03 Chapters PDF

1.
Introduction
1.1 Polymer blends
Polymer blend (PB) - A mixture of at least two polymers or copolymers.
Polymer blends are physical mixtures of two or more polymers with/without any
chemical bonding between them. The objective of polymer blending is a practical one of
achieving commercially viable products through either unique properties or lower cost than some
other means might provide. The subject is vast and has been the focus of much work, both
theoretical and experimental.
Property of polymer blends is superior to those of component
homopolymers. Blending technology also provides attractive opportunities for reuse and
recycling of polymer wastes. The various economic and property advantages accomplished by
blending are:
The opportunity to develop or improve on properties to meet specific customer needs
The capability to reduce material cost with or without little sacrifice in properties
Permit the much more rapid development of modified polymeric materials to meet
emerging needs by by-passing the polymerization step
Extended service temperature range
Light weight
The ability to improve the processability of materials which are otherwise limited in
their ability to be transformed into finished products
Increased toughening
Enhanced ozone resistance
Improved modulus and hardness
Improved barrier property and flame retardant property
Improved impact and environmental stress cracking resistance, etc.
In short, unique materials are generated through blending as far as its processability and
or performance are concerned. When two or more polymers are mixed, the phase structure of the
resulting material can be either miscible or immiscible. Due to their high molar mass, the entropy
of mixing of polymers is relatively low and consequently specific interactions are needed to
obtain blends, which are miscible or homogeneous on a molecular scale [1]. In the case of
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immiscible systems the overall physicomechanical behaviour depends critically on two

demanding structural parameters [2]: a proper interfacial tension leading to a phase size small
enough to allow the material to be considered as macroscopically homogeneous and an
interphase adhesion strong enough to assimilate stresses and strains without disruption of the
established morphology. Rubber plastic blends are commercialised as rubber toughened
plastics or as thermoplastics elastomers (TPEs). They bridge the gap between thermoplastics and
elastomers [3-9].
1.2 Types of Polymer Blends
1.2.1 On the basis of miscibility
Basically there are three different types of blends depending on the miscibility.
1. Completely miscible blends has got
H m <0 due to specific interactions.
Homogeneity is observed at least on a nanometer scale, if not on the molecular level.

This type of blends exhibits only one glass transition temperature (T g), which is in
between the glass transition temperatures of the blend components in a close relation
to the blend composition. A well-known example of a blend, which is miscible over a
very wide temperature range and in all compositions is PS/PPO
2. In partially miscible blends a small part of one of the blend component is dissolved in
the other part. This type of blend, which exhibits a fine phase morphology and
satisfactory properties, is referred to as compatible. Both blend phases are
homogeneous, and have their own Tg. Both Tg s are shifted from the values for the
pure blend components towards the T g of the blend component. An example is the
PC/ABS blends. In these blends, PC and the SAN phase of ABS partially dissolve in
one another. In this case interface is wide and the interfacial adhesion is good.
3. Fully immiscible blends have a coarse morphology, sharp interface and poor adhesion
between the blend phases. So these blends are of no use without compatibilisation.
Thee blends will exhibit different Tgs corresponding to the Tg of the component
polymers. Examples of fully immiscible blends are PA/ABS, PA/PPO, PA/EPDM
and PA/PP. Now these blends have become commercially successful, after being
efficiently compatibilised using suitable compatibilisers.
Figure 1.1. Polymer blend phase diagram

1.2.2 Thermodynamics of Miscibility
Majority of polymers are immiscible at molecular level as given by the laws of
thermodynamics. Given enough time, the internal disorder of the polymer system will eventually
result in phase separation on a macroscopic scale. The relative miscibility of polymers controls
their phase behaviour, which is of crucial importance for final properties. The rules governing
miscible behaviour of polymer blends are understood in a thermodynamic sense through the
Gibbs free energy of mixing, Gm. The free energy of mixing can be described in terms of
enthalpic and entropic contributions as
Gm= m S m
(1.1)
where, Gm is the free energy of mixing per unit volume and 2 is the volume fraction of
component 2, H m and S m are enthalpy and entropy of mixing respectively. H m is
independent of molecular weight and is a measure of energy change associated with
intermolecular interactions. As seen in Figure 1.2, G m for a binary mixture can vary with
composition.
Figure 1.2. Gibbs free energy of mixing for binary mixtures

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For a binary blend to be miscible, the following conditions should be satisfied: (i) The free
energy of mixing should be negative or zero and (ii) the second derivative of free energy
function with respect to volume fraction of major component should be positive.
Gm0
(1.2)
2
2
>0
(1.3)
2 Gm

These criteria are met by curve B for all compositions. Blends described by curve A violate
equation 1.2 and are completely immiscible. A system described by curve C is partially miscible,
in which a single amorphous phase can be formed at compositions to the left and right of the
minima of curve C. In miscible polymer blends, molecular level mixing of the components is
obtained and is characterized by a single- phase morphology. Immiscible blends do not satisfy
the conditions proposed in equations (1.2) and (1.3), and show a two-phase morphology. In the
case of partially miscible blends, the second criterion is not satisfied and will show either two
phase or single-phase morphology. However, the manifestation of superior properties depends on
the miscibility behaviour of homopolymers.
The term immiscible means that the Gibbs free energy of mixing, Gm is positive
whereas incompatible is defined with respect to properties and means that the properties of the
blend are inferior to those of pure polymers. But, most pairs of high molecular weight polymers
are immiscible or incompatible. Polymer-polymer miscibility depends on a variety of
independent variables, viz., composition, molecular weight, temperature, pressure etc. Another
generic term found often in blend literature is compatibility. Components, which resist gross
phase segregation and show desirable blend properties, are considered to have a good of
compatibility, even though they are immiscible in a thermodynamic sense.
1.3 Compatibilisation strategy
Compatibilisation is very useful for improving the dispersity in polymer
blends. It
reduces interfacial tension, facilitate dispersion, stabilize the morphology against abusive stresses
and strains (arising out of processing), enhance adhesion between phases and improve the overall
mechanical properties [10] of the products. The driving forces for the phase segregation of blend
components are gravity and interfacial tension. The rate of demixing depends on interfacial
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tension, viscosity and density differences [11-12]. Compatibilised blends are not necessarily
miscible blends, but blends that satisfy certain industrial criteria for usefulness, such as
satisfactory mechanical properties.
The key to solve problems of coarse morphology is to reduce interfacial tension in the
melt and to enhance adhesion between the immiscible phases in the solid state. One solution is to
select the most suitable blending technique so that a co-continuous or
interpenetrating phase
morphology can be obtained, which results in direct load sharing. The second solution is the
addition of a third homopolymer or block or graft copolymer or low molecular reactive
compounds, which is miscible with either of the two phases. This can be considered as non
reactive compatibilisation. The third way is to blend suitably functionalized [13] polymers,
which are capable for specific interactions or chemical reactions (reactive compatibilisation).
1.3.1. Physical Compatibilisation
In physical blending, the compatibilising agent is chemically synthesized prior to the
blending operation, and subsequently added to the blend components as a non-reactive
component. Owing to its chemical and molecular characteristics, the added agent is able to locate
at the interface, reducing the interfacial tension between the blend components (emulsification
effect) and promoting adhesion between the phases [14,15].
1.3.2 Reactive Compatibilisation
Although numerous chemical reactions are encountered in reactive processing, it is
possible to distinguish major classes such as bulk polymerization, reactive compatibilisation,
controlled degradation, coupling, grafting and functionalisation. All these types of reactions can
be classified under reactive processing. In reactive compatibilisation, copolymers can be formed
in-situ through covalent or ironic bonding duration melt blending. In this kind of reactive
compatibilisation, generally one phase contains reactive groups inherent in the polymer, while
the other has no inherent functionality. Reactive groups can be incorporated into the second
phase by adding to it a functionalized polymer, which is miscible. In some cases, both polymers
have to be functionalised.
1.4 Blends based on TPU and PP
Thermoplastic polyurethane and polypropylene form a highly incompatible blend due to
their large differences in polarity and high interfacial tensions. However, TPU/PP blends have
been prepared with an aim to reduce costs and improve the processability of polyurethane. The
mechanical, thermal and chemical properties of polyurethane are improved by blending it with
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the polyolefin. Polyurethane, in turn, increases the impact strength, adhesion, printability and
paintability characteristics of polypropylene.
Potschke et al. [16, 17] have studied the surface tension and interfacial tension of
different PU and PP polymers. The reported experimental values indicated that low interfacial
tension between polyether based TPU soft segment and PP results in better dispersion. Potschke
et al. [18-20] have also carried out PP/TPU blend study without compatibilisers. They reported
that, at similar viscosity ratios (d/m), blends with polyether based TPU produced a finer
morphology than blends with polyester based TPU, due to low interfacial tension between their
polyether based TPU soft segments and PP.
Lu et al. have studied TPU / PP based blends in the ratio of 70 / 30 with compatibilisers
like maleic anhydride- g- PP and primary / secondary amine g-PP [21, 22]. Song et al.
investigated the phase morphology of nanoclay-polyurethane nanocomposite by small angle xray scattering (SAXS) and atomic force microscopy (AFM) [23]. It was observed that with
increase in clay content, the surface energy of the polyurethane hard segments decreased from 45
dyne-cm /cm to 32 dyne-cm/cm for 3% wt nanoclay loading. This result suggested that organic
modification of nanoclay had a surface activation function to some extent. Compatibilisation can
be further improved by introducing functionalised PP (MA-g-PP) in the nanoclay containing
blends.
1.5 Scope and Objectives of the work
The aim of this work was to develop TPU-based blend nanocomposites with best overall
performance, using both blending and nanocomposite technologies. Thermoplastic polyurethane
is attractive because of its high abrasion resistance, tensile and tear strength, flexibility and shock
absorbing capabilities. However, it has certain disadvantages like high cost, moderate thermal
stability and mechanical strength, limitations in chemical resistance and processability. Maleic
anhyride -graft- polypropylene is well known as a compatibiliser for blends of polypropylene
and more polar polymers like nylon and polyurethane. The effect of MA-g-PP on the
dispersibility of organoclay was studied by determining the physical, mechanical and thermal
properties of the TPU/organoclay/PP blend nanocomposites. Cloisite 10A, a more hydrophobic
organoclay, when pre-mixed with TPU, is also thought to function as a compatibiliser for
TPU/PP blends because of its affinity for the non-polar PP. The probable mechanism is that it
brings down the surface energy of the TPU hard segments to reduce the interfacial tension due to
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the large differences in polarity between TPU and PP. 70/30 TPU / PP blend ratio was chosen
for these studies so that the main properties of TPUs like elastomeric property, abrasion
resistance, damping and low temperature flexibility are retained. The study mainly focused on
the effect of nanocaly (sequence of addition) and the role of compatibiliser (MA-g-PP) in esterTPU/PP and ether-TPU/PP blend systems.
The main objectives of the work can be summarized as follows:
(a) Preparation of ester- and ether-TPU/C10A nanocomposites by direct melt blending.
(b) Melt-blending of the prepared nanocomposites with PP using MA-g-PP as the compatibiliser.
(c) Preparation of test specimens by injection molding.
(d) Characterization by X-ray diffraction (XRD), fourier transform infrared
spectroscopy (FTIR), scanning electron microscope (SEM), transmission electron
microscope (TEM), differential scanning calorimetry(DSC) and dynamic mechanical
analysis (DMA).
(e) Evaluation of tensile, abrasion and water absorption properties of the blends and
blend nanocomposites.
(f) Evaluation of electrical properties like volume resistivity, dielectric constant, loss
factor and dissipation factor.
(g) Comparison of dispersion characteristics and properties of ester- and ether-TPU
based blend nanocomposites.
(h) Comparison of the experimental results with the theoretical models.
(i) Investigation of the water diffusion of the TPU/PP blends and the effect of
compatibilisation, nanoclay addition and temperature on the diffusion behaviour.
(j) Investigation of the blend ratio, compatibilisation and nanoclay addition on the flame
retardant properties.
2.1 Materials
Ester-TPU (385 S) and ether-TPU (KU2-8600) were supplied by Bayer (TPU) India Ltd.,
Chennai. The MFI value of 385 S and KU2-8600E is 10 g /10 minute
and 11g/minute
respectively (190 0C / 2.16 Kg). The hardness value of 385S and KU2-8600E is Shore A 85 and
84 respectively. PP (MA 1100) was supplied by Reliance Industries Ltd., Jamnagar, India. The
MFI value of PP (MA 1100) is 11 g / 10 minute (230 0C / 2.16 Kg ). MA-g-PP compatibiliser
was purchased from Pluss Polymers, New Delhi. The compatibiliser is a maleic anhydride
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functionalised polypropylene (MA-g PP), containing 1 wt% of maleic anhydride. The MFI
value of MA-g PP compatibiliser is 12 g / 10 minute (190 0C / 2.16 Kg).The organoclay used in
this study (Cloisite 10 A) was obtained from Southern Clay Products, USA. It is a Na
montmorillonite, chemically modified with dimethyl benzyl hydrogenated tallow quaternary

ammonium ions (N
2MBHT), where N
denotes quaternary ammonium ions, HT denotes
hydrogenated tallow. HT is made of approximately 65 % C 18 H37, 30 % C 16 H33, and 5 % C 14 H29.

Cation exchange capacity is 125 meq / 100 g clay.
2.2 Preparation of nanoclay filled TPU / PP blends
Ester-TPU/C10A nanocomposites were prepared by melt blending TPU and nanoclay
using twin screw extruder. 3 wt% of the nanoclay was used. The ester-TPU pellets were dried at
100 0C for 4 h. The nanoclay was dried at 100 0C for 12 h in vacuum oven. The dried pellets
were fed into a co-rotating twin screw extruder (Berstrof ZE 25) and the temperature of the die
zone was maintained at 190 oC. The extrudate was received as strands and cut into small
granules for melt blending with PP.
Later, the granules of nanocomposites, along with pellets of PP and MA-g-PP were predried at 100 oC for 4 h in a vacuum oven. Blending was done in the co-rotating twin screw
extruder at a die zone temperature of 190 oC and the extrudate was again obtained in the form of
strands. Blends of different compositions shown in Table 2.1 were prepared by the method
described above. Neat ester -TPU / PP blends were prepared in the ratio of 70/30.
Sequence I: TPU/C10A nanocomposites were prepared and subsequently blended with PP
using MA-g-PP as compatibiliser. 3 wt% of the nanoclay was used. The ester- TPU pellets were
dried at 1000C for 4 h. The nanoclay was dried at 100 0C for 12 h in a vacuum oven. The dried
pellets were fed into a co- rotating twin screw extruder and the temperature of the die zone was
maintained at 190oC. The extrudate was received as strands, which were cut into small granules
for melt blending with PP. The granules of nanocomposites, along with pellets of PP and MA-gPP were pre-dried at 100oC for 4 h in a vacuum oven. Blending was done in the same corotating twin screw extruder with a die zone temperature of 190oC and the extrudate was again
obtained in the form of strands. Neat TPU / PP blends were prepared in the ratio of 70 / 30.
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Sequence II: Nanoclay was added to PP by similar extruder melt blending and
subsequently melt blended with TPU using MA-g-PP as compatibiliser (Table 2.1). Ether-TPU
based samples were also prepared by similar method.
Table 2.1. Sequence I and II of Blend compositions
Sequence I
Blend
TPU(nano)*
(wt %)
PP
(wt %)
MA-g-PP
(wt %)
Ester-TPU(nano)/PP
70
30
Ester-TPU(nano)/PP/MA-g-PP
70
25
Ether-TPU(nano)/PP
70
30
Ether-TPU(nano)/PP/MA-g-PP
70
25
[TPU(nano)* = 3% nano content]

Sequence II
Blend
TPU
(wt %)
PP
(wt %)
PP-nano
(wt %)
MA-g-PP
(wt %)
Ester-TPU/PP/MA-g-PP
70
25
Ester-TPU/PP-nano
70
30*
Ester-TPU/PP-nano/MA-g-PP
70
25**
Ether-TPU/PP/MA-g-PP
70
Ether-TPU/PP-nano
70
30*
Ether-TPU/PP-nano/MA-g-PP
70
25**
25
[PP-nano* *= 8.4 % nano content, PP-nano* = 7.0 % nanocontent]

2.3 Experimental Techniques
2.3.1 Phase morphology
The phase morphology was studied using cryogenically fractured samples. By immersing
the samples in liquid nitrogen, a brittle fracture is obtained avoiding large deformations in the
surface to be examined. These samples are immersed in xylene solutions to remove the PP from
TPU base. This setup kept in oil bath at 80C for 3 hours. Then the sample is taken out and dried
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in oven at 100C in order to remove excess of xylene. Thus chemical etching of the sample is
obtained. Morphological studies were performed on the chemically etched and gold sputtered
samples using JOEL (JSM-5800) scanning electron microscope.
2.3.2 Transmission electron microscopy (TEM)
The samples for TEM analysis were prepared by ultra-cryomicrotomy with a Leica
Ultracut UCT (Leica Mikrosystems GmbH, Vienna, Austria). Freshly sharpened glass knives
with cutting edges of 45C were used to obtain cryosections of 100-120 nm thickness. Because
these samples were elastomeric in nature, the sample and glass knife temperatures during
ultracryomicrotomy were kept constant at -75 and -85C, respectively [these temperatures were
well below the glass transition temperature (T g' s) of PUs]. The cryosections were collected
individually in a sucrose solution and directly supported on a copper grid of 300 meshes in size.
Microscopy was performed with a JEOL JEM 2000 TEM instrument (Japan), operating at an
accelerating voltage of 120 kV.
2.3.3 Mechanical Properties
Tensile testing
Tensile tests were carried out as per ASTM D 638 on a universal testing machine
(International Equipments, Mumbai) at a crosshead speed of 200 mm/min. The dumbbell
specimen sizes are: 165 x 12.8 x 3.2 mm. A slip between the specimen and grip occurred at very
high strain levels (1100%) and the specimens could not be broken. Hence the large strain data
is not considered to be very reliable and is not discussed here. Stress at 20%, 100% and 200%
strain was recorded to avoid tensile strength variation at break. Injection molded specimens were
used for this test.
2.3.4 X-ray diffraction (XRD)
The change in gallery spacing of silicate layers in the blend nanocomposites was
determined on an X-ray diffractometer (Panalytical X-pert PRO, Netherlands) using Cu
(=1.5406) as the radiation source. The samples were scanned at a rate of 3 o /min (the
increment step was 0.01 o and the step time was 0.2 s) at room temperature for 2-theta values
starting from 1o to 10 o.
2.3.5 Fourier transform infra-red spectroscopy (FTIR)
13
Fourier transform infra-red spectroscopy (FTIR) has numerous applications in qualitative

and quantitative analysis. Atoms or atomic groups in molecules are in continuous motion with respect
to one another. They vibrate about some mean position. IR spectrum of a compound is the superposition
of absorption bands of specific functional groups. FTIR spectroscopy was performed for the prepared
nanocomposites and blend nanocomposites in the ATR mode for convenience of measurement. A
Thermo Nicolet (Avatar 370) spectrometer was used. Measurements were done in the spectral
range 4000-400 cm-1 at a resolution of 0.9 cm-1.
2.3.6 Differential scanning calorimetry (DSC)
The thermal properties of the blend nanocomposites were measured by a differential
scanning calorimeter (Mettler Toledo, DSC 822e). Sample weight of 3 to 5 mg was scanned in
nitrogen atmosphere at a heating rate of 10 0C/min. Thermograms were taken by heating the
samples in the temperature range from 100 0C to 300 0C.
2.3.7 Dynamic mechanical analysis (DMA)
Dynamic mechanical measurements were performed for the prepared blend
nanocomposites (60 mm 13 mm 3.5 mm) using a Netzsch DMA 242 instrument provided
with a dual cantilever. Analysis was done in the temperature range -100 0C to 200
C at a
frequency of 1,10,20 Hz and a heating rate of 5 0C/min.

2.3.8 Thermogravimetric analysis (TGA)
The thermal degradation studies of the blends were carried out in Netzsch analyzer. The
samples (10mg) were degraded under nitrogen flow (30cm3 min-1 ) in the thermo balance under
dynamic condition at the heating rate of 10 0C/min. The samples were scanned from room
temperature to 800 0C. From the TG curves, the thermal degradation characteristics such as onset
degradation (Ton), temperature at maximum rate of degradation (Tmax), temperatures at different
weight losses and were calculated
2.3.9 Rheological properties
The melt rheology of the individual polymers and their blends was studied using a
dynamic rheometer (Haake RT 10), employing a parallel plate sensor with a diameter of 35 mm
at 190C over a frequency range 100 - 1 rad s-1.
2.3.10 Electrical property measurements

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The electrical measurements were carried out using circular samples of diameter 10mm
and thickness of 3.2mm at room temperature using Novo control, Germany-Alpha ATP. The test
samples were coated with conductive graphite paint on either side and copper wires were fixed
on both sides of the samples as electrodes. All measurements were done at the frequencies
ranging from 100HZ to 1MHz. The capacitance, impedance and dielectric loss factor were
measured directly. Electrical properties such as volume resistivity, dielectric permittivity, loss
factor and dissipation factor were studied.
2.3.11 Flame retardant properties
The flame retardant properties of blends were investigated by limited oxygen index
(LOI), underwriters laboratories-94 (UL-94), rate of burning and ignition response test. LOI
test, UL-94 test, rate of burning test and ignition response test were carried as per ASTM D
2863, UL-94, ASTM D 635 and ASTM D 8713 respectively.
2.3.12 Optical contact angle measurement
Different samples surface energy was calculated from this test using Dataphysics OCAH
230 instrument.
2.3.13 Sorption experiments
Circular samples for diffusion experiments were punched our form the injection moulded
sample specimen using sharp steel, disc (diameter 1.9cm). The samples were vacuum dried for
24 hrs at 800C and then kept in a vacuum desiccator for 2 hrs. The thickness was measured using
a dial gauge. Previously weighed samples were immersed in water taken in sorption bottles kept
at constant temperature in an air oven. At regular intervals the samples were taken out and the
swollen samples were blotted of carefully with soft tissue paper and weighed in an electronic
balance immediately in airtight bottles.
3. Results and discussion
3.1 Phase Morphology
3.1.1 Phase morphology of uncompatibilised blends by SEM
The SEM images of ester -TPU/PP and ether -TPU/PP 70/30 blends are shown in Figure
3.1(a) and 3.2(a). The micrographs demonstrate two-phase morphology. From the figure it is
clear that, PP is dispersed as spherical domains in a continuous TPU matrix. The dispersion of
PP was slightly finer in ether-TPU blends than the corresponding ester-TPU blends. This is
accounted for by the fact that the surface energy of the polyether soft segment is lower than that
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of the polyester soft segment and, consequently, closer to that of the nonpolar PP.
3.1.2 Phase morphology of compatibilised blends
The effects of MA-g-PP as compatibiliser on the morphology of ester-and ether-TPU
(70/30) blends are given in Figures 3.1 and 3.2 respectively. From the SEM micrographs it is
clear that the size of dispersed PP domains is reduced by the addition of compatibilisers. A
similar behaviour was observed for ether-TPU blend compositions also. This reduction in
domain size of dispersed PP on the addition of MA-g-PP is due to the reduction in interfacial
tension between the dispersed PP phase and TPU matrix and suppression of coalescence, which
result in the stabilization of blend morphology.
In addition, the presence of the graft copolymer at blend interface broadens the interfacial
region through the penetration of the copolymer chain segments into the corresponding adjacent
phases [24]. The average domain size of the compatibilised blends as a function of
compatibiliser concentration is given in Figure 3.3. The average domain diameter of the
uncompatibilised ester-TPU (70/30) blend is 3.53 m . In the case of compatibilised blends
addition of 5% MA-g-PP compatibiliser reduces the domain size to 1.10 m thereby causing a
reduction in size upto 70%. Beyond 5% concentration, increase of size of dispersed particle is
due to inefficiency of compatibiliser to suppress coalescence beyond CMC, it cause miscelle.
n, D
w, D
The values of D
vs
and interfacial area / unit volume of MA-g-PP compatibilised
blends are given in Table 3.1. On adding 5% of MA-g-PP the dispersed size is reduced to the
maximum extent and attained maximum interfacial area / unit volume.
(a)
(b)
16
(c)
(d)
Figure 3.1. Scanning electron micrographs of 70/30 ester-TPU/PP blends with addition of
(a) 0 (b) 3 (c) 5 (d) 7 weight % MA-g-PP
(a)
(b)
(c)
(d)
Figure 3.2. Scanning electron micrographs of 70/30 ether-TPU/PP blends with addition of
(a) 0 (b) 3 (c) 5 (d) 7 weight % MA-g-PP
17
Dn(m)
4
3.5
3
2.5
2
1.5
1
0.5
0
Ether-TPU based blends

Ester-TPU based blends
Weight % of compatibiliser
Figure 3.3. Effect of compatibiliser concentration on the dispersed domain diameter of TPU/PP
(70/30) blends
Figure 3.4. Chemical reaction between urethane linkage and maleic anhydride
(Reproduced from Q.W.Lu, T. R. Hoye and C.W. Macosko, J.Polym. Sci. Part A:
Polym. Chem., 40, 2310 (2002) [ Ref. 25 ]
Table 3.1. Effect of compatibilisation on dispersed domain diameter, interfacial area / unit
volume and inter particle distance of ester-TPU/PP (70/30) blends
Sample
w,
D
Interfacial area/ unit
(m)
(m)
(m)
volume (m )
Inter Particle
Distance(m)
TPU/PP (70/30)
3.53
3.79
4.23
0.56
0.74
3% MA-g-PP
1.30
1.61
1.90
1.31
0.25
5% MA-g-PP
1.10
1.36
1.70
1.52
0.20
7% MA-g-PP
1.22
1.44
1.73
1.39
0.23
vs
18
-1
Figure 3.5. Schematic of hydrogen bonding and chemical reaction among PP, MA-g- PP,
nanoclay and TPU
( Reproduced from M.Kannan, S.S. Bhagawan, Tomlal Jose, Sabu Thomas, Kuruvilla Joseph,
Polym.Eng. Sci., 2010, 50(9), 1878-1886) [ Ref.26]
The equilibrium concentration at which the domain size levels off can be considered as
the so-called critical micelle concentration (CMC) ie; the concentration at which micelles are
formed. The CMC has been estimated by the intersection of the straight lines at the low and high
concentration regions [27-29], the CMC value for MA-g-PP is 5%. The CMC value indicates the
critical amount of compatibiliser required to saturate the unit volume of the interface. Generally,
CMC is estimated form the plot of interfacial tension versus copolymer concentration. As the
interfacial tension is directly proportional to domain size, CMC can be estimated from the plot of
domain size versus co-polymer concentration [30]. Several studies have been reported on the
interfacial saturation by the addition of compatibilisers [31-35]. Our present study and almost all
the reported studies on physical and reactive compatibilisation of immiscible polymer blends and
19
the theoretical prediction of Noolandi and Hong [36-38] suggest that a critical concentration of
the compatibiliser is required to saturate the interface of binary polymer blends.
Table 3.2. Effect of compatibilisation on dispersed domain diameter, interfacial area / unit
volume and inter particle distance of ether-TPU/PP blends
n
w,
D
(m)
(m)
TPU/PP(70/30)
3.51
3% MA-g-PP
Interfacial area/unit
Inter Particle Distance
(m)
volume (m-1)
(m)
3.69
4.19
0.59
0.71
1.47
1.67
1.99
1.27
0.29
5% MA-g-PP
1.26
1.41
1.76
1.47
0.24
7% MA-g-PP
1.41
1.5
1.79
1.35
0.27
Sample
vs
3.1.3 Influence of nanoclay addition on compatibilised blend phase morphology

The effect of nanoclay concentration on the morphology of dispersed phase in
TPU(nano)/PP/MA-g-PP (70/30) blends can be evaluated from the SEM micrographs of
cryogenically fractured and xylene extracted surfaces of the specimen demonstrated in Figure
3.6(a).It should be noted that in both blends (ester and ether based),after the initial sharp decline
in particle size, a quasi equilibrium state is obtained at 3wt% of nanoclay in TPU component.
The nanoclay emulsification curve for the both the blend is shown in Figure 3.6(b).
SEM micrographs of chemically etched surfaces of the ester TPU / PP, ester TPU / PP/
MA-g-PP and ester TPU (nano) / PP/ MA-g-PP are shown in Figure 3.7. It is observed that the
size of dispersed PP particle is considerably reduced in the ester TPU (nano) / PP / MA-g-PP
(Figure 3.7 b) system. For nanocomposite SEM sample preparation, the PP portion was removed
by chemical etching method which gives very fine holes. In non clay polymer blends also PP
was removed by etching ; however, the PP domains are not as fine as clay nanocomposites due
to high interfacial tension between TPU and PP and hence fine holes are not evident in SEM
micrographs.
20
(a)
(d)
(b)
(e)
(c )
(f)
Figure 3.6(a). Ester TPU blend TPU (nano)/PP/MA-g-PP (70/25/5)(a) 1% nano (b) 3% nano
(c) 5% nano: Ether TPU blend TPU (nano)/PP/MA-g-PP (70/25/5)(d) 1% nano (e) 3% nano (f)
5% nano (Nano content in TPU)
Figure 3.6(b). Nanoclay emulsification curve- TPU(nano)/PP/MA-g-PP (70-nano/25/5)

3.1.4 Influence of sequence of nanocaly addition on phase morphology
SEM micrographs of chemically etched surfaces of the ester- and ether-based TPU/PP,
TPU/PP/MA-g-PP , TPU / PP(nano)/MA-g-PP , and TPU(nano)/PP/MA-g-PP blend systems are
shown in Figure 3.1,3.2 and 3.7 respectively. It is observed that the size of dispersed PP particle
21
is considerably reduced in TPU(nano)/PP/MA-g-PP. Compared to the sequence II blend

nanocomposites, the sequence I blends show better miscibility as confirmed by SEM analysis.
The clear difference between sequence I and sequence II is that the case of sequence I the effect
of nanoclay is fully utilized by changing the surface tension of the TPU hard segment from
around 45 dynes/cm to around 30 dynes/cm[23]. This change in surface tension favours for
better dispersion of PP in TPU material, and also hydroxyl group of silicate layers forms
hydrogen bonding with the carbonyl group of TPU and maleic anhydride
Compared to the ether-TPU based blend nanocomposites, the ester-TPU blends show
better compatibility as confirmed by SEM analysis. The clear difference between ester-TPU and
ether-TPU is that ester-TPU has carbonyl groups both in the polyol segements as well as the
TPU hard segments. This may lead to more extensive hydrogen bonding in the blend system thus
improving the compatibility.
(a)
(b)
(c)
(d)
Figure 3.7. Effect of sequence of nanoclay addition in compatibilised TPU/PP blends
(a) Ester-TPU/PP (nano)/MA-g-PP (b) Ester-TPU (nano)/PP/MA-g-PP
(c) Ether-TPU/PP (nano)/MA-g-PP (d) Ether-TPU (nano)/PP/MA-g-PP
22
3.1.5 XRD Studies

X-ray diffraction (XRD) is an extremely useful tool to study the structure and
morphology of polymer nanocomposites. Since the layer spacing increases due to intercalation of
polymer chains between the layers, the process can be monitored by X-ray diffraction [23,39-44 ].
The interlayer spacing of Cloisite 10A is 1.92 nm before compounding. For the uncompatibilised
system, the XRD patterns exhibits no significant increase in interlayer spacing. This indicates
that the polymer material does not intercalate into the interlayer, even in the organically modified
nanoclay. In contrast, for compatibilised systems, the XRD peaks are shifted to lower angles,
indicating the increase in interlayer spacing by the intercalation of polymer.
Figure 3.8 (a). Influence of nanoclay addition on ester-TPU based blends XRD pattern
23
Figure 3.8 (b). Influence of nanoclay addition on ether-TPU based blends XRD pattern
3.1.6 Compatibiliser effect on nanoclay dispersion in TPU/PP (70/30) blends
The diffraction characteristics of nanoclay filled compatibilised
TPU(nano)/PP/MA-g-PP blend
ester-
are shown in Figure 3.8. The peak is absent in ester-
TPU(nano)/PP/MA indicating good dispersion, it appears that the compatibiliser MA-g-PP aids
the dispersion of nanoclay in the blend.
Thus, it is confirmed that the compatibiliser makes the nanoclay better dispersed with the
polymers [44-47]. This is because maleic anhydride undergoes chemical reaction with the
urethane groups in the TPU hard segments and also forms hydrogen bonds with the silicate
layers of nanoclay (C10A).
XRD results are often reported to be misleading in terms of clay
dispersion [47]. Therefore, only with the XRD analysis of these nanocomposites blends, it cannot
be concluded that these nanocomposites show the intercalated or the exfoliated clay structures. In
this regard, TEM pictures were taken and the results are reflecting similar trend as XRD results.
3.1.7 Influence of sequence of nanoclay addition in compatibilised blend morphology
The diffraction characteristics of compatibilised TPU (nano)/PP blends are shown in
Figure 3.8. In TPU/PP (nano)/ MA, a peak appears at 2~4.8 0 with reduced intensity as
compared to neat nanoclay. This is an indication that the non-polar PP chains have been
incorporated in the gallery space because of their affinity for the nanoclay. The peak is much
weakened in ester-TPU(nano)/PP/MA indicating nearly exfoliation dispersion, it appears that
24
the compatibiliser MA-g-PP aids the dispersion of nanoclay in the blend . As mentioned in the
previous section, TEM images were taken and the results showed similar trend as XRD results.
In the section on TEM analysis, effects of nanoclay dispersion are discussed with blend
morphology of these blends. Compared to the ether-TPU based blend nanocomposites, the esterTPU blends show better compatibility as confirmed by XRD analysis. As discussed earlier, this
observation may be due to the formation of more hydrogen bonding in ester-TPU based
nanocomposites.
3.1.8 TEM Investigation
It is well known that the difficulty in studying the nanocomposites is that no single
characterization method can adequately describe the state of clay dispersion in the
nanocomposites. The combined analyses are necessary and especially TEM is proved to be
quite effective [47-51].
(a)
(b)
Figure 3.9. TEM images of ester- TPU (a) 3% , (b) 5% nanoclay loading
(a)
(b)
Figure 3.10. TEM images of ether- TPU (a) 3%, (b) 5% nanoclay loading
25
(a) Ester- TPU(3%nano)/PP
(b) Ester-TPU(3%nano)/PP/MA-g-PP
Figure 3.11. TEM images
(a) Ether TPU(3%nano)/PP
(b) Ether-TPU(3%nano)/PP/MA-g-PP
(a)
Ester-TPU/PP(nano)/MA-g-PP
(b)

26
(a) Ether-TPU/PP(nano)/MA-g-PP
(b) Ether-TPU(nano)/PP/MA-g-PP

3.1.9 Influence of nanoclay addition on uncompatibilised blend morphology
To confirm the XRD results and clearly see the dispersion state of clays in the
nanocomposites, TEM pictures were taken and discussed. The TEM images of the esterTPU/nano, ester-TPU (nano)/PP, ether-TPU/nano and ether-TPU (nano)/PP are shown in
figures 3.9, 3.10, 3.11(a) and 3.12(a). The TEM images presented in those figures, present
evidence that efficient dispersion and exfoliation of clay particles did not occur in this
composition. The dispersion of nanoclay particles was found to be poor in this composition. In
the TEM images for the ester-TPU/nanoclay/PP nanocomposites (Figure 3.11a), thick
agglomerated clay particles are observed indicating poor dispersion
of clay. Figure 3.12a
shows clay dispersion in the ether-TPU/nanoclay/PP nanocomposites.

3.1.10 Influence of nanoclay addition on compatibilised blend morphology
Kawasumi et al.[52], Kato et al.[53], Hasegawa et al .[54] and other authors [55-58]
showed that there are two important factors to achieve the exfoliation of the clay layer silicates
(1) the compatibiliser should be miscible with polypropylene matrix, and (2) it should include a
certain amount of polar functional groups in a molecule to react with TPU. Generally, the maleic
anhydride grafted polypropylene (MA-g-PP) fulfills the two requirements and are used as
compatibiliser for this blend system. When MA-g-PP is not introduced into the system, only
intercalated structure is obtained, and many larger aggregates exist in the matrix (Figure 3.11a
and 3.12a). When the compatibiliser is introduced in the system, the nanoclay dispersion
improves.
27
The TEM image in Figure 3.11b shows exfoliated and well dispersed nanoclay particles.
In view of this, a true nanocomposites was produced in the case of ester-TPU(nano)/PP/MA-gPP and 3 wt% nanoclay loading. The TEM image of the composite supports this and shows that
individual clay layers were well dispersed in the polymer. These results are well correlated with
the XRD results where almost no peaks were observed for ester-TPU(nano)/PP/MA-g-PP
nanocomposites. TEM images of nanocomposite of ether-TPU shown in Figure 3.12b, where
the degree of dispersion of clay is observed to be poorer than ester-TPU nanocomposites. This
is in agreement with the XRD result that some changes in clay layers were expected.
3.1.11 Influence of sequence of nanocaly addition on phase morphology
In sequence I, nanoclay was first added to TPU and this nanocomposite was blended
with PP, using MA-g-PP as compatibiliser. In the case of sequence II, nanoclay was added first
to PP and blended with TPU, using MA-g-PP as compatibiliser. Compared to the sequence II
blend nanocomposites, the sequence I blends of TEM images (Figures 3.13 and 3.14) shows
better nanoclay dispersion for both ester- and ether- based TPU nanocomposites. The clear
difference between sequence I and sequence II is that the effect of nanoclay is fully utilized for
changing the surface tension of TPU hard segment in sequence I. The hydroxyl group of silicate
layers forms hydrogen bonding with the carbonyl group of TPU and maleic anhydride moieties
leading to reduction in surface tension of TPU hard segment. This change in surface tension
favors for better dispersion of PP in TPU material.
3.1.12 Comparison of the experimental data with theory
According to Noolandi [37], the effect of copolymer on surface tension between the two
phases is mainly influenced by the contributions from a series of factors such as lowering of
interaction energy between the immiscible homopolymers, the entropy reduction in the system,
decrease in energy of interaction of the two blocks with each other and a large decrease in the
interaction energy of the oriented blocks with homopolymers. Based on these facts and by
neglecting the loss of conformational entropy, Noolandi derived and equation for the interfacial
tension reduction as
=dc [ 1/ 2 1/Z c 1/Z c exp [ Z c /2 ] ]
(3.1)
where d is the width at half height of the copolymer profile reduced by the Kuhn
statistical segment length, c the bulk copolymer volume fraction of the copolymer in the
system, ZC the degree of polymerization of the copolymer and the Flory-Huggins interaction
28
parameter between A and B segments.Although Noolandis theory was developed for the action
of a symmetrical diblock copolymer, A-b-B, in incompatible binary blends (A/B), it can be
applied to other systems too where the compatibilising action is not strictly by the addition of
block copolymers [36-38]. As the interfacial tension reduction is directly proportional to the
particle size reduction at low volume fraction of the dispersed phase, as suggested by Wu, it can
be argued that
D=Kd c [ 1 /2 1Zc exp Z c /2 ]
(3.2)
where K is proportionality constant. The plot of domain size reduction as a function of the
volume fraction of the MA-g-PP for the TPU/PP(70/30) blend is shown in Figure 3.15(a). It can
be seen that at low MA-g-PP concentration (below CMC), there is a drastic decrease in domain
diameter with the increase in volume fraction of the graft copolymer whereas at higher
concentration (above CMC) a leveling off is observed in agreement with the predictions of
Noolandi and Hong.
Figure 3.15(a). Variation of particle size reduction as a function of volume % of compatibiliser

Leibler examined the emulsifying effect of an A-B copolymer in an immiscible blend of
polymers A and B and predicted a reduction of interfacial tension caused by equilibrium
adsorption of the copolymer at the interface. According to the author, the interfacial tension
reduction is given by the relation.
= kT /a2 3/ 41/3 /a 2 5 /3 Z CA Z
2/3Z CB Z 2/3
A
B
29
(3.3)
where Z CA and Z CB are the number of A and B units in the copolymer, respectively, Z A and ZB
the degree of polymerisation of A and B, respectively, a the monomers unit length, the
interfacial area per copolymer. Based on the assumption that the reaction between reactive
compatibiliser and the polymer with a different functional group occurs near the interface, one
can use the following equation for the interfacial tension reduction ( ) obtained by the brush
limit which is independent of the homopolymer molecular weights
=
0
48 2 N
1
2
(3.4)
where 0 is the interfacial tension of polymer blend without a compatibiliser and is the
chemical potential which is given by the equation
(3.5)
=ln fN
where f is the volume fraction of the component in copolymer which is miscible to homopolymer
forming the dispersed phase and
=
(3.6)
[ m d exp { N AN B } ]
where 0,
m and d represent the volume fraction of the copolymer, matrix and dispersed
phase, respectively, NA and NB are the number of segments of the component in the copolymer
miscible to the homopolymer forming the dispersed phase and that miscible to homopolymer
forming the matrix phase, respectively. Since the value of exp
{ N AN B }
is negligible
compared to m , is expressed by 0 /m . Since the dispersed particle reduction is directly

proportional to the interfacial tension reduction, the following equation can be used:
0 D D 0 D
=
=
=
0
0
D
D0
(3.7)
The variation in values of as a function of MA-g-PP in TPU/PP (70/30) blend is given

in Figure.3.15(b). As the amount of PP-g-MA increases, values diminish indicating enhanced
interaction between the phases at interface in presence of compatibiliser. However, note that the
theoretically calculated
values from Libelers theory show apparent conflict with the
experimental observation, which shows a decrease in particle size followed by a quasi

equilibrium state beyond CMC state owing to interfacial saturation. In the calculation process,
the reference segment size is equal to 100 g mo1-1. The total numbers of chain segments N values
are obtained by the assumption that the total number of chain segments of copolymer is just the
30
summation of two number averaged molecular weights of PP and MA-g-PP divided by the
Interaction parameter ()
reference segment size.

0.058
0.048
0.038
0.028
Ether-TPU based blends
Ester-TPU based blends
0.018
0.008
0
Weight % of MA-g-PP
Figure 3.15(b). Effect on MA-g-PP on the values by Leibler's theory

3.2 Mechanical Properties
3.2.1 Mechanical properties of uncompatibilised blends
Plots showing the stress-strain behavior of TPU/PP blend of different composition and
virgin components are presented in Figure 3.16. Stress to break and strain to break could not be
measured since most specimens did not break at even at the maximum strain the machine could
impose. Also, possibilities of sample slippage from grip increase at large strains. A slip between
the specimen and grip occurred at very high strain levels (1100%) and the specimens could not
be broken. Hence the large strain data is not considered to be very reliable and is not discussed
here. Stress at 20%, 100% and 200% strain was recorded to avoid tensile strength variation at
break. The differences in the deformation characteristics of the blends under an applied load are
evident from the figure. In general, the stress-strain curves of PP and PP rich blends show linear
elastic region followed by yielding and necking in the inelastic region, which is typical of
plastics. The addition of more TPU considerably reduces the modulus and eliminates the necking
tendency of PP. The phase change in morphology is also reflected in the nature of the stressstrain curves. The experimental results for uncompatibilised blends are given in Table 3.3 & 3.4.
31
Table 3.3 Mechanical properties of uncompatibilised ester-TPU based blends

Impact
Blend
composition
Strength
Izod J/M
Stress at % strain (MPa)
Shore D
Tensile
Modulus
(MPa)
20%
100%
200%
Hardness
TPU/PP (100/0)
NF
42
905
3.00.05
3.90.05
4.30.05
TPU/PP (70/30)
NF
52
2535
5.30.05
5.70.05
6.40.05
TPU/PP (50/50)
NF
56
6135
12.90.05
14.80.05
15.90.05
TPU/PP (30/70)
38
58
10205
22.90.05
24.80.05
25.20.05
TPU/PP (0/100)
29
62
14505
32.60.05 (at break)
35
30
25
20
15
10
5
0
Stress (MPa)
Stress (MPa)
NF No failure
50
100
150
200
250
300
Strain %
TPU/PP(100/0)
TPU/PP (50/50)
TPU/PP (0/100)
35
30
25
20
15
10
5
0
50
100
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
TPU/PP(70/30)
TPU/PP(30/70)
150 200
Strain %
250
300
TPU/PP (70/30)
TPU/PP (30/70)
Figure 3.16(a). Stress-strain curves for
Figure 3.16(b). Stress-strain curves for
uncompatibilised ester-TPU/PP blends
uncompatibilised ether-TPU/PP blends
32
Table 3.4. Mechanical properties of uncompatibilised ether-TPU based blends

Impact
Blend
composition
Strength Hardness
Izod
Shore D
J/M
Tensile
Modulus
(MPa)
20%
100%
200%
TPU/PP (100/0)
NF
42
905
3.40.05
4.00.05
4.30.05
TPU/PP (70/30)
NF
53
2745
5.70.05
6.60.05
6.70.05
TPU/PP (50/50)
NF
57
6435
15.10.05 16.20.05
16.30.05
TPU/PP (30/70)
40
59
10555
25.10.05 27.60.05
27.20.05
TPU/PP (0/100)
29
62
14505
32.6 0.05 (at break)
NF No failure
Materials, which undergo strain hardening during stretching, have higher strength at
break than materials that do not undergo strain hardening [59].
3.2.2. Modeling of Tensile Moduli
Mechanical properties are widely suited for analysis of multicomponent composites,
through a comparison of experimental results and prediction based on various models. The
application of various composite models gives insight into the properties of individual
components. It also helps to check the assumptions regarding structure, mechanism and
properties of the interface. Several theories have been proposed to predict the tensile properties
in terms of various parameters. These theories can be classified into two categories: (i) based on
composition and (ii) based on morphology [60].Most of these theories assume perfect adhesion
between the phases and a macroscopically homogenous and isotropic sample. The different
models examined to predict the mechanical behaviour of the blends include the parallel, series,
Halpin-Tsai, Takayanagi, Kerner, and Kunori models. The highest upper bound parallel model
(Voight prediction) is given by the rule of mixtures. The application of these models requires the
knowledge of the experimental mechanical behaviour of the pure component polymers TPU and
PP. The two simple models are the so-called parallel and series models, which should represent
the upper and lower bounds of the tensile strength predictions
33
Figures 3.17 and 3.18 show comparison of the variation in theoretical and experimental
curves of the tensile strength and tensile moduli of ester and ether TPU/PP blends as functions of
volume fractions of PP. The predictions of these theories have been made with E 1= 3.9 for
ester,E1= 4.0 for ether at 100% strain and E2 =32.6 MPa for the tensile strength for TPU and PP
respectively. The predictions of these theories also have been made with E 1=90 (both ester and
ether) and E2 =1450 for the tensile modulus for TPU and PP respectively. In the experimental
curve, that there is only marginal increase in tensile strength with the addition of up to 30wt. %
of PP to TPU. In immiscible blends, the tensile strength usually depends on the particle size of
the dispersed phase. Smaller and more uniformly distributed particles are more effective in
initiating crazes and terminating it before they develop into catastrophic sizes. The lower values
for the tensile strength in this blend system upto 30% PP may be due to poor interfacial adhesion
between the dispersed PP phase and the continuous TPU matrix.
35
25
20
15
10
5
0
0
0.2
0.4
Coran
Experiment
Kerner
Parallel
Series
Halpin Tsai
30
Tensile Strength(MPa)
30
Tensile Strength(MPa)
35
Coran
Experiment
Kerner
Parallel
Series
Halpin Tsai
0.6
0.8
25
20
15
10
5
0
Volume fraction of PP
0.2
0.4
0.6
0.8
(a)
(b)
Figure 3.17. Theoretical model for uncompatibilised (a) ester (b) ether-TPU blends (Tensile
strength)
34
1600
1600
Coran
Experiment
Kerner
Parallel
Series
Halpin Tsai
1200
1000
Coran
Experiment
Kerner
Parallel
Series
Halpin Tsai
1400
Tensile Modulus (MPa)
Tensile Modulus (MPa)
1400
800
600
400
200
0
1200
1000
800
600
400
200
0
0.2
0.4
0.6
0.8
0.2
0.4
0.6
0.8
(a)
(b)
Figure 3.18. Theoretical model for uncompatibilised (a) ester (b) ether-TPU blends (Tensile
Modulus)
3.2.3 Mechanical properties of compatibilised blends with nanoclay addition
The addition of compatibilisers affects the mechanical properties of immiscible polymer
blends are shown in Figures 3.19 & 3.20. The uncompatibilised TPU/PP(70/30) blend has low
tensile strength and exhibits considerable improvement by the addition of compatibiliser. With
increase in compatibiliser concentration, the tensile strength is found to increase upto 5 wt.%
continuously and then levels off or decrease. This increase in tensile strength is due to the
increase in interfacial adhesion between TPU and PP. This observation complements the other
studies discussed in other chapters. Figure 3.19 & 3.20 shows the variation of tensile strength of
70/30 TPU/PP blends with weight 5% of the compatibiliser, MA-g-PP. Similar results have been
reported for Nylon /PP [61] and NBR/PP systems [62]. The experimental results for
compatibilised blends are given in Table 3.5 & 3.6. The stress required for 20,100 & 200% strain
is improved with compatibilisation, which are also attributed to improved interfacial interactions.
35
10
10
Stress (MPa)
12
Stress (MPa)
12
8
6
4
8
6
4
0
0
50
100
150 200
Strain %
250
300
100
150
200
Strain %
250
Uncompatibilised
3% MA-g-PP
Uncompatibilised
3% MA-g-PP
7% MA-g-PP
5% MA-g-PP
7% MA-g-PP
5% MA-g-PP
Figure 3.19. Effect of compatibiliser on

ester-TPU blends
300
Figure 3.20. Effect of compatibiliser on

ether-TPU blends
12
10
10
Stress (MPa)
12
Stress (MPa)
50
8
6
4
2
8
6
4
2
0
0
50
100
150 200
Strain %
250
300
50
100
150
200
250
300
TPU(nano)/PP/MA-g-PP
TPU/PP(nano)/MA-g-PP
Strain %
TPU/PP/MA-g-PP
TPU/PP
TPU/PP/MA-g-PP
TPU/PP
Figure 3.21. Stress-strain curves for

ester-TPU blends (compatibilised)
Figure 3.22. Stress-strain curves for

ether-TPU blends (compatibilised)
36
Table 3.5. Mechanical properties of compatibilised ester-TPU based blends

Impact
Strength
Izod J/M
Hardness
Shore D
Tensile
Modulus
(MPa)
20%
100%
200%
TPU/PP (70/30)
NF
52
2535
5.30.05
5.70.05
6.40.05
TPU/PP/MA
(70/25/5)
NF
53
2985
5.70.05
6.70.05
6.90.05
TPU/PP(nano)/MA
(70/25/5)
NF
53
3565
7.70.05
8.00.05
8.40.05
TPU(nano)/PP/MA
(70/25/5)
NF
55
4305
7.90.05 10.10.05 10.30.05
Blend
composition
Table 3.6. Mechanical properties of compatibilised ether-TPU based blends

Blend
composition
Impact
Hardness
Strength
Shore D
Izod J/M
Tensile
Modulus
(MPa)
20%
100%
200%
TPU/PP
(70/30)
NF
52
2745
5.70.05
6.60.05
6.70.05
TPU/PP/MA
(70/25/5)
NF
53
3105
6.10.05
6.90.05
7.20.05
TPU/PP(nano)/MA
(70/25/5)
NF
53
3675
7.10.05
7.80.05
8.30.05
TPU(nano)/PP/MA
(70/25/5)
NF
54
4365
7.50.05
9.50.05
9.80.05
Tensile test indicates that ester-TPU materials have better tensile properties than etherTPU materials. Compatibilised ester- and ether-TPU blend nanocomposites exhibited higher
stresses at the respective elongations than the uncompatibilised blends. The tensile test results
substantiate the compatibilisation offered by MA-g-PP as seen earlier in the other results. EsterTPU(nano)/PP/MA exhibited the best tensile properties as shown in the Table 3.5 & 3.6.
Nanoclay filled thermoplastic polyurethane (TPU) / polypropylene (PP) blends
compatibilised with maleic anhydride grafted polypropylene (MA-g-PP) have been studied with
emphasis on sequence of nanoclay addition. In sequence I [TPU(nano) / PP/ MA-g-PP],
nanoclay was first added to TPU and this nano composite was blended with PP, using MA-g-PP
as compatibiliser. In the case of sequence II [TPU/ PP(nano)/MA-g-PP], nanoclay was added
first to PP and blended with TPU, using MA-g-PP as compatibiliser. The results indicated that
37
sequence I imparted greater compatibility to the polymers and better nanoclay dispersion than
sequence II. Overall the TPU (nano) / PP/ MA-g-PP blend system shows better dispersion than
TPU/ PP(nano)/MA-g-PP.
Nanoclay was used to reduce the surface energy of the TPU hard
segments and makes them more compatible with the non-polar PP. More miscible blends have
been obtained by using MA-g-PP as the compatibiliser. Better dispersion of organoclay may be
attributed to two reasons. Firstly, maleic anhydride forms hydrogen bonds with the hydroxyl
groups of the silicate layers. Secondly, there is a possible chemical reaction between maleic
anhydride and the urethane linkages in the TPU hard segments. Compared to the sequence II
blend nanocomposites, the sequence I blends show better miscibility as confirmed by tensile test.
3.3 Thermal Properties
3.3.1 Thermal degradation
3.3.1.1 Neat polymers
Polymers are useful in certain range of temperature- a low temperature limit below which
they are brittle and a high temperature limit above which they soften, melt degrade and ultimately
decompose. The TGA and DTG thermograms of TPU and PP in nitrogen atmosphere at a heating
rate of 10C/min are shown in the Figure 3.23 & 3.24. TPU major degradation starts at 290C and
gets completed at 460 C.The peak of the DTG curves gives the temperature corresponding to
maximum degradation (Tmax). In the DTG curve of ester-TPU, the peak appeared at 370.3C.
Thermal decomposition of TPU has been studied by various researchers [63-71].
120
Weight loss (%)
100
80
60
40
Neat PP
Neat ether TPU
Neat ester TPU
20
0
0
100
200
300
400
500
600
700
Temperature,C
Figure 3.23. Neat polymers TGA analysis
38
800
0
-2
DTG (%/min)
-4
-6
-8
-10
Neat PP
Neat ether TPU
Neat ester TPU
-12
-14
-16
0
100
200
300
400
500
600
700
800
Temperature,C
Figure 3.24. Neat polymers DTG analysis

The degradation of PP (Figure 3.23) starts around 390C and almost completed at 490C.
PP has got greater thermal stability in nitrogen atmosphere than TPU, which is evident from the
displacement of the weight loss curve to much higher temperature. DTG curve , also supports the
thermal stability of PP (Tmax 474.1C) when compared to TPU (Tmax 370.3C).
3.3.1.2 Uncompatibilised blends
The TGA and DTG thermograms of the blends are presented in Figure 3.25 & 3.26
respectively. Compared to the degradation pattern of the individual components, the degradation
behaviour of the blends is slightly different. The weight loss of neat polymers and their blends at
different temperatures is given in the Table 3.7. It can be seen from Table 3.7 that degradation
temperature corresponding to different percentage weight loss decreases gradually by the
addition of PP in blends. TPU (nano)/PP/MA-g-PP possesses highest Tmax values, which indicate
that high thermal stability than other blend system. As the weight percentage of the PP in the
blend increases, a gradual decrease in weight loss can be noticed indicating an increase in
thermal stability. This indicates improved thermal stability upon the incorporation of PP.
Thermal stability of the polymer blends depends mainly on the morphology and miscibility of
the system. It should be noted that in TPU/PP (30/70) blends, the thermally more stable PP forms
the matrix where as in TPU/PP (70/30) blends TPU is the continuous phase. A thermal
degradation result suggests that even though the TPU/PP blends are immiscible, the thermal
stability of TPU can be improved by the addition of PP.
39
Weight loss %
120
100
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
80
60
40
20
0
0
100
200
300
400
500
600
700
800
Temperature,C
(a)
DTG (%/min)
2
0
-2
-4
-6
-8
-10
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
-12
-14
-16
0
100
200
300
400
500
600
700
800
Temperature,C
(b)
Figure 3.25. Effect of blend ratio on the thermograms of TPU/PP blends
(a) Ester-TPU based thermograms
(b) Ester-TPU based derivative thermograms
Weight loss %
120
100
80
60
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
40
20
0
0
100
200
300
400
500
600
700
800
700
800
Temperature,C
(a)
DTG (%/min)
2
0
-2
-4
-6
-8
-10
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
-12
-14
-16
0
100
200
300
400
500
600
Temperature,C
(b)
Figure 3.26. Effect of blend ratio on the thermograms of TPU/PP blends
(a) Ether-TPU based thermograms (b) Ether-TPU based derivative thermograms
Table 3.7(a). Weight losses at different temperatures of ester-TPU/PP blend
40
Sample
Tonset( C)
T50
Weight loss at
400C (%)
Tmax ( C)
TPU/PP (100/0)
275
370.5
75.5
370.3
TPU/PP (70/30)
283.2
386.5
55.2
392.1,442.2
TPU/PP (50/50)
307.2
406.5
48.1
401.2,452.1
TPU/PP (30/70)
322.5
417.8
41.9
412.7,462.1
TPU/PP (0/100)
390
470.5
2.3
474.1
Table 3.7(b). Weight losses at different temperatures of ether-TPU/PP blend

Sample
Tonset( C)
T50
Weight loss at
400C (%)
Tmax ( C)
TPU/PP (100/0)
277
371.9
73.2
372.3
TPU/PP (70/30)
283.7
389.1
53.2
393.3,443.6
TPU/PP (50/50)
307.9
409.7
46.1
401.8,454.2
TPU/PP (30/70)
323.7
421.5
38.1
414.2,464.3
TPU/PP (0/100)
390
470.5
2.3
474.1
3.3.1.3 Compatibilised blends

The TGA and DTG curves of TPU/PP blends compatibilised with MA-g-PP are shown in
Figures.3.27&3.28 respectively. Compatibiliser has substantial influence on the thermal
properties of the blends. The thermal stability of the blends was found to be increased by the
incorporation of MA-g-PP. In Figure 3.27, the peak corresponding to the major weight loss is
shifted to higher temperatures upon compatibilisation. Table 3.8 shows the degradation
temperature and weight loss at different temperature for the compatibilised blends.
The addition of 5 % of MA-g-PP resulted in the improvement of the onset temperature
for degradation. Further addition of the nanoclay showed again improvement in degradation
temperature of the blend. The addition of nanoclay in TPU (nano)/PP/MA-g-PP sequence has got
the maximum degradation temperature. .It also be seen from the table that the T max to the major
weight loss (DTG peak value) increased upon compatibilisation. The percentage weight loss at
different temperatures decreased upon compatibilisation.
Table. 3.8(a). Degradation temperatures and weight loss at different temperature of
nanoclay filled 70/30 ester-TPU/PP blend compatibilised with MA-g-PP
41
Sample
Tonset
T50
Weight loss at
400C (%)
Tmax ( C)
TPU/PP (70/30)
283.2
386.5
55.2
392.1,442.2
TPU/PP/MA-g-PP
(70/25/5)
285.2
394.1
53.3
431.9
TPU/PP(nano)/MA
-g-PP (70/25/5)
290.3
399.3
50.5
442.1
TPU(nano)/PP/MA
295.2
403.3
49.2
453.1
-g-PP (70/25/5)
Table. 3.8(b). Degradation temperatures and weight loss at different temperature of
nanoclay filled 70/30 ether-TPU/PP blend compatibilised with MA-g-PP
Sample
TPU/PP (70/30)
TPU/PP/MA-g-PP
(70/25/5)
TPU/PP(nano)/MA
-g-PP (70/25/5)
TPU(nano)/PP/MA
-g-PP (70/25/5)
Weight loss at
400C (%)
Tonset
T50
Tmax ( C)
283.7
389.1
53.2
393.3,443.6
284.3
393.3
52.4
428.9
288.3
397.7
51.1
434.1
292.2
401.9
48.9
443.1
The increase in degradation temperature of compatibilised blends is due to the improved

interfacial adhesion between the two components as the result of compatibilisation, which is
having a direct influence on the thermal properties. MA-g-PP can increase compatibility of
TPU/PP blends through interfacial chemical reaction between its anhydride groups and the
urethane groups of TPU. The resulting copolymer will locate at the interface and decreases
interfacial tension thus provides a good interfacial adhesion between the TPU and PP phases.
This in turn will contribute towards the improvement of thermal stability. Therefore the
enhanced thermal stability of TPU/PP (70/30) blends upon compatibilisation addition can be
attributed to the compatibilising efficiency of MA-g-PP.
It is important to not that there is a strong link between the thermal properties and
morphology of the blends. The compatibilising efficiency of MA-g-PP is well evident from the
finely dispersed uniform morphology compared to uncompatibilised blend. The morphological
parameters of TPU/PP blends derived from SEM micrographs are shown in the Figure 3.6. From
the micrograph it was clear that the domain size of the dispersed PP in the compatibilised system
42
is decreased considerably. It has been revealed from this study stabilization of morphology
through chemical reaction has profound effect on the thermal properties of the blends.
TPU/PP (70/30)
TPU/PP/MA-g-PP (70/25/5)
TPU/PP(nano)/MA-g-PP (70/25/5)
TPU(nano)PP/MA-g-PP (70/25/5)
120
Weight loss %
100
80
60
40
20
0
0
100
200
300
400
500
600
700
800
900
Temperature,C
(a)
TPU/PP (70/30)
TPU(nano)/PP/MA-g-PP (70/25/5)
DTG (%/min)
-2
-4
-6
-8
-10
-12
-14
0
100
200
300
400
500
600
700
800
900
Temperature,C
(b)
Figure 3.27. Effect of blend ratio on the thermograms of compatibilised TPU/PP blends
(a) Ester-TPU based thermograms
(b) Ester-TPU based derivative thermograms
43
120
TPU/PP (70/30)
100
Weight loss %
TPU/PP(nano)/PP (70/25/5)
80
60
40
20
0
250
300
350
400
450
500
Temperature,C
(a)
0
DTG (%/min)
-2
TPU/PP (70/30)
-4
-6
(70/25/5)
(70/25/5)
-8
-10
-12
-14
0
100
200
300
400
500
600
700
800
900
Temperature,C
(b)
Figure 3.28. Effect of blend ratio on the thermograms of compatibilised TPU/PP blends
(a) Ether-TPU based thermograms
(b) Ether-TPU based derivative thermograms
3.3.2 Melting and crystallisation behaviour

3.3.2.1 Uncompatibilised blends
The DSC heating and cooling scans can be used to determine a number of parameters
signifying the melting and non-isothermal crystallization behaviour of the components in the
blends. The melting peak temperature (Tm), crystallisation temperature (Tc), heat of fusion (
H
) and heat crystallization ( H c ) were directly obtained from these graphs. The TPU
used in this study is a ester and ether based TPU. It shows a wider melting range compared to
the other semicrystalline.The melting point (Tm) of the TPU which we used in this study depends
44
on both composition and the susceptibility of the mixed components. The T m of the crystalline
component in a blend is dependent on both morphological and thermodynamic factors [72]. This
is related to crystallization condition like temperature, time, blend composition and scanning
rate. These factors can cause increase or decrease in Tm. Figure 3.29(b) represents the second
heating endotherms of TPU and some of its selected blends with PP.
Table 3.9. Melting behaviour of uncompatibilised ester-TPU/PP blends
Tg (C )
Tm(C )
Hf ( J/g)
Normalised
Xc %
Crystallinity
TPU/PP (0/100)
-------
168.2
85.05
41
TPU/PP (30/70)
-50.1
167.9
83.9
40
TPU/PP (50/50)
-54.3
168.0
82.5
40
TPU/PP (70/30)
-61.2
167.7
81.3
39
TPU/PP (100/0)
-63.1
------
-----
-------
Heatflow (mW)
Sample
0.4
-0.1
-0.6
-1.1
-1.6
-100
100
200
300
Temperature, C
Figure 3.29 (a). Neat PP DSC thermogram

Table 3.10. Melting behaviour of uncompatibilised ether-TPU/PP blends
Sample
Tg (C )
Tm (C )
Hf ( J/g)
Normalised
Xc %
Crystallinity
TPU/PP (0/100)
-------
168.2
85.05
41
TPU/PP (30/70)
-51.2
167.7
82.1
40
TPU/PP (50/50)
-58.2
167.3
81.6
39
TPU/PP (70/30)
-61.6
167.9
80.1
39
TPU/PP (100/0)
-65.3
------
------
-----
45
0
TPU/PP (100/0)
TPU/PP (70/30)
-0.2
TPU/PP (50/50)
-0.3
TPU/PP (30/70)
-0.4
-0.5
-0.6
-0.7
-0.8
-0.9
-100
-80
-60
-40
-20
20
Temperature, C
Figure 3.29 (b).
Effect of blend ratio on the Tg of ester-TPU/PP blends
abcd-
Exo-heatflow (mW)
Heatflow (mW)
-0.1
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
a
b
c
d
50
100
Temperature, C
(a)
46
150
200
40
d - TPU/PP (0/100)
Endo-heatflow (mW)
c - TPU/PP (30/70)
b - TPU/PP (50/50)
a - TPU/PP (70/30)
a
b
c
d
50
100
150
200
Temperature, C
(b)
Figure 3.30. a) Effect of blend ratio on PP crystallization behaviour of ester TPU/PP blends.
(b) Effect of blend ratio on the PPs (H f ) enthalpy of fusion in the heating curves of esterTPU/PP blends
0
TPU/PP (50/50)
TPU/PP (30/70)
-0.2
TPU/PP (100/0)
Heatflow (mW)
TPU/PP (70/30)
-0.4
-0.6
-0.8
-1
-1.2
-100
-50
50
Temperature, C
Figure 3.31. Effect of blend ratio on the TPUs Tg in the heating curves of ether-TPU/PP blends
47
Exo-heatflow (mW)
abcd-
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
a
b
c
d
50
100
150
200
Temperature, C
(a)
Endo-heatflow (mW)
d
c
b
a
TPU/PP
TPU/PP
TPU/PP
TPU/PP
(0/100)
(30/70)
(50/50)
(70/30)
a
b
c
d
50
100
Temperature, C
150
200
(b)
Figure 3.32. (a) Effect of blend ratio on PP crystallization behaviour of ether TPU/PP blends.
(b) Effect of blend ratio on the PPs (H f ) enthalpy of fusion in the heating curves of etherTPU/PP blends
The crystalline melting point (Tm ) is almost same in all blends during second heating.
This reveals that blending has no effect on the melting point of the TPU and PP. This also
indicates that the two polymers are highly immiscible and the blends are incompatible.
The onset of Tm and the melting temperature (Tm ) of PP appeared at 130.6 and 168.2C
respectively. On adding TPU, the thermogram exhibits a different behaviour. The normalized
48
value of enthalpy of fusion, H
decreased to 81.3 for TPU rich blends (TPU/PP 70/30) in
ester-TPU and to 80.1 in ether-TPU. The % crystallinity and enthalpies of fusion of the blends
are significantly depending on the blend composition. The glass transition values of the TPU are
also increased (12C). This can be attributed due to the encroachment of PP into the TPU
structure. This causes considerable increase of chain rigidity, which increases the T g of TPU due
to the restricted mobility of TPU chains. The glass transition temperature (T g) of the sample were
obtained from the inflexion of the thermograms in the DSC trace. The T g of pure ester and ether
TPU are found to be -63.1 and 65.3 C respectively. The effect of blend ratio on the %
crystallinity is given in the Figure 3.22.
3.3.2.2 Compatibilised blends
The heating and cooling curves of TPU/PP (70/30) blend are shown in the Figure 3.34
and 3.35 respectively. The obtained from DSC thermogrames are tabulated in Table 3.11 and
3.12. The observed value indicates that compatibilisation does not show appreciable effect on
the melting and crystallization behaviour of the TPU/PP (70/30) blends. It is well evident from
the figure and table that compatibilisation does not have much contribution towards melting and
crystallisation parameter.
Table 3.11. Melting and crystallization behaviour of compatibilised ester- TPU/PP (70/30)
blends
Tc
(C)
Hc ( J/g)
Hf ( J/g)
Xc %
Enthalpy of
Enthalpy
Crystallinity
of fusion Crystallisation
Sample
Tg (C)
Tm
(C)
TPU/PP (70/30)
-61.2
167.9
118.1
81.3
-82.9
39
TPU/PP/MA-g-PP
(70/25/5)
-58.3
168.0
116.5
80.9
-82.1
39
TPU/PP(nano)/
MA-g-PP (70/25/5)
-53.1
167.7
116.5
80.1
-81.7
38
TPU(nano)/PP/
MA-g-PP (70/25/5)
-47.1
167.7
116.0
79.6
-81.2
38
49
1.5
0.5
TPU/PP/MA-g-PP
Heatflow (mW)
TPU/PP
-0.5
-1
-1.5
-2
-2.5
-3
-3.5
-4
-100
-50
50
100
Temperature,C
Figure 3.33. Effect of nanoclay on compatibilised ester TPU blends Tg
Endo-heatflow (mW)
a - TPU(nano)/PP/MA-g-PP
b - TPU/PP
c - TPU/PP/MA-g-PP
d - TPU/PP(nano)/MA-g-PP
a
b
c
d
50
100
150
200
Temperature, C
Figure 3.34. Effect of compatibiliser and nanoclay on melting behaviour of ester 70/30 TPU/PP
blends
50
a - TPU/PP (0/100)
Exo-heatflow (mW)
b - TPU/PP (70/30)
c - TPU/PP/MA-g-PP (70/25/5)
d - TPU(nano)/PP/MA-g-PP (70-nano/25/5)
a
b
c
d
50
100
Temperature, C
150
200
Figure 3.35. Effect of compatibiliser and nanoclay on crystallization behaviour on ester 70/30
TPU/PP blends
Table 3.12. Melting and crystallization behavior of compatibilised ether- TPU/PP (70/30) blends
Hc ( J/g)
Xc %
Enthalpy of
Crystallinity
Crystallisation
Sample
Tg
(C)
Tm
(C )
Tc
(C )
Hf ( J/g)
Enthalpy
of fusion
TPU/PP (70/30)
-62.5
167.9
118.1
80.1
-81.4
39
TPU/PP/MA-g-PP
(70/25/5)
-60.1
168.0
116.1
79.7
-80.9
39
TPU/PP(nano)/
MA-g-PP (70/25/5)
-57.2
167.6
115.9
79.1
-80.3
38
TPU(nano)/PP/
MA-g-PP (70/25/5)
-54.3
167.4
115.7
78.7
-79.8
38
51
1.5
TPU/PP
TPU/PP/MA-g-PP
Heatflow (mW)
0.5
-0.5
-1
-1.5
-100
-50
50
100
Temperature, C
Figure 3.36 (a). Effect of compatibiliser and nanoclay on Tg of ether 70/30 TPU/PP blends
Endo-heatflow (mW)
a
b
c
d
TPU/PP
TPU/PP/MA-g-PP
a
b
c
d
Figure 3.36(b).
TPU/PP blends
50
100
Temperature, C
150
200
Effect of compatibiliser and nanoclay on melting behaviour of ether 70/30
52
a - TPU/PP (0/100)
b - TPU/PP (70/30)
c - TPU/PP/MA-g-PP (70/25/5)
Exo-heatflow (mW)
d - TPU(nano)/PP/MA-g-PP (70-nano/25/5)
a
b
c
d
50
100
150
200
Temperature,C
Figure 3.36(c). Effect of compatibiliser and nanoclay on crystallization behaviour on ether 70/30
TPU/PP blends
3.3.3 Rheological properties
For the design and development of multiphase polymer blend systems, a thorough
knowledge of the relationship between molecular characteristics of the component polymers,
their rheological and interfacial properties, the melt processing conditions and the flow induced
microstructure is essential. Melt flow studies give us valuable viscosity of polymers which are
highly important for optimizing the processing conditions and in designing processing
equipments.
The plot of complex viscosity (*) vs frequency () and the plot of storage modulus(G')
vs frequency () and loss modulus (G") vs frequency () for the ester TPU based blends with
nanoclay and compatibiliser are shown in Figures 3.37 and 3.38. Neat TPU had a much higher
viscosity than neat PP in all range of the frequencies carried out in this experiment. The greater
the content of TPU was, the higher was the viscosity. The introduction of PP into TPU resulted
in a reduction of the viscosity and thus the processability of the blends was improved. Very often
compatibilisation affects flow properties of the blends. Interactions occurring between blend
components generally increase the viscosity of the system. In Figures showing * vs , G' vs
, and G" vs , where they showed change in complex viscosity at varying frequency, while
53
those with nanoclay and compatibiliser blend system exhibited higher complex viscosity. Higher
complex viscosity was attributed to the enhanced better dispersion in nanoclay and
compatibiliser containing blend system. Similar trend with ether-TPU based blend
nanocomposites were observed again indicating better dispersion in nanoclay and compatibiliser
added blend system. High increase of complex viscosity was observed in ester based blend
system.
1.E+05
1.E+04
G' (Pa)
* (Pa.s)
1.E+05
1.E+04
1.E+03
1.E+02
1.E+00
1.E+01
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
(rad/s)
1.E+03
1.E+00
1.E+02
1.E+01
(rad/s)
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
TPU/PP (70/30)
TPU/PP (30/70)
(a)
1.E+02
TPU/PP (70/30)
TPU/PP (30/70)
(b)
1.E+05
1.E+05
TPU/PP/MA-g-PP
TPU/PP
G" (Pa)
1.E+04
* (Pa.s)
1.E+04
1.E+03
1.E+00
1.E+01
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
(rad/s)
1.E+02
1.E+03
1.E+00
TPU/PP (70/30)
TPU/PP (30/70)
(c)
1.E+01
(rad/s)
(d)
54
1.E+02
1.E+05
1.E+05
TPU/PP/MA-g-PP
G" (Pa)
TPU/PP
G' (Pa)
1.E+04
1.E+03
1.E+00
1.E+01
(rad/s)
1.E+02
1.E+04
1.E+00
TPU/PP/MA-g-PP
TPU/PP
1.E+01
1.E+02
(rad/s)
(e)
(f)
Figure 3.37. Uncompatibilised-ester TPU (a) * vs , (b) G' vs , (c ) G" vs

compatibilised-ester TPU (d) * vs , (e) G' vs , (f ) G" vs
1.E+05
1.E+04
G' (Pa)
* (Pa.s)
1.E+05
1.E+04
1.E+03
1.E+02
1.E+00
1.E+01
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
(rad/s)
1.E+03
1.E+00
1.E+02
1.E+01 (rad/s) 1.E+02
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
TPU/PP (70/30)
TPU/PP (30/70)
(a)
(b)
55
TPU/PP (70/30)
TPU/PP (30/70)
1.E+05
1.E+05
TPU/PP/MA-g-PP
TPU/PP
1.E+04
* (Pa.s)
G" (Pa)
1.E+04
1.E+03
1.E+00
1.E+01
(rad/s)
1.E+02
TPU/PP (100/0)
TPU/PP (70/30)
TPU/PP (50/50)
TPU/PP (30/70)
1.E+03
1.E+00
TPU/PP (0/100)
( c)
1.E+01
(rad/s)
1.E+02
(d)
1.E+05
TPU/PP/MA-g-PP
TPU/PP
G" (Pa)
1.E+05
G' (Pa)
1.E+04
1.E+03
1.E+00
1.E+01
(rad/s)
1.E+02
1.E+04
1.E+00
TPU/PP/MA-g-PP
TPU/PP
1.E+01
(rad/s)
(e)
(f)
Figure 3.38. Uncompatibilised-ether TPU (a) * vs , (b) G' vs , (c ) G" vs

compatibilised-ether TPU (d) * vs , (e) G' vs , (f ) G" vs
56
1.E+02
3.4 Dynamic Mechanical Analysis

3.4.1 Uncompatibilised Blends
Figures 3.39(a), (b), (c) and (d) show the wide temperature range DMA measurements
[storage modulus, log storage modulus, loss modulus and loss tangent factor (tan )] for TPU/PP
blends at 10 Hz. TPU records the minimum and intermediate values for the compatibilised
blends. At low temperature, since the polymers are in the glassy state, effect of temperature on
modulus improvement could not be observed for all compositions. The highest damping value is
seen for TPU. Damp value decreases upon incorporation of PP, as seen in the figure and have
higher loss tangent values.
The damping is low below Tg because the chain segments are frozen in. Below T g the
deformations are thus mainly elastic and molecular slip resulting in viscous flow is low. As
temperature increases, damping goes through a maximum near Tg, in the transition region and
then a minimum in the rubbery region. Above Tg where rubbery region exists, the damping is
also low because molecular segments are very free to move about and there is very little
resistance for flow. Thus, when the segments are either frozen in or are free to move, damping is
low. The Tg due to TPU is seen at -60C. There is change in T g value due to TPU phase, on the
addition of PP into TPU. The Tg due to TPU transitions obtained from E " max and tan
max
are
given in Table 3.13 for ester and ether- based TPU blends. There is considerable change in T g
value due to TPU phase, on the addition of PP into TPU.
McGrum and colleagues have demonstrated that the tan curve of PP exhibits three
relaxations localized in the vicinity of -80 (), 10 () and 108 C (). However DMA analysis
[Figure 3.39(d) and 3.40(d)] do not show any clear separate tan peak corresponding to the
relaxation [glass transition temperature of PP (Tg)], but more definite tan peak was observed
corresponding to T at approximately at 108 C. The tan value at around 108C, corresponding
to the transition (T), is believed to be the result of molecular motions which resist the
softening effect of the applied heat. While Tg reflects mobility within the amorphous regions, T
dictates the onset of segmental motion within the crystalline regions. Clear tan peak was
observed corresponding to the relaxation for the TPU/PP blend composition of 0/100 and
30/70, but not in the case of 50/50, 70/30 and 0/100. The tan peak corresponding T for TPU/PP
(0/100) and (30/70) blend composition are given in Table 3.13.
eliminates the relaxation in the blend system.
Table 3.13. Uncompatibilised (a) Ester- (b) Ether- TPU/PP blend
57
Increase of TPU portion
(a)
Material
(b)
Tg from
E "(C)
Tg from
Tan (C)
-36
-24
TPU/PP 70/30
-34
-22
TPU/PP 50/50
-24
-16
TPU/PP 30/70
-20
-7& 103 (T)
TPU/PP 0/100
-11
3& 108 (T)
18000
TPU/PP (0/100)
16000
Storage Modulus (MPa)
Log Storage Modulus (MPa)
TPU/PP 100/0
TPU/PP (30/70)
14000
TPU/PP (50/50)
12000
TPU/PP (70/30)
10000
8000
TPU/PP (100/0)
6000
4000
2000
0
-100
100
Tg from
E "(C)
Material
Tg from
Tan (C)
TPU/PP 100/0
-44
-30
TPU/PP 70/30
-39
-25
TPU/PP 50/50
-32
-21
TPU/PP 30/70
-28
-14& 101 (T)
TPU/PP 0/100
-11
3& 108 (T)
4.5
4
3.5
3
2.5
2
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
1.5
1
0.5
0
-100
200
Temperature,C
100
200
Temperature,C
(a)
(b)
Figure 3.39 (a). Storage modulus (b). Log storage modulus of ester-TPU based
uncompatibilised blends
1000
900
800
700
0.16
500
400
300
0.12
0.1
0.08
0.06
200
0.04
100
0.02
100
TPU/PP (30/70)
TPU/PP (0/100)
0.14
600
0
-100
TPU/PP (100/0)
TPU/PP (70/30)
TPU/PP (50/50)
0.18
Tan delta
Loss Modulus(MPa)
0.2
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
0
-100
200
-50
50
100
150
200
Temperature, C
Temperature,C
( c)
(d)
Figure 3.39 . ( c). Loss modulus (d). Tan of ester- TPU based uncompatibilised blends
58
18000
TPU/PP (0/100)
TPU/PP (30/70)
16000
14000
12000
TPU/PP (50/50)
TPU/PP (70/30)
10000
TPU/PP (100/0)
8000
6000
4000
2000
0
-100
100
200
4.5
4
3.5
3
2.5
2
1.5
1
0.5
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (0/100)
0
-100
100
200
Temperature,C
Temperature,C
(a)
(b)
Figure 3.40(a). Storage modulus (b). Log storage modulus of ether-TPU based
1000
TPU/PP (0/100)
900
TPU/PP (30/70)
800
TPU/PP (50/50)
TPU/PP (70/30)
700
TPU/PP (100/0)
600
Tan delta
Loss Modulus(MPa)
uncompatibilised blends
500
400
300
200
100
0
-100 -50
50
100
Temperature,C
150 200
0.2
0.18
0.16
0.14
0.12
0.1
0.08
0.06
0.04
0.02
0
-100
TPU/PP (100/0)
TPU/PP (70/30)
TPU/PP (50/50)
TPU/PP (30/70)
TPU/PP (0/100)
100
200
Temperature,C
Figure 3.40. (c). Loss modulus (d). tan of ether-TPU based uncompatibilised blends
Figures 3.39(a), 3.39(c), 3.40(a)and 3.40(c)upper and lower curves show the temperature
dependence on the storage and loss modulus of the uncompatibilised samples from -100 to 200 C.
The effects of temperature on tan values of the blends are seen in Figures 3.39(d) and 3.40(d). At
very low temperature modulus of the blends are high. The modulus decreased with increase in
temperature and finally levels off at high temperature. The storage and loss moduli values of TPU are
high at low temperature and decreased sharply around-60 C indicating distinct transition from
59
glassy to rubbery region. TPU rich blend (TPU/PP 70/30) also shows same trend. At low
temperature, the molecules are frozen in and exhibit very high modulus. Some secondary relaxations
occur after the glassy transitions.TPU is having very low modulus in the rubbery plateau. The
modulus values finally levels off as temperature increases. The decrease in modulus above PP T g is
more pronounced in PP rich blends. Around the glass transition temperature of TPU the blends are in
the glassy state and the modulus is high.
The E' intensity follows nearly the composition. Thus it can be concluded that the stiffness of
the samples decreases with TPU content. A high modulus observed in TPU/PP 30/70 is mainly due
to major contribution from PP. A sharp increase in damping value in TPU/PP 70/30 blend is due to
the major contribution of TPU phase. It is observed that at room temperature, the storage and loss
moduli of PP are greater than TPU due to the high brittleness of PP because of its high T g. Thus the
unmodified TPU/PP shows typical behavior for immiscible blends. The above results are very much
in agreement with that of systems based on blends of polypropylene and ethylene propylene diene
monomer (PP)/EPDM studied by Papke and Karger-Kocsis[73-74]
The chain mobility of the polymer can be understood from the area under the loss modulus
versus temperature curve [75]. As expected, loss modulus increases up to transition zone, until they
reach a maximum and then decreases with temperature. The damping behaviour of the blends
increases with increase in concentration of TPU.
3.4.1.1. Modulus Composition Models
Various models exist for predicting elastic properties of polymeric materials. Different
models like parallel, series, Halpin- Tsai, Kerner, Davies and Budiansky were used to predict the
mechanical behavior of the blends. The two simple models are the so-called parallel and series
models, which could represent the upper and lower bounds of the tensile strength predictions.. This
model is applicable to materials in which the components are connected parallel to one another so
that the applied stress elongates each component to the same extent. Figure 3.41(a) and (b) gives a
comparison of theoretical and experimental values of storage modulus of the ester- and ether-TPU
based blends at 10C and frequency of 10 Hz. The experimental values are in between series and
parallel models. Experimental and theoretical curves of storage modulus of TPU/PP blend as a
function of volume fraction of PP. Poisson ratio for homopolymers was assumed to be 0.48 for TPU
and 0.40 for PP.
60
7000
5000
4000
6000
Storage Modulus(MPa)
7000
Experiment
Parallel
Series
Halpin Tsai
Coran
Kerner
3000
2000
1000
Experiment
Parallel
Series
Halpin Tsai
Coran
Kerner
6000
5000
4000
3000
2000
1000
0
0
0
0.2
0.4
0.6
0.8
0.2
0.4
0.6
0.8
(a)
(b)
Figure 3.41. TPU based blends theoretical model (a) Ester based blends (b) Ether based blends
The predictions of these theories have been made with E1 =293 for ester, E1= 331 for
ether and E2= 6028 MPa for the storage modulus for TPU and PP respectively.
3.4.2. Effect of Compatibilisation with nanoclay
Preparation of ester- and ether- TPU/C10A nanocomposites by direct melt blending [23, 39-44],
using 3 wt% Cloisite 10A (organically modified montmorillonite clay) as the nanoscale reinforcement.
Nanocomposites with PP using MA-g-PP as the compatibiliser were prepared by melt blending.
Low temperature DMA measurements on few selected samples of the compatibilised blends
carried out at a frequency of 10 Hz. gave the following reports. The effect of temperature on storage
modulus, loss modulus and tan of MA-g-PP compatibilised blends are seen in Figure 3.42.(a), (c),(d)
and 3.43 (a),(c),(d)respectively. Indication of miscibility; while two separate Tg s indicate immiscibility of
the system. Experimental evidence of miscibility is often found when a single and a sharp glass transition
temperature, Tg, is observed in between the Tg s of the individual components. In the glass transition
region of linear polymers, the storage modulus usually decreases by three to four orders of magnitude
over a temperature range of 20-30C. Also, in the glass transition region, E" and tan go through
maxima. The quantities E " and tan can be utilized in mechanical damping applications to reduce
mechanical vibrations and noise emission. Tg from E "max and tan
max
are given in Table 3.14.The
dynamic mechanical parameters (storage modulus) for the various blend nanocomposites are plotted as a
function of temperature, at a constant frequency of 10 Hz (Figure 3.42(a)and 3.43(a). The storage moduli
at -50 0C, 0 0C, 20 0C and 30 0C are shown in Table 3.14 and 3.15.The storage modulus at -40 0C of
61
ester-TPU/PP blends, without nanoclay and compatibilised with the same wt% of MA-g-PP, prepared
under identical conditions, is reported to be 7.23 GPa. Thus, a 3 wt% C10A reinforcement increased the
storage modulus of the blend by ~ 40%. At room temperature, the storage modulus value of the esterTPU (nano)/ PP/ MA blend nanocomposite is more than that of the other blends. It is possible that welldispersed clay platelets resulted in an increase of storage modulus. The dissipation factor (tan) of the
materials is presented as a function of temperature in Figure 3.42(d) and 3.43(d). The tan peak is
associated with the soft segment glass transition temperature and the peak positions are given in Table
3.14. The temperature corresponding to the tan peak increases in the order- ester-TPU/PP< esterTPU/PP/MA-g-PP < ester-TPU(nano)/PP/MA. This is attributed to the increasing order of dispersion for
the blends. In DMA testing, one way of calculating Tg is based on tan delta. Each tan delta peak
temperature indicates the Tg of TPU soft segment for that particular composition. A shift in this peak
indicates an effect on the dispersion level of blend system. The temperature corresponding to the tan delta
peak increases in the order: TPU / PP < TPU / PP / MA-g-PP < TPU / PP(nano) / MA-g-PP < TPU
(nano) / PP / MA-g-PP (-22 0C < -15 0C< -11 0C < -7 0C for ester and -25 0C < -18 0C< -14 0C < -10 0C
for ether). The same order was observed in DSC experiment also (-61.5 0C < -59.3 0C < - 53.5 0C). The
Tg may have different numerical values but it follows the same order. DMA and DSC experiments are
based on different concepts and hence the numerical values may not match. Ether based blends also
shows same type of trend with less shift in Tg values.
Table 3.14 Tg of compatibilised (a) Ester- and (b) Ether- TPU/PP (70/30) blends
(a)
(b)
Tg
(E")
Tg
(tan)
TPU/PP 70/30
-34
-22
TPU/PP/MA-g-pp
-26
Material Composition
Tg
(E")
Tg
(tan)
TPU/PP 70/30
-39
-25
-15
TPU/PP/MA-g-pp
-34
-18
-24
-11
-32
-14
-19
-7
-27
-10
Material Composition
62
Table 3.15. Storage modulus of compatibilised ester-TPU based blends

Storage modulus, E (MPa)
Blend composition
-50C
0C
20C
30C
TPU/PP
7101
1434
721
348
TPU/PP/MA-g-PP
7605
2656
1763
1361
8206
2701
1804
1411
10173
3612
2230
1760
TPU(nano)/PP/MA
12000
14000
TPU/PP(nano)/MA
TPU/PP/MA
10000
TPU/PP
8000
6000
4000
2000
0
-100
100
Temperature,C
4.5
4
3.5
3
2.5
2
1.5
TPU(nano)/PP/MA
TPU/PP(nano)/MA
TPU/PP/MA
TPU/PP
1
0.5
200
0
-100
100
200
Temperature, C
(a)
(b)
Figure 3.42(a). Storage modulus (b). Log storage modulus of compatibilised ester-TPU based
blends
900
0.3
TPU(nano)/PP/MA
TPU/PP(nano)/MA
TPU/PP/MA
TPU/PP
700
600
500
400
300
200
TPU/PP(nano)/MA
TPU/PP/MA
TPU/PP
0.2
0.15
0.1
0.05
100
0
-100
TPU(nano)/PP/MA
0.25
Tan delta
Loss Modulus(MPa)
800
100
0
-100
200
Temperature,C
100
Temperature,C
Figure 3.42(c). Loss modulus (d). Tan of compatibilised ester-TPU based blends
63
200
Table 3.16. Storage modulus of compatibilised ether-TPU based blends

Storage modulus, E (MPa)
Blend composition
-50C
0C
20C
30C
TPU/PP
5489
763
523
431
TPU/PP/MA-g-PP
6116
902
578
464
6613
1159
760
598
7763
1921
1144
917
4.5
TP U(nano)/PP /MA
12000
TP U/PP(nano)/MA
10000
TP U/PP/MA
14000
TP U/PP
8000
6000
4000
2000
0
-100
100
200
Temperature,C
4
3.5
3
2.5
2
1.5
TP U(nano)/P P/MA
TP U/PP (nano)/MA
0.5
0
-100
TP U/PP /MA
TP U/PP
100
Temperature, C
200
(a)
(b)
Figure 3.43(a). Storage modulus (b). Log storage modulus of compatibilised ether-TPU based
blends
0.25
800
TPU(nano)/PP/MA
700
TPU/PP(nano)/MA
600
TPU/PP/MA
500
TPU/PP
TPU(nano)/PP/MA
TPU/PP(nano)/MA
0.2
Tan delta
Loss Modulus(MPa)
900
400
300
200
TPU/PP/MA
TPU/PP
0.15
0.1
0.05
100
0
-100
100
200
100
200
Temperature,C
Temperature,C
Figure 3.43(c ). Loss modulus
0
-100
(d). Tan of compatibilised ether-TPU based blends

64
There is change in Tg values due to TPU on adding MA-g-PP to the blend system. The
twostep curves in the figure for the blends, is due to two-phase morphology indicating
immiscibility. Thus the transitions due to TPU and PP phases indicate that addition of
compatibilisers do not make the system single phase. Or compatibiliser addition could not
promote molecular level miscibility. This observation is in agreement with conclusions made by
Paul[76] that if two polymers are far from being miscible, then no compatibiliser is likely to
make the system single phase.
The Tg corresponding to TPU transition is shifted to higher temperature upon
compatibilisation. MA-g-PP with nanoclay compatibilised blends showed maximum shift .
Nanoclay reinforcement, besides giving substantial increase in modulus and tensile strength, also
functions as a surface modifier for TPU hard segments.. The reduced interfacial tension between
the thermoplastic polyurethane and the polypropylene due to the incorporation of nanoclay gives
better compatible blends. Compatibilisation effect is further improved by introducing
functionalised PP (MA-g-PP) in the nanoclay containing blends. At room temperature, the
storage modulus value of the ester-TPU blend nanocomposite is more than that of the ether-TPU
blend nanocomposite.As mentioned in the introductory chapter, the high polarity difference
between thermoplastic polyurethane and polypropylene limits the miscibility of their blends.
Nanoclay was used to reduce the surface energy of the TPU hard segments and makes them more
compatible with the non-polar PP. More miscible blends have been obtained by using MA-g-PP
as the compatibiliser. Better dispersion of organoclay may be attributed to two reasons. Firstly,
maleic anhydride forms hydrogen bonds with the hydroxyl groups of the silicate layers.
Secondly, there is a possible chemical reaction between maleic anhydride and the urethane
linkages in the TPU hard segments. Compared to the ether-TPU based blend nanocomposites,
the ester-TPU blends show better miscibility as confirmed by DMA analysis.
The clear
difference between ester-TPU and ether-TPU is that ester-TPU has carbonyl groups both in the
polyol segments as well as the TPU hard segments. This may lead to more extensive hydrogen
bonding in the blend system thus improving the miscibility.
65
3.4.3. Effect of sequence of nanoclay addition on TPU/PP blend

In sequence I, TPU/nano nanocomposites were prepared and subsequently blended
with PP using MA-g-PP as compatibiliser. In sequence II, nanoclay was added to PP by similar
extruder melt blending and subsequently melt blended with TPU using MA-g-PP as
compatibiliser
Compared to sequence II blend nanocomposites, the sequence I shows better
miscibility. The clear difference between sequence I and sequence II is that the effect of
nanoclay is fully utilized for changing the surface tension of TPU hard segment in sequence I. In
the case of sequence II, the dispersion and the reaction of nanoclay with TPU was reduced since
nanoclay is first added to PP.
Table 3.17. Effect of sequence of nanoclay addition on Tg
Material
Tg (0C) from
E
Tg (0C) from
Tan
TPU/PP(nano)/MA-g-PP (Ester)
-22
-9.0
TPU(nano)/PP/MA-g-PP (Ester)
-19
-7.0
TPU/PP(nano)/MA-g-PP (Ether)
-29
-12.0
TPU(nano)/PP/MA-g-PP (Ether)
-27
-10.0
14000
TPU(nano)/PP/MA
12000
TPU/PP(nano)/MA
Loss modulus (MPa)
16000
10000
8000
6000
4000
2000
0
-100 -50
0
50 100 150 200
Temperature,C
900
800
700
600
500
400
300
200
100
0
-100 -50
TPU/PP(C10A)/MA
TPU(C10A)/PP/MA
50
100 150 200
Temperature, C
(a) Ester-TPU storage modulus
(b) Ester-TPU loss modulus
66
0.3
TPU(nano)/PP/MA
Storage modulus (MPa)
0.25
Tan delta
12000
TPU/PP(nano)/MA
0.2
0.15
0.1
0.05
0
-100
100
Temperature,C
200
6000
4000
2000
50
100 150 200
Temperature,C
(d) Ether-TPU storage modulus

TPU(nano)/PP/MA
TPU/PP(nano)/MA
Tan delta
Loss modulus (MPa)
8000
0
-100 -50
( c) Ester-TPU Tan
800
700
600
500
400
300
200
100
0
-100 -50
TPU(nano)/PP/MA
TPU/PP(nano)/MA
10000
0.25
TPU(nano)/PP/MA
0.2
TPU/PP(nano)/MA
0.15
0.1
0.05
50
0
-100
100 150 200
100
200
Temperature,C
Temperature,C
(e) Ether-TPU loss modulus
(f) Ether-TPU Tan
Figure 3.44. Effect sequence of nanoclay addition on compatibilised TPU/PP blends

3.5 Flame-Retardant Properties
Table 3.18 shows the flame-retardant properties of the neat and flame-retardant TPU/PP
blends with different compositions. The limited oxygen index (LOI) value of the neat and
TPU/PP blend were 18%, and those of the flame-retardant PP/TPU blends and nanoclay filled
TPU/PP blends were increased about 910 units as compared with that of the neat TPU/PP
blend, which showed the studied flame retardants and nanoclay could greatly increase the LOI
value of the system. However reduction of mechanical properties is observed for conventional
flame retardant based compositions.
Table 3.18. LOI test and UL 94 test values for nanoclay based 70/30 TPU/PP blends
67
LOI values
Material
UL-94
PP
Ester-TPU
Ether-TPU
Ester-TPU/PP and Ether-TPU
(70/30)
(3%nanoclay) (70/25/5)
(5%nanoclay) (70/25/5)
(3%nanoclay) (70/25/5)
(5%nanoclay) (70/25/5)
V2
V2
V2
(ASTM D 2863)
18
17
17
V2
17
V1
23
V0
28.5
V1
22
V0
27.5
The results of the vertical burning test (UL-94) of the studied samples are also shown in
Table 3.18. The pure TPU/PP blend and the nanoclay filled TPU/PP blend containing 3%
nanoclay could not pass the UL-94 test, dripping occurs. However, the vertical burning
behaviour of the PP/TPU blends was improved and no dripping occurred with the incorporation
of the 5% nanoclay and reached a V0 rating.
Nanocomposites are a new class of polymer systems. Modified layered silicates as fillers
are dispersed at a nm-level within a polymer matrix. For nanocomposites new extraordinary
properties are observed. The thermal stability and the flame retardancy of polymers forming
nanocomposites are improved. The flame retardancy mechanism of layered silicate
nanocomposites is based on the char formation and its structure; the char insulates the polymer
from heat and acts as a barrier, reducing the escape of volatile gases from the polymer
combustion. The suggested mechanism by which clay nanocomposites function involves the
formation of a char and accumulation of minerals at the surface that serves as a potential barrier
to both mass and energy transport [77-82]. Visually a smooth char layer is formed at the surface
of the nanocomposite leaving a black char residue at the end of the experiment.
68
Table 3.19. LOI test and UL 94 test values for flame retardant based 70/30 TPU/PP blends
Material
LOI values
V0
32
V0
31
Ester-TPU/PP
UL-94
(20% DECA)
Ether-TPU/PP
(20% DECA)
DECA Decabromodiphenyl oxide (Flame retardant)

In summary, the flame retardant composed of 5% nanoclay and MA-g-PP compatibiliser
showed a good flame-retardant effect on the TPU/PP (70:30) blend, having the highest LOI
value (28.5%) and a UL-94 V-0 rating.
3.5.1. Mechanical Properties
Table 3.20 provides the mechanical properties of the neat and the flame-retardant
PP/TPU blends. A slip between the specimen and grip occurred at a very high strain levels (
600 to 800) and the specimens could not be broken. The ultimate elongations for these samples
were thus unavailable. As shown in Table 3.20, the tensile stress at 200 % strain and flexural
modulus of the ester-TPU/PP (70/30) blend are 6.4 MPa and 350 MPa, respectively. The
introduction of the nanoclay as the flame retardant to the TPU/PP blend system increased the
mechanical properties. The tensile stress at 200 % strain of the flame-retardant TPU/PP blend
was increased by 120% for 5% nanoclay loading; the increase of which was the largest;
the
flexural modulus was increased by 80%90%. Sample ester-TPU(nano)/PP/MA-g-PP(5%

nanoclay loading) had the best integrated mechanical properties among the flame-retardant
PP/TPU blends; its tensile stress at 200 % strain, and flexural modulus are 14.2 MPa, and 710
MPa, respectively.
69
Table 3.20. Mechanical properties of nanoclay based TPU/PP blends

Tensile stress at 200% strain
(MPa)
Flexural
modulus (MPa)
32.6 ( at break)
1650 1
Neat ester-TPU
4.3 0.05
61 1
Neat ether-TPU
4.3 0.05
60 1
Ester-TPU/PP (70/30)
6.4 0.05
350 1
Ether-TPU/PP (70/30)
6.7 0.05
365 1
Ester-TPU(3%nano)/PP/MA-g-PP (70/25/5)
10.3 0.05
605 1
Ester-TPU(5%nano)/PP/MA-g-PP (70/25/5)
14.2 0.05
710 1
Ether-TPU(3%nano)/PP/MA-g- PP(70/25/5)
9.8 0.05
565 1
Ether-TPU(5%nano)/PP/MA-g-PP(70/25/5)
13.7 0.05
673 1
Materials
Neat PP
Table 3.21. Mechanical properties of flame retardant based TPU/PP blends

Materials
Ester-TPU/PP
(20% DECA)
Ether-TPU/PP
(20% DECA)
Tensile
strength (MPa)
Elongation
31.1 0.1
2001
12051
30.6 0.1
2101
11581
70
(%)
Flexural
modulus (MPa)
Table 3.22. Rate of burning and ignition response test

Rate of burning
Ignition response time
(mm/min)
(seconds)
Neat PP
17.54
5-10
Neat ester-TPU
20.93
5-10
Neat ether-TPU
20.9
5-10
Ester-TPU/PP
18.3
5-10
Ether-TPU/PP
18.2
5-10
Ester-TPU (3%nano) /
PP/MA-g-PP
16.3
15-20
Ester-TPU (5%nano) /
PP/MA-g-PP
15.0
20-25
Ether-TPU (3%nano) /
PP/MA-g-PP
16.4
15-20
Ether-TPU (5%nano) /
PP/MA-g-PP
15.5
20-25
Material
3.6. Electrical Properties

3.6.1. Uncompatibilised blends electrical properties
3.6.1.1. Effect of blend ratio on volume resistivity
Basically, polymers have high value of resistivity, owing to the non-availability of free
electrons for conduction. Resistivity studies are important for insulating materials, because the
most desirable characteristic of an insulator is its ability to resist the leakage of electrical current.
Volume resistivity is numerically equal to the direct current resistance between opposite faces of
a one centimeter cube of a material, expressed in ohm centimeters. Figure 3.45 shows the
variation of volume resistivity v of TPU/PP blends as a function of TPU concentration. Polar
polymers have lower resistivity than non-polar polymers due to the polarization of polar
polymers under the influence of electrical field, which promote the conducting process.
From the Figure 3.45 it is clear that PP is a good insulator with very high value of volume
resistivity where as the volume resistivity of TPU is very low. In the case of blends the volume
71
resistivity values are in between that that of TPU and PP. As the concentration of TPU increases
Log volume resisitivity (Ohm-cm)
the volume resistivity values decreases.

7.3
7.2
7.1
7
6.9
6.8
6.7
6.6
6.5
6.4
6.3
6.2
Ether - TPU
Ester - TPU
Frequency: 1 MHz
20
40
60
80
100
120
Weight % of TPU
Figure 3.45. Variation of volume resistivity of TPU/PP blends with TPU content at 30 C
Volume resistivity of TPU, PP and their blends as a function of frequency is given in the
Figure 3.46. It can be seen from the Figure 3.46 that, with the incorporation of TPU, which is
comparatively a less insulating material reduces the volume resistivity.
Log volume resistivity (Ohm-cm)
14
12
10
8
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
6
4
2
0
0
Log frequency (Hz)
Figure 3.46 (a). Volume resistivity of ester-TPU, PP and their blends as a function of
frequency at 30 C
In TPU/PP (30/70) blend where PP forms the matrix, the curve is very close to PP curve
and in TPU/PP (30/70) the curve is very close to TPU. In all cases reduction in volume
resistivity is observed with increase in frequency. This can be attributed to the increase in
molecular mobility at high frequencies.
72
14
12
10
8
6
TPU/PP (0/100)
TPU/PP (30/70)
TPU/PP (50/50)
TPU/PP (70/30)
TPU/PP (100/0)
4
2
0
0
Log frequency (Hz)
Figure 3.46(b). Volume resistivity of ether-TPU, PP and their blends as a function of

frequency at 30 C
3.6.1.2. Dielectric constant (')
The dielectric constant (') is an important parameter in the case of an insulating material.
It is an expression of the extent to which a material concentrates electric flux. The dielectric
material is a substance that is a poor conductor of electricity, but an efficient supporter of
electrostatic fields. Materials with high dielectric constants are useful in the manufacture of high
value capacitors. The variation of dielectric constants of TPU, PP and their blends as a function
of frequency is shown in the Figure 3.47. It is evident from the figure that
' values of neat
TPU and their blends decrease with increasing the applied frequency. Generally the dielectric
constant of a polymer arises from various polarization phenomena that come into play when the
polymer is subjected to an electric field. The dielectric constant increases with increase in
polarizability. The different types of polarization possible in a material are (1) electronic
polarization (2) atomic polarization and (3) orientation polarization [83]. The orientation
polarization contributes a major part of the total polarization for polar polymers. In
heterogeneous materials, there is a possibility for interfacial polarization, which arises due to the
difference in conductivities of the two phases [84]. Therefore in the case of TPU, which is a
polar polymer, all the three types of polarization contribute towards the dielectric constant. As a
result, TPU exhibits high dielectric constant, especially at low frequencies.
73
8
a
Dielectric constant (')
abcde-
2
1
TPU/PP (100/0)
TPU/PP (70/30)
TPU/PP (50/50)
TPU/PP (30/70)
TPU/PP (0/100)
0
0
Log frequency (Hz)
Figure 3.47(a). Variation of dielectric constant of ester-TPU /PP blends with frequency at
30 C
8
a
abcde-
2
1
TPU/PP (100/0)
TPU/PP (70/30)
TPU/PP (50/50)
TPU/PP (30/70)
TPU/PP (0/100)
0
0
Log frequency (Hz)
Figure 3.47(b). Variation of dielectric constant of ether-TPU /PP blends with frequency at
30 C
74
3.6.1.3. Dissipation factor and loss factor (")

The tangent of the dielectric phase angle or the tangent of the dielectric loss angle is
represented by the tan . The measurement of dissipation factor (tan ) and loss factor (") of an
insulating material is important. In electrical applications, it is desirable to keep the electrical
losses to a minimum. Electrical loss indicates the inefficiency of an insulator. The loss tangent is
a measure of the alternating current electrical energy, which is converted into heat in an insulator
[85-86]. This heat raises the temperature, leading to deterioration of the polymeric materials. The
variation of tan and loss factor with frequency for TPU, PP and their blends is depicted in the
Figure 3.48 and 3.49. Addition of TPU into PP increases dissipation and loss factor. The increase
in the value is due to orientation polarization of polar TPU followed by oscillation under electric
fields.
Dissipation factor (tan)
0.6
TPU/PP (0/100)
TPU/PP (50/50)
TPU/PP (100/0)
0.5
0.4
TPU/PP (30/70)
TPU/PP (70/30)
0.3
0.2
0.1
0
0
Log frequency (Hz)
Figure 3.48(a).Variation of dissipation factor of ester-TPU /PP blends with frequency at 30 C
Loss factor (")
4
3.5
TPU/P P (100/0)
TPU/P P (70/30)
TPU/P P (50/50)
TPU/P P (30/70)
2.5
TPU/P P (0/100)
2
1.5
1
0.5
0
0
Log frequency (Hz)
Figure 3.48(b). Variation of loss factor of ester-TPU /PP blends with frequency at 30 C
75
0.5
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
0.4
TPU/PP (30/70)
TPU/PP (70/30)
0.3
0.2
0.1
0
0
Log frequency (Hz)
Figure 3.49(a).Variation of dissipation factor of ether-TPU /PP blends with frequency at

30 C
Loss factor (")
4
3.5
TPU/P P (100/0)
TPU/P P (70/30)
TPU/P P (50/50)
TPU/P P (30/70)
2.5
TPU/P P (0/100)
2
1.5
1
0.5
0
0
Log frequency (Hz)
Figure 3.9(b). Variation of loss factor of ether-TPU /PP blends with frequency at 30 C
3.6.2 Compatibilised blends electrical properties
The two polymers TPU and PP are incompatible. The immiscible blends have got
unfavorable interactions which lead to unstable morphology and poor interfacial adhesion, which
leads to the inferior properties of the blends. These limitations can be overcome by
compatibilisation. Hence a reactive route was employed to compatibles the system using MA-gPP as the compatibiliser. The urethane group of the TPU can react with the anhydride group of
the compatibiliser to form a graft polymer, which can locate at the interface. Analysis of phase
morphology, mechanical, DMA and thermal properties proved that MA-g-PP could act as an
effective compatibiliser in TPU/PP blend system. In this context we, analyze the effect of
compatibilisation on the dielectric properties of 70/30 (TPU/PP) blends. Both ester- and etherbased TPU was used for these studies because soft segment of ester and ether TPU has different
76
surface tension values. Further to that nanoclay was incorporated in the system to reduce the
surface tension of TPU hard segment to make the blend more compatible.
3.6.2.1.Volume Resistivity
14
12
10
8
6
TPU/PP (70/30)
4
2
14
12
10
8
6
TPU/PP (70/30)
4
2
0
0
2
4
5
6
Log frequency (Hz)
4
5
6
Log frequency (Hz)
(a)
(b)
Figure 3.50 (a). Effect of compatibiliser concentration on the volume resistivity as a function of
frequency at 30C for ester based TPU blends
Figure 3.50(b). Effect of compatibiliser concentration on the volume resistivity as a function of
frequency at 30C for ether based TPU blends
The effect of compatibilisation on the volume resistivity of the TPU/PP (70/30) blends is
given in the Figure 3.50.It is well evident from the figure that compatibilisation resulted in the
increase of volume resistivity. The highest value of volume resistivity is observed at 5% of
compatibiliser concentration. With the incorporation of 3 wt% of MA-g-PP, the resistivity
becomes almost close to that of the uncompatibilised blends. During the 3% addition of the
compatibiliser, the anhydride group will react with the urethane groups of TPU, contributing
towards the reduction in overall polarity of the system. When the concentration of the
compatibiliser increases above level, the amount of polar groups in the system increases. This is
reflected in the volume resistivity at high compatibiliser loading. The morphology of the
compatibilised blends suggests that, by the incorporation of 5 wt% of the compatibiliser, CMC is
reached. Therefore further addition of the compatibiliser will leads to the formation of micelles.
It is expected that, the micellar aggregates of the compatibiliser will result in the increase of the
polarity.
77
14
14
12
10
8
6
TPU/PP (70/30)
4
2
0
2
Log frequency (Hz)
12
10
8
6
TPU/PP (70/30)
4
2
0
2
4
5
6
Log frequency (Hz)
(a)
(b)
Figure 3.51 (a). Effect of nanoclay addition on the volume resistivity as a function of frequency
at 30C for compatibilised ester based TPU blends
Figure 3.51(b). Effect of nanoclay addition on the volume resistivity as a function of frequency
at 30C for compatibilised ether based TPU blends
3.6.2.2. Dielectric constant
The results of the effect of compatibilisation on the dielectric constant of TPU/PP (70/30)
blends are given in the Figure 3.52. It can be observed from the figure that compatibilisation
resulted in a substantial decrease of dielectric constant. The lowest value of dielectric constant
was observed at 5% of compatibiliser addition. Further addition of the compatibiliser increased
the dielectric constant. As discussed earlier, this observation may be due to the formation of
aggregates of the compatibiliser beyond CMC. Nanoclay addition to the compatibilised blends
resulted in decrease of dielectric constant values. Compared to sequence II blend
nanocomposites, the sequence I shows high volume resistivity and low dielectric constant values.
78
6.5
6.5
Dielectric constant (
')
5.5
5
4.5
4
TPU/PP (70/30)
TPU/PP/MA- g- PP (70/23/7)
3.5
TPU/PP/MA- g- PP (70/27/3)
TPU/PP/MA- g- PP (70/25/5)
5.5
5
4.5
TPU/PP (70/30)
TPU/PP/MA- g- PP (70/23/7)
TPU/PP/MA- g- PP (70/27/3)
TPU/PP/MA- g- PP (70/25/5)
4
3.5
3
0
Log frequency (Hz)
(a)
3
4
5
Log frequency (Hz)
(b)
Figure 3.52. Effect of compatibiliser concentration on the dielectric constant as a function of

frequency at 30C (a) Ester TPU based (b) Ether TPU based
7
Dielectric constant ( ')
5
4
3
TPU/PP/MA- g- PP (70/25/5)
TPU(nano)/PP/MA- g- PP (70/25/5)
TPU/PP (70/30)
TPU/PP(nano)/MA- g- PP (70/25/5)
6
5
4
3
TPU/P P/MA- g- P P (70/25/5)
TPU(nano)/PP /MA- g- P P (70/25/5)

TPU/P P (70/30)
TPU/P P(nano)/MA- g- P P (75/25/5)
0
0
Log frequency (Hz)
(a)
Log frequency (Hz)
(b)
Figure 3.53. Effect of nanoclay addition on the dielectric constant as a function of frequency
at 30C for compatibilised (a) Ester -TPU based (b) Ether-TPU based
3.6.2.3. Dissipation factor and loss factor
Figures 3.54 to 3.57 show the variation of dissipation factor (tan ) and loss factor (")
on compatibilisation. As the frequency increases tan and loss factor decreases and then levels
off. The loss factor and dissipation factor reaches a minimum at 5% loading of the
compatibiliser. Increase in loss factor and dissipation factor at high concentration of MA-g-PP
can be attributed to the increase in the polarity of the systems at high loadings The lower values
79
of tan and " at the TPU(nano)/PP/MA-g-PP (compatibiliser loading of 5%,nanoclay loading

of 3%) implies that insulating property can be improved by using optimum concentration of the
0.3
compatibiliser and nanoclay.
0.25
0.2
0.15
TPU/PP (70/30)
0.1
0.05
0
0
0.3
0.25
0.2
0.15
TPU/PP (70/30)
0.1
0.05
0
0
Log frequency (Hz)
Log frequency (Hz)
Figure 3.54
Figure 3.55
Figure 3.54. Effect of compatibiliser concentration on the dissipation factor as a function of

frequency at 30 for ester-TPU based blends
0.3
0.3
0.25
0.25
Figure 3.55. Effect of compatibiliser concentration on the dissipation factor as a function of

frequency at 30 for ether-TPU based blends
0.2
0.15
0.1
TPU/PP (70/30)
0.05
0.15
0.1
TPU/PP (70/30)
0.05
0
0
0
0.2
Log frequency (Hz)
Log frequency (Hz)
(a)
(b)
Figure 3.56. Effect of nanoclay addition on the dissipation factor as a function of frequency
at 30C for compatibilised (a) Ester -TPU based (b) Ether-TPU based
80
3
TPU/P P (70/30)
TPU/P P/MA- g- P P (70/25/5)
TPU/P P(nano)/MA- g- P P (70/25/5)
TPU(nano)/P P/MA- g- P P (70/25/5)
TPU/PP (70/30)
2.5
Loss factor (")
Loss factor (")
2.5
1.5
1
1.5
1
0.5
0.5
0
0
Log frequency (Hz)
Log frequency (Hz)
(a)
(b)
Figure 3.57. Effect of nanoclay addition on the loss factor as a function of frequency at 30C
for compatibilised (a) Ester -TPU based (b) Ether-TPU based
3.7.FTIR Analysis
3.7.1. Neat Polymer FTIR Analysis
Transmittance %
120
100
80
60
Hydrogen bonded - NH
40
Free C=O
20
Hydrogen bonded C=O
0
3600
3100
2600
2100
1600
1100
600
Wavenumber (1/cm)
Figure 3.58 (a). Neat ester-TPU FTIR

120
Transmittance %
100
80
60
Free C=O
Hydrogen bonded -NH
40
Hydrogen bonded C=O
20
0
3600
3100
2600
2100
1600
Wavenumber (1/cm)
Figure 3.58(b). Neat Ether-TPU FTIR
81
1100
600
120
Transmittance %
100
80
60
40
20
0
3600
3000
2400
1800
1200
600
Wavenumber (1/cm)
(a)
Transmittance %
120
100
(b)
80
Figure
60
3.59.
40
(a)
20
0
3600
3000
2400
1800
1200
600
Wavenumber ( 1/cm )
Polypropylene FTIR (b) MA-g-PP FTIR

Figure 3.58(a) and 3.58(b) show the FTIR spectra of neat ester- and ether polyol soft
segment based TPUs respectively. As reported in the literature, the hard segments of TPU
contains NH and C=O groups, which can interact and form intermolecular hydrogen bonding.
Two infrared regions are of interest in this study on TPU/PP blends,i.e. N-H (3500-3000 cm -1)
and C=O (1800-1640 cm-1) stretching vibration absorption regions. Both the NH and C=O
absorption peaks are contributions of overlapping bands of their free and hydrogen bonded
group respectively.
In figure 3.58 , the NH absorption peak is observed at 3340 cm -1 which is due to the
hydrogen bonded NH in the urethane linkage. Similar behaviour is exhibited in FTIR spectra at
82
the regions of 1780-1640 cm-1 as shown in Figure 3.58 for C=O groups. Two peaks of carbonyl
absorption for pure TPU could be seen, which were attributable to a free carbonyl stretching
vibration at 1730 cm-1 and hydrogen bonded one at 1710 cm-1. For ether-TPU sample, the peak
at 3340 cm1 due to the N-H stretching(H-bonded to carbonyl), the peak at 2956-2850 cm 1 due
to the asym and sym CH2 stretching, the peak at 1728 cm1 due to the free C=O stretching and
the peak at 1704 cm1 due to hydrogen bonded C=O stretching. There was no distinct peak
assigned to NCO group at about 2230 cm1 for all samples, suggesting that the NCO group failed
to reach a detectable level. In the case of carbonyl peak, difference is observed between ester and
ether based TPU. The intensity of free carbonyl group is more for ester category, but in ether
category hydrogen bonded carbonyl group is more.
3.7.2 Uncompatibilised and compatibilised TPU/PP blends FTIR analysis
Relative Transmittance %
( a ) TPU/PP
( b ) TPU/PP/MA
( c ) TPU/PP(nano)/MA
( d ) TPU(nano)/PP/MA
a
1
2
3600
3100
2600
2100
3
1600
1100
600
Wavenumber (1/cm)
Figure 3.60. Ester-TPU based compatibilised blends FTIR

Parts a, b,c and d of Figure 3.60 show the FTIR spectra of
ester based TPU/PP,
TPU/PP/MA-g-PP, TPU/PP(C10A)/MA-g-PP and TPU(C10A)/PP/MA-g-PP blend systems

83
respectively. Three significant peaks are considered for discussion. Peak at 3340 cm
number represents the hydrogen bonded NH group. Peak at 1730 cm
-1
-1
wave
and peak at 1700 cm -1
wave number represents free C= O ( carbonyl ) and hydrogen bonded C= O respectively.

The NH groups in the urethane linkage of TPU/PP composition form hydrogen bonds
with carbonyls of other urethanes in TPU hard segments and with carbonyl group in the soft
segments of TPU[39-43]. In the case of TPU/PP/MA-g-PP composition NH groups form
additional hydrogen bonding with maleic anhydride group of compatibiliser. In the case of TPU
(nano)/PP/MA-g-PP and TPU/PP (nano)/MA-g-PP composition NH groups form further
hydrogen bonding with oxygen group of silicate layers of nanoclay. The increase of hydrogen
bonding is reflected in the FTIR spectra by increase of 3340 cm
-1
peak intensity.
The peak
intensity of hydrogen bonded NH group increases in the order: TPU/PP< TPU/PP/MA-g-PP <
TPU/PP(nano)/MA-g-PP < TPU(nano)/PP/MA. The intensity of 1730 cm
intensity of 1700 cm
-1
-1
peak decreases and
peak increases from a to d of Figure 3.60. The C= O of ester-TPU
hard and soft segments form hydrogen bonds with NH group of urethane linkage leading to
free C= O peak and hydrogen bonded C= O peak corresponding to 1730 cm
1700 cm
-1
-1
peak and
of Figure 3.60a. In the case of Figure 3.60b, C= O forms additional hydrogen
bonding with maleic anhydride group and in Figure 3.60c and Figure 3.60d, C= O forms
further hydrogen bonding with hydroxyl groups of nanoclay silicate layer. Hence, the intensity
of 1730 cm
-1
peak decreases and intensity of 1700 cm
-1
peak increases from Figure 3.60a to
Figure 3.60d.
Table 3.23. Ratio of the areas under the specific peaks
Ester-TPU Based blends
Ether-TPU Based blends
ANH/ACH
AHCO/ AFCO
ANH/ACH
AHCO/ AFCO
TPU/PP
0.21
0.56
0.12
3.12
TPU/PP/MA
0.23
0.61
0.15
3.32
TPU/PP(nano)/M
0.29
0.73
0.18
3.48
0.35
overlap
0.28
3.96
Material
A
TPU(nano)/PP/M
A
ANH: area under the hydrogen bonded NH peak; ACH: area under the -CH peak stretching
peak; AHCO: area under the hydrogen bonded C=O peak; AFCO : area under the free C=O peak.
84
450
400
350
( a ) TPU/PP
( b ) TPU/PP/MA
( c ) TPU/PP(nano)/MA
( d ) TPU(nano)/PP/MA
Relative Transmittance %
300
250
200
150
100
a
2
50
3600
3100
2600
2100
1600
1100
600
Wavenumber (1/cm)
Figure 3.61 Ether-TPU based compatibilised blends FTIR

Parts a, b,c and d of Figure 3.61 show the FTIR spectra of ether based TPU/PP,
TPU/PP/MA-g-PP, TPU/PP(nano)/MA-g-PP and TPU(nano)/PP/MA-g-PP blend systems
respectively. Ether based blend system also reflects the same trend of ester which is discussed in
earlier.
The intensity of free carbonyl group is more for ester category, but in ether category
hydrogen bonded carbonyl group is more. Typically the NH groups in the urethane linkage
form hydrogen bonds with carbonyls of the urethane linkage in the hard segment in both cases of
ether-TPU and ester-TPU. The NH groups are also able to form hydrogen bonds with ether
oxygen of ether-polyol in the soft segment in case of ether TPU and with carbonyl of esterpolyol in the soft segment in case of ester-TPU. Ester based blends has totally (inclusive of free
and hydrogen bonded) more C=O groups than ether based blends as confirmed by FTIR
analysis. The FTIR results indicate that the ester-TPU exhibited better compatibility than etherTPU. The clear
difference between ester-TPU and ether-TPU is that ester-TPU has carbonyl

85
groups both in the polyol segments as well as the TPU hard segments. This may lead to more
extensive hydrogen bonding in the blend system thus improving the compatibility.
Cloisite 10A, a more hydrophobic nanoclay, when pre-mixed with TPU, is also thought
to function as a compatibiliser for TPU/PP blends because of its affinity for the non-polar PP.
Compared to the other blend system, the ester-TPU(nano)/ PP/MA-g-PP blends show better
dispersion as confirmed by FTIR analysis. Presence of nanoclay in ester TPU(nano)/PP/MA-gPP may lead to more extensive hydrogen bonding in the blend system ,thus improving the
dispersion.
3.7.3. Effect of sequence of nanoclay addition on TPU/PP blends by FTIR analysis
In this work, studies were made on nanoclay filled MA-g-PP compatibilised TPU/PP
blends by considering the sequence of nanoclay addition. Figure 3.60 and 3.61 indicates that,
compared to sequence II (TPU/PP(nano)/MA-g-PP) blend nanocomposites,
the sequence I
(TPU(nano)/PP/MA-g-PP) shows better compatibility for both ester- and ether-based blends. The
effect of nanoclay is fully utilized for changing the surface tension of TPU hard segment in
sequence I. The areas under hydrogen bonded (A HCO) and free carbonyl peaks (AFCO) were
calculated and presented Table 3.23. In addition, the area under CH stretching (2860-2940 cm
-1
) was also calculated and used as internal standard. Table 3.23 indicates that, the ratio of
ANH/ACH and
AHCO/ AFCO value increases in the order: TPU/PP< TPU/PP/MA-g-PP <
TPU/PP(C10A)/MA-g-PP < TPU(C10A)/PP/MA for ester- and ether-based blends.

3.8. Transport Properties
3.8.1. Effect of blend composition
The amount of water uptake by neat TPU, PP and their blends at room temperature (30
C) is given in the Figure 3.62.
It is clear from the Figure 3.62 that water uptake percentage
varies with blend composition at 30C (RT). Neat TPU exhibits the highest water uptake value.
This indicates that TPU is highly prone to water absorption due to the presence of carbony1,
ester/ether groups in TPU, which can form hydrogen bonds with water. In addition to this, since
TPU is hygroscopic in nature, diffused water molecule can form hydrogen bonding with already
bonded water molecules. A very interesting observation of the neat TPU curve is that, it exhibits
an overshoot effect in which a maximum uptake occurs followed by a decrease. This over shoot
effect is caused by penetrant rejection during chain relaxation. The chain relaxation is attributed
to chain rearrangement after maximum penetrant uptake, and change in morphology due to the
86
presence of swollen molecule and also due to sample thickness [87-91]. The degree of the over
shoots effect decreases as the PP content increased and is absent at 30, 50 and 100% PP.
2
TPU/PP (100/0)
TPU/PP (50/50)
TPU/PP (0/100)
1.8
Qt (mol%)
1.6
TPU/PP (70/30)
TPU/PP (30/70)
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
50
100
150
200
1/2
(t)
(min)
250
300
350
1/2
(a)
1.8
1.6
Qt (mol%)
1.4
TPU/PP (100/0)
TPU/PP (70/30)
TPU/PP (50/50)
TPU/PP (30/70)
TPU/PP (0/100)
1.2
1
0.8
0.6
0.4
0.2
0
0
50
100
150
(t)
1/2
200
(min)
250
300
350
1/2
(b)
Figure 3.62. Sorption curves showing % uptake of water for polymers and their blends at
room temperature. (a) Ester- TPU based (b) Ether-TPU based
In the case of PP, water absorption is almost negligible. All the blends show a significant
initial increase in water uptake with time and reaches equilibrium after a few days. The Q t values
systematically increases with increase in the TPU content. The higher percentage water uptake
for the 50, and 70% of TPU can be explained on the basis of the morphology of the blends. In
87
TPU/PP (70/30) blend PP is dispersed as domains in the continuous TPU matrix. So with
increase in the TPU content, the hydrophilic TPU forms the continuous phase and facilitates the
entry of the water, thus increases the water sorption of the blends.
3.8.2. Effect of compatibilisation
As discussed in the previous sections, owing to the lack of favourable interfacial
interactions, TPU and PP are highly immiscible. We employed compatibilisation strategy to
improve the compatibility between the polymers. The compatibiliser used is MA-g-PP, which
ensures compatibility through hydrogen bonding and chemical reaction between urethane linkage
and maleic anhydride moiety. There are several examples in the literature for the urethaneanhydride reactive compatibilisation [21,22,25]. We have investigated the effect of addition of
different levels of compatibiliser, MA-g-PP on the water sorption behaviour of TPU/PP (70/30)
blends. The influence of addition of MA-g-PP on the water uptake of TPU/PP (70/30) blends is
shown in the Figure 3.63. It is evident from the figure that water sorption decreases with
compatibiliser addition. This is due to the compatibilising action of the copolymer.
2
1.8
TPU/PP (70/30)
1.6
Qt (mol%)
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
50
100
150
1/2
(t)
(min)
(a)
88
200
1/2
250
300
350
1.8
1.6
Qt (mol%)
1.4
TPU/PP (70/30)
1.2
1
0.8
0.6
0.4
0.2
0
0
50
100
150
1/2
200
(t) (min)
1/2
250
300
350
(b)
Figure 3.63. Effect of compatibilisation using MA-g-PP on the water sorption of TPU/PP
(70/30) blends at RT (30C) (a) Ester-TPU based blends (b) Ether TPU based blends
A detailed analysis of the action of the compatibiliser molecules in reducing the water up
take indicates that, prior to compatibilisation, the blends is characterized by a sharp interface due
to the high interfacial tension and poor adhesion between the components. Upon the addition of
the compatibiliser the situation undergoes a drastic change. The maximum uptake reduction is
observed for 5% of the compatibiliser loading. This is because interfacial saturation has occurred
at around 5% of MA-g-PP and further addition of the compatibiliser could not modify the
interface any more.
3.8.3 Effect of nanoclay addition
The sorption curves of TPU/PP (70/30) blends compatibilised with 5% of MA-g-PP and
two different sequence of nanoclay addition is shown in the Figure 3.64.
89
2
TPU/PP (70/30)
1.8
1.6
Qt (mol%)
1.4
1.2
1
0.8
0.6
0.4
0.2
0
0
50
100
150
200
250
300
350
(t)1/2 (min)1/2
(a)
1.2
Qt (mol%)
1
0.8
0.6
0.4
TPU/PP (70/30)
0.2
0
0
50
100
150
200
250
300
350
(t)1/2 (min)1/2
(b)
Figure 3.64. Effect of compatibilisation using 5% of MA-g-PP with different sequence of
nanoclay addition on the water sorption of TPU/PP (70/30) blends
(a) Ester-TPU based blends (b) Ether TPU based blends
The equilibrium uptake is highest for TPU/PP (70/30) and lowest for TPU
(nano)/PP/MA-g-PP. The other systems show intermediate values. The transport of the water
through the nanoclay filled compatibilised system is in the order: TPU (nano)/PP/MA-gPP(70/25/5)< TPU/PP(nano)/MA-g-PP (70/25/5)< TPU/PP/MA-g-PP(70/25/5) < TPU/PP(70/30).
90
These observations can be also explained on the basis of surface tension values which were
explained in earlier. Ether based TPU blends uptake of water is less compare to ester based
systems.
4. Conclusion
Nanoclay reinforcement, besides giving substantial increase in modulus and
tensile strength also function as a surface modifier for TPU hard segments. The reduced
interfacial tensions between the thermoplastic polyurethane and the polypropylene due to the
incorporation of nanoclay gives better compatible blends. Cloisite 10A, a more hydrophobic
nanoclay, when pre-mixed with TPU, is also thought to function as a compatibiliser for TPU/PP
blends because of its affinity for the non-polar PP. Compatibilisation can be further improved by
introducing functionalised PP (MA-g-PP) in the nanoclay containing blends. The strategy of
compatibilisation is supposed to be hydrogen bonding between carbonyl functional groups of
TPU, hydroxyl group of nanoclay silicate layers and anhydride moiety of MA. Different
characterisation techniques such as XRD, DSC, TGA, SEM, TEM and DMA studies were
carried out to characterize the prepared samples. Evaluation of tensile, abrasion and water
absorption properties of the blends and blend nanocomposites were carried out for analyses
purpose. Comparison of dispersion characteristics and properties of ester- and ether-TPU blend
nanocomposites and effect of sequence of nanoclay addition were evaluated. The melt blending
technique that we have adopted offers an advantage of introducing no foreign materials (like
solvents) into the blend. For this reason and because of the simplicity and speed of melt mixing it
has an economic advantage, which makes it a commercially acceptable blending method.
Most of the polymer products have to undergo cyclic stressing during their service
period. This cyclic stressing will generate heat, which can cause failure of the material. Hence
the study of the dynamic mechanical thermal properties is of crucial importance. The storage
modulus for the blends was between the E'/T curves of the pure TPU and PP, which also
suggested that the TPU and PP are partially miscible. Variation of the storage modulus (E') as a
function of the temperature was studied for the pure TPU and PP, as well as for the TPU/PP
blends. The values of storage modulus decreased monotonically with increasing temperature.
The E' curve of TPU shows a typical behaviour of an elastomer.The storage modulus curves of
the blends around the glass transition zone were intermediate between the E'/T curves of the pure
TPU and PP. The value of storage modulus of blends steady increases with increasing PP content
in blends. The damping factor, tan, of the pure TPU, PP, and TPU/PP blends were discussed. A
91
very good correlation was found between morphology and dynamic mechanical properties.
Various composite models were used to predict the behaviour of the blends. Compatabilisation
of the blends and nanoclay addition showed significant increase in storage modulus because of
the enhanced interfacial interaction.
Mechanical properties of polymeric material are of crucial importance in designing a product.
The results obtained from mechanical property measurements and SEM analyses were
complementary. The mechanical properties of pure TPU, PP, and TPU/PP blends were measured by
stressstrain tests and obtained results are discussed. Pure TPU is ductile elastomer, while pure PP is
a rigid material. Simultaneously, the TPU had higher elongation at break in comparison to pure PP. It
is generally expected that an increase in the amount of stiff material in elastomeric material results in
an increase in tensile strength of blends. Compatibilisation improved the mechanical properties. The
increase in mechanical properties can be assigned to the increase in interfacial adhesion between
TPU and PP phases. Compatibilisation led to a fine morphology and made the interface stronger,
where effective stress transfer is possible. MA-g-PP was found to be a good compatibiliser for this
blend system. Nanoclay addition led to a further fine morphology in the blend system. Effect of
sequence of nanoclay addition in the blend system also studied.
The analysis of thermal stability of polymeric materials is necessary for the development of
durable products. The thermal degradation of TPU/PP blends was investigated using
thermogravimetric method. The thermogravimetric (TGA) studies revealed that the addition of PP to
TPU improved the thermal stability of the blends significantly. All the blends showed improved
initial decomposition temperature up on the addition of PP to TPU. Phase morphology was found to
be one of the decisive factors that affected the thermal stability since the thermal stability depended
on the stability of the matrix phase. The effect of compatibilisation of TPU/PP blend using MA-g-PP
on thermal degradation was also investigated. It was observed that the compatibiliser improved the
thermal stability of the blends considerably, by providing improvement in the interfacial interaction
between TPU and PP. The compatibiliser increased the decomposition temperature of these systems
especially at a critical value of its concentration in the blends. Nanoclay addition in the
compatibilised TPU/PP blends
was also found to provide improvement in the decomposition
temperature. Nanoclay filled compatibilised blend showed the highest decomposition temperature.
Among the different composition systems used, sequence I nanoclay filled ester-TPU based system
showed higher activation energy values.
92
XRD studies of the uncompatibilised blends revealed a slight reduction in crystallinity and
increase in interplanar distance of the PP as the incorporation of TPU. Compatibilisations did not
show much appreciable change in the crystallization pattern. In the case of nanoclay addition
marginally reduced the crystallinity of the system.
The transport properties of blends were studied to get an idea about the barrier properties of
the material. The transport properties are mainly depending on blend ratio, solvent polarity and
temperature. Since TPU is a hygroscopic thermoplastic, there is a good practical importance in
investigating water sorption behaviour of TPU based blends. The electrical properties such as
volume resisitivity, dielectric constant, loss and dissipation factors were measured over a wide range
of frequencies. Compared to polar TPU, PP exhibited good insulating properties. Among the neat
polymers, PP possessed the maximum volume resistivity and minimum dielectric constant. The
volume resistivity values of the blends fell in between those of TPU and PP. Ester-TPU has got high
dielectric constant. With the addition of PP, the dielectric constant decreased due to the decrease in
the overall polarity of the system. Among the different composition based systems used, the
nanoclay filled compatibilised ester-TPU based system, showed the lowest dielectric constant value.
The mixed system showed an intermediate value. Finally it can be concluded that thermoplastic
elastomer from compatibilised nanoclay filled TPU/PP system could be utilized for many
applications such as electrical, automotive etc.
SCOPE OF FUTURE WORK
1.
Interfacial thickness can be measured using small angle X-ray scattering (SAXS), small
angle neutron scattering (SANS) ellipsometry
2.
Computer software could be developed to predict the miscibility and phase behaviour of binary
polymer blends. Computational modeling of the behaviour of these blends can be done.
3.
The effect of fillers on morphology and properties is an area to be explored. The effect of
other nanofillers like carbon nanotube (CNT), nanoclaciumcarbonate, etc, can be studied.
4.
NMR spectroscopy can be utilized to assess the extent of compatibility of these blends.
5.
The studies can be extended to free volume measurements by positron annihilation technique.
6.
Variation in maleic anhydride content of MA-g-PP can change the properties of the blends
under discussion to a great extent. This could be future programme.
REFERENCES
1.
D.J. Walsh, S. Rostami, Adv. Polym. Sci., 70, 119 (1985)

93

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1.

Property of polymer blends is superior to those of component

immiscible systems the overall physicomechanical behaviour depends critically on two

H m <0 due to specific interactions.

Homogeneity is observed at least on a nanometer scale, if not on the molecular level.

Figure 1.1. Polymer blend phase diagram

Figure 1.2. Gibbs free energy of mixing for binary mixtures

montmorillonite, chemically modified with dimethyl benzyl hydrogenated tallow quaternary

denotes quaternary ammonium ions, HT denotes

hydrogenated tallow. HT is made of approximately 65 % C 18 H37, 30 % C 16 H33, and 5 % C 14 H29.

[TPU(nano)* = 3% nano content]

[PP-nano* *= 8.4 % nano content, PP-nano* = 7.0 % nanocontent]

Fourier transform infra-red spectroscopy (FTIR) has numerous applications in qualitative

frequency of 1,10,20 Hz and a heating rate of 5 0C/min.

2.3.10 Electrical property measurements

and interfacial area / unit volume of MA-g-PP compatibilised

Ether-TPU based blends

Interfacial area/ unit

Inter Particle Distance

3.1.3 Influence of nanoclay addition on compatibilised blend phase morphology

Figure 3.6(b). Nanoclay emulsification curve- TPU(nano)/PP/MA-g-PP (70-nano/25/5)

is considerably reduced in TPU(nano)/PP/MA-g-PP. Compared to the sequence II blend

3.1.5 XRD Studies

are shown in Figure 3.8. The peak is absent in ester-

XRD results are often reported to be misleading in terms of clay

(a) Ester- TPU(3%nano)/PP

(a) Ether TPU(3%nano)/PP

Figure 3.13. TEM images

Figure 3.14. TEM images

of clay. Figure 3.12a

shows clay dispersion in the ether-TPU/nanoclay/PP nanocomposites.

Figure 3.15(a). Variation of particle size reduction as a function of volume % of compatibiliser

compared to m , is expressed by 0 /m . Since the dispersed particle reduction is directly

The variation in values of as a function of MA-g-PP in TPU/PP (70/30) blend is given

values from Libelers theory show apparent conflict with the

experimental observation, which shows a decrease in particle size followed by a quasi

reference segment size.

Figure 3.15(b). Effect on MA-g-PP on the values by Leibler's theory

Table 3.3 Mechanical properties of uncompatibilised ester-TPU based blends

Stress at % strain (MPa)

32.60.05 (at break)

Figure 3.16(a). Stress-strain curves for

Figure 3.16(b). Stress-strain curves for

uncompatibilised ester-TPU/PP blends

uncompatibilised ether-TPU/PP blends

Table 3.4. Mechanical properties of uncompatibilised ether-TPU based blends

Stress at % strain (MPa)

32.6 0.05 (at break)

Tensile Modulus (MPa)

Figure 3.19. Effect of compatibiliser on

Figure 3.20. Effect of compatibiliser on

Figure 3.21. Stress-strain curves for

Figure 3.22. Stress-strain curves for

Table 3.5. Mechanical properties of compatibilised ester-TPU based blends

7.90.05 10.10.05 10.30.05

Stress at % strain (MPa)

Table 3.6. Mechanical properties of compatibilised ether-TPU based blends

Stress at % strain (MPa)

Weight loss (%)

Figure 3.23. Neat polymers TGA analysis

Figure 3.24. Neat polymers DTG analysis

Table 3.7(b). Weight losses at different temperatures of ether-TPU/PP blend

3.3.1.3 Compatibilised blends

[PP-nano* = 8.4 % nano content, PP-nano = 7.0 % nanocontent]