that the evaluating

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Ercan et al. 9

Figure 4. Dependence of storage modulus of (a) MB and (b) SM samples on the shear strain.
SM: solution mixed; MB: melt blended.

of low-frequency behavior of polymer nanocomposites depending on the composition

can be used to probe the microstructural features of such materials. Especially above a
certain fraction of organoclay which can be defined as the ‘‘percolation threshold,’’ G0
becomes frequency independent (G00  !0) at low-frequency region. This is also called
solid-like (or pseudosolid-like) behavior which indicates the formation of physical
network by the fillers and/or strong interactions between the filler and polymer phases.39
The solid-like behavior and the quantification of microstructure and rheological beha-
viors of samples were also reported for other nanocomposite systems.39–42
The values of reduced modulus (G0 R) can be plotted as a function of volume fraction
of organoclay (f) to compare the reinforcing effect of filler dispersion on the rheological
behavior of composites and estimate the percolation threshold of filler. The reduced
modulus can be defined as the ratio of low-frequency (! ¼ 0.1) modulus of composite to

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10 Journal of Thermoplastic Composite Materials

Figure 5. Dependence of storage and loss modulus of (a and b) MB and (c and d) SM samples on
the angular frequency.
SM: solution mixed; MB: melt blended.

that of neat polymer (G0 c/G0 p). This relationship is illustrated in Figure 5 for the MB and
SM series of samples. Two distinct regions where the rheological behavior of samples
changes from the liquid like to solid like can be clearly noticed in the plots. It can also be
distinguished that the storage modulus increases dramatically at a certain point of the
organoclay loading. After a particular amount of organoclay, increase in the G0 R follows
a power-law dependence with the volume fraction of organoclay. This critical volume
fraction is defined as the percolation threshold (p). Based on the melt rheology data,
determination of percolation threshold has not been speculated in this study, because
only three compositions were tested for each preparation method. But it can be roughly
concluded that the MB series of samples showed slightly lower percolation threshold
than the series of SM samples. The result given in Figure 6 provides an important
quantification to compare the effect of preparation method on the dispersion of orga-
noclay layers into TPU matrix. The melt rheology data of samples also implied that the
MB method probably yielded better dispersion therefore higher improvement in the low-
frequency modulus. This conclusion obtained from the analysis of rheological behaviors
of samples is very consistent with the XRD results.
Dependence of dynamic viscosity (*) of samples on the angular frequency (!) is
given in Figure 7(a) and (b) for the series of samples prepared with MB and SM methods,

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Ercan et al. 11

Figure 6. Plot of the reduced modulus (G0 R) versus volume fraction of organoclay (f) for the sam-
ples prepared with different methods.

respectively. The effects of amount and/or dispersion quality of fillers on the viscosity of
nanocomposite samples can be observed at low shear rate (or low frequency) region. It
was found that the * value of SM TPU (S-TPU) was higher than the extruded TPU
(E-TPU). This was possibly due to the thermomechanical effects of melt-processing
operation on the molecular weight of TPU, as discussed before.
As seen in Figure 7(a) and (b), it was found that the dynamic viscosity of
nanocomposite samples including of 5 and 8 wt% of organoclay, dramatically
increased at low-frequency region, which indicated the characteristic shear-thinning
behavior while E-TPU and S-TPU samples exhibited a Newtonian plateau (frequency-
independent behavior) at this region. The shear-thinning behavior can be accepted as
another indicator for comparing the level of filler dispersion and network formation for
PCNs.

Uniaxial tensile creep behaviors of film samples

Figure 8(a) and (b) demonstrates the uniaxial tensile creep behaviors of MB and SM
TPU/organoclay nanocomposite films including various amounts of organoclay,
respectively. All the samples exhibited a permanent, irrecoverable strain even though the
applied load was well within the linear region. It is also clearly shown that the intro-
ducing of organoclay into the TPU structure resulted in a considerable reduction in the
creep strain. This effect is more pronounced for the series of samples prepared with MB
in a twin screw extruder. The total creep strain of extruded TPU (E-TPU) was about 43%
while the SM TPU (S-TPU) exhibited the strain value about 25% for an hour. It is seen
that the nanocomposite samples prepared with the SM method yielded the creep strain
value about 13–18% depending on the amount of organoclay.

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12 Journal of Thermoplastic Composite Materials

Figure 7. Dependence of complex viscosity of (a) MB and (b) SM samples on the angular
frequency.

Creep deformation is defined as the time-dependent strain under a constant stress or

force. It is well known that perfectly elastic material responses instantaneously against an
applied stress but a viscoelastic material exhibits a time-dependent strain behavior. Several
mathematical approaches have been devoted to explain the viscoelastic creep behavior of
polymers. Each model uses the typical spring and dashpot elements connected with various
configurations to simplify elastic and viscous behaviors of a viscoelastic material. Find-
ley43 offered the simple equation for the relationship of creep strain and time:
"ðtÞ ¼ "0 þ mtn ; ð2Þ

where ε0 is the instantaneous strain, m is the amplitude of transient creep strain, and n is
the time exponent. The empirical approach does not provide a physical representation for
the creep deformation and recovery behavior under different loading conditions. Some
mechanical and molecular models have also been applied to analyze the creep responses

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Ercan et al. 13

Figure 8. Creep curves of (a) MB and (b) SM films. SM: solution mixed; MB: melt blended.

of viscoelastic materials. Findley parameters are listed in Table 2. It was found that the
MB samples showed lower instantaneous deformation values than the SM samples
which referred to better dispersion of clay platelet.
The Burger’s (or four-element) model, a combination of Maxwell and Kelvin–Voigt
elements, is one of the most used viscoelastic models to explain the creep behavior of
thermoplastic polymers and the microstructure–property relationships of the polymers
and composites.44 When a constant force is applied to a viscoelastic material, the
Maxwell spring, SM, instantaneously deforms. Then, the Kelvin spring, SK, and dashpot,
DK, deform by showing a delayed response followed by a continuous deformation of
Maxwell dashpot, DM. Total strain could be defined as the sum of the strains of Maxwell
and Kelvin elements:
  
  EK t t
"ðtÞ ¼ þ 1  exp þ ; ð3Þ
EM EK K M

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14 Journal of Thermoplastic Composite Materials

Table 2. The viscoelastic parameters predicted by the modeling of creep behaviors of samples.

Findley model Burger model

Samples ε0 (%) m (sn) EM (MPa) EK (MPa) K (MPas) M (MPas) (s) Recovery (%)

E-TPU 13.0 9.23 0.074 0.070 21 472 300 98

MB-2 6.5 6.81 0.111 0.121 47 903 388 96
MB-5 4.8 3.82 0.145 0.188 78 948 415 88
MB-8 3.5 4.01 0.169 0.196 94 1006 480 82
S-TPU 6.1 8.64 0.111 0.120 35 977 292 96
SM-2 10.2 3.06 0.142 0.170 60 1067 353 92
SM-5 10.9 1.55 0.163 0.230 85 1139 370 88
SM-8 10.2 0.79 0.183 0.290 136 1390 469 78

TPU: thermoplastic polyurethane; SM: solution mixed; MB: melt blended.

where  is the applied stress, EM and EM are the elastic and viscous components of
Maxwell element, spring, and EK and EK are the elastic and viscous components of
Kelvin element, dashpot. When the applied force is removed, the Maxwell spring, SM,
recovers completely. The Kelvin spring, SK, and dashpot, DK, show a delayed recovery.
But the Maxell dashpot, DM, exhibits a permanent deformation. Typical creep curve of a
viscoelastic solid shows such behaviors defined in three distinct regions on the curve
which are the immediate elastic deformation in spring, delayed viscoelastic deformation
in spring and dashpot and viscous deformation in dashpot.
In PCNs, better and/or uniform dispersion of clay layers or stacks and strong inter-
action between polymer and filler plays an important role on the improvement of elastic
behavior of polymers. The Burger’s parameters for the samples are also listed in Table 2.
The results showed that the organoclay improved the elasticity (EM) of TPU for the both
series of samples. Introducing of nanofillers into the polymer matrix increased the elastic
modulus of samples due to the physical interactions between the organoclay layers and
urethane (hard) and polyester (soft) segments of TPU. Similar behavior was reported by
Luduena et al. for polycaprolactone (PCL)/clay nanocomposites.45,46 The EM values of
SM series of samples were found to be slightly higher than those of MB series of samples
at a given organoclay amount while organoclay dispersion in MB samples was found to
be better than the SM ones for the organoclay amount of 5 and 8 wt%. Yang et al. studied
on the creep behaviors of polyamide 66 nanocomposites including various types of
nanofillers at three different temperatures and stress levels.47 They reported that the EM
values of nanocomposite samples were not altered much by the type of nanofiller at 20 C
but the increasing of test temperature and applied load decreased the EM values of
samples. The retardant elasticity (EK) and viscosity (K) are related to the stiffness of
amorphous polymer chains in the short time and dependent on the applied load and test
temperature. It was found that the viscoelastic parameters of Kelvin–Voigth unit, EK and
K, readily increased with the increasing amount of organoclay for the both series of
samples prepared with MB and SM methods. The MB samples showed lower EK and K
values than the SM samples. The ratio of K to EK is defined as the characteristic

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Ercan et al. 15

relaxation time ( ). As seen in Table 2, the values increased with the increasing amount
of organoclay. It was obtained that the relaxation time values of MB samples were
slightly higher than those of SM counterparts. This result could be attributed to the fact
that the better dispersion of clay layers into the TPU phase in the MB samples leads to
higher stiffness and thus restricted the mobility of polymer chains against to the applied
forces.
The irrecoverable creep strain parameter (M) is not dependent on temperature and
related to irreversible deformation of amorphous regions in polymer. The M values of
samples listed in Table 2 represents that the organoclay addition into the TPU matrix
increased the irrecoverable strain of matrix polymer.
Improvement in the elastic properties of composite sample depending on the amount
and physical features of fillers can be quantified by the empirical Halpin–Tsai (H-T)
model. The H-T equation is based on a well-known theory to predict the stiffness of a
composite material as a function of filler loading and aspect ratio by regarding the
micromechanical point of view.48,49 H-T equation is defined as:
Ec 1 þ 2Af μf
¼ ; ð4Þ
Ep 1  μf
where Ec and Ep are the elastic modulus of composite and polymer, respectively. Af
refers to the aspect ratio of the filler. f is the volume fraction of the filler and μ is the
geometric factor which can be written as:
Ef =Ep  1
μ¼ ; ð5Þ
Ef =Ep þ 2Af
where Ef is the elastic modulus of the filler. Modulus ratio of the filler and polymer
(Ef/Ep) is also defined as relative modulus (ER). As explained in the experimental part
(see section Dynamic mechanical analysis), the creep curves of the samples were con-
verted to SS curves and the E values of samples which can be taken as the analogous
values to the Young’s modulus in conventional tensile test were determined and used in
the H-T modeling study. The elastic modulus values of a clay platelet and TPU were
taken as 200 and 2.6 GPa, respectively.50
As shown in Figure 9, the H-T model predicts that the Ec increases almost linearly
with the increasing volume fraction of organoclay. It was found that the H-T model
successfully fits the experimental data obtained from the DMA analysis and the esti-
mated Af values were in the range of 15–30 for the series of samples. It is also clearly
seen that the Af values of samples decreases slightly with the increasing of organoclay
amount. This is possibly due to the increasing of filler–filler interactions and thus for-
mation of agglomerated structure.

Gas and water vapor permeability

It is known that the barrier properties of nanocomposites films depend on many para-
meters such as particle size, geometry, level of dispersion and orientation of nanofillers,
interfacial interactions between polymer and fillers, and structural properties of matrix. It

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16 Journal of Thermoplastic Composite Materials

Figure 9. Application of Halpin–Tsai micromechanical model to estimate the average aspect ratio
of organoclay layers.

can be accepted that the permeation properties of thermoplastic nanocomposites with the
amorphous polymer matrix such as polyurethane, polystyrene, polycarbonate, and so on,
completely depend on the properties and dispersion of nanofillers into polymer phase.
The theory suggested by Nielsen defines a relationship between the relative gas per-
meability and the aspect ratio (Af) and amount of non-spherical fillers.51 According to
the Nielsen approach, the impermeable and vertically aligned clay platelets against the
gas diffusion direction form a tortuous structure so that the gas molecules travel a longer
path to diffuse through the film. The Nielsen equation can be defined as:
Pc 1  f
PR ¼ ¼
; ð6Þ
Pp 1 þ A2f f

where PR is the relative permeability, PC and PP are the permeability values of nano-
composite and polymer films, and f represents the volume fraction which is calculated
according to the following equation:
1
f ¼ ; ð7Þ
f ð1Mf Þ
1þ
P Mf

where f and p are the densities of filler and polymer, respectively and Mf is the mass
fraction of filler.
Gas permeability values of film samples are given in Table 3. It is seen that the
oxygen, nitrogen, and carbon dioxide permeability values of both MB and SM series of
samples steadily decreased with the introducing of organoclay. The MB samples
exhibited noticeably smaller relative permeability values than the SM samples when
comparing samples with similar clay content. For example, introducing of 5 wt%
organoclay yielded to reduce 19%, 21%, and 9% in the O2, N2, and CO2 permeability,

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Ercan et al. 17

Table 3. Gas and water vapor permeability values of samples.

Permeability (cm3, 100 μ m2 day1 bar1)

Water Vapor Transmission Rate
Sample O2 N2 CO2 (WVTR) (g m2 day1)

E-TPU 877 348 2400 196

MB-2 836 291 2225 117
MB-5 707 275 2175 103
MB-8 626 220 2026 81
S-TPU 875 342 2400 209
SM-2 840 309 2282 147
SM-5 779 284 2278 125
SM-8 633 223 2105 95

O2: oxygen; N2: nitrogen; CO2: carbon dioxide; TPU: thermoplastic polyurethane; SM: solution mixed;
MB: melt blended.

Figure 10. Nielsen model applied to O2 permeability data of samples for estimating the average
aspect ratio of organoclay layers.
O2: oxygen.

respectively, for the MB films. On the other hand, it was found that such amount of filler
leads to decrease 11%, 18%, and 5% in the permeability values of gases for the SM
samples.
Figure 10 illustrates the estimation of aspect ratio values of samples according to the
Nielsen’s model. It is seen that the average aspect ratio for the MB samples was higher
than the SM samples. This result suggests that dispersion of organoclay is better in the
MB samples than the SM ones.
The water vapor permeability (WVP) values of samples are also listed in Table 3. As
expected, WVP values decreased with the increasing of organoclay amount. It was found

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18 Journal of Thermoplastic Composite Materials

Figure 11. High-resolution SEM images of a clay stack embedded into the SM 8 sample.
SM: solution mixed; SEM: scanning electron microscopy.

that the MB samples displayed lower WVP values than the SM counterparts. This result
might be due to the better dispersion of organoclay layers into the polymer matrix and the
higher aspect ratio of clay stacks.
The estimated average aspect ratio value of a sample was confirmed by the analysis of
SEM image. Figure 11 shows an image of organoclay stack embedded into the TPU
phase and taken with the magnification of 100.000. It should be remarked that the SM-8
sample exhibited an intercalated structure, based on the XRD analysis. As seen in the
image, the lateral size and thickness of the stack were found to be about 700 nm and 45 nm,
respectively. These values yielded the average aspect ratio of 15–16. The XRD analysis
pointed out that the intergallery distance between organoclay layers was determined as
3.60 nm for the sample. Considering the thickness of 2:1 layer of montmorillonite is about
1 nm, it can be predicted that this stack consists of approximately 10 layers.

Conclusion
In this study, microstructural and physical properties of TPU/organoclay nanocompo-
sites prepared with MB and SM methods were quantified and compared. Based on the
XRD and SEM analysis, it was obtained that the film samples prepared with the MB
method formed exfoliated nanocomposite structure while those prepared with the SM
method exhibited intercalated structure. The uniaxial creep behaviors of the samples
indicated that the exfoliated samples showed higher creep resistance than the inter-
calated ones, related to the amount of organoclay and dispersion quality of organoclay
layers. It was also found that the MB films showed higher gas barrier performances
compared to the SM counterparts for a given amount of organoclay. Consequently, it can
be concluded that the TPU-based organoclay filled nanocomposite films showing

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Ercan et al. 19

exfoliated structure and superior physical performances can be prepared with the MB
method as an easy and environmentally friendly technique.

Declaration of Conflicting Interests

The author(s) declared no potential conflicts of interest with respect to the research,
authorship, and/or publication of this article.

Funding
The author(s) received no financial support for the research, authorship, and/or publica-
tion of this article.

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