Studies on Electrical Properties of Nanoclay Filled

Thermoplastic Polyurethane/Polypropylene Blends

Murugasamy Kannan,1 S.S. Bhagawan,1 Sabu Thomas,2 Kuruvilla Joseph3

1
Department of Chemical Engineering, Amrita Vishwa Vidyapeetham, Coimbatore, 641112, India

2
School of Chemical Sciences, Mahatma Gandhi University, Kottayam, 586560, India

3
Department of Chemistry, Indian Institute of Space Science and Technology, Thiruvananthapuram, 695 547,
India

The electrical properties of ester/ether-based thermo- ing materials and to gain an insight into the nature of
plastic polyurethane (TPU) and polypropylene (PP) their electrical response [5].
blends are presented in this article. Special attention
has been paid to analyze the effect of blend ratio,
Polyvinyl chloride (PVC) is one of the main basic
compatibilization, and effect of nanoclay on the electri- materials for cable sheathing due to its relatively low
cal properties of TPU/PP blends. The electrical proper- cost, excellent electrical and mechanical properties, and
ties measured were dielectric constant (e0 ), volume good flame-retardant characteristics [6, 7]. However, dur-
resistivity (qt), loss factor (e00 ), and dissipation factor ing the incineration of PVC cables as well as house and
(tan d). Addition of PP into TPU increases the volume
resistivity and reduces the dissipation and loss factor
building fires, a great deal of hydrogen chloride, other
due to the decrease in the overall polarity of the sys- corrosive gases, toxic smog, and dioxin are generated [6–
tem. Further addition of compatibilizer and nanoclay to 8], which makes firefighting and the evacuation of people
this system reduced the dissipation factor and loss difficult, and results in death from suffocation, corrosion,
factor with increased volume resistivity. Compared and destruction of equipment. Moreover, when PVC
with the ether-TPU based blend nanocomposites, the
ester-TPU blends show better compatibility as con-
cables are buried in soil, lead (Pb) ions migrate from the
firmed by analysis. POLYM. COMPOS., 35:1671–1682, 2014. lead stabilizer, which greatly harms the environment [7].
C 2013 Society of Plastics Engineers
V Electrical properties of various polymer blends have
been investigated by several researchers [9–17]. During
the past few decades, a wide range of polymers have
INTRODUCTION been used for alternative PVC cable materials, including
cross linked polyethylene (XLPE) [18], polypropylene
The electrical properties of polymer cover an
(PP) [19], ethylene vinyl acetate copolymer (EVA) [20],
extremely diverse range of molecular phenomena. Many
and thermoplastic polyurethane (TPU) [21]. Among the
of the thermoplastic elastomers (TPEs) have found exten-
alternatives for PVC cable materials, much attention has
sive application as dielectric materials in cables and
capacitors. Polymeric insulators are widely used due to been paid to TPU due to its high strength, elongation, and
their superior service properties in the presence of heavy elasticity, low-temperature flexibility, excellent wear and
pollution and wet conditions, and also very desirable oil resistance, and excellent weatherability. However, the
characteristics from the observation point of transporta- higher cost has limited its wide use in electrical insulation
tion (no damage at transportation) and framing (lower applications. PP, as a relatively low-cost material, makes
weight) compared with the porcelain glass insulator [1– up for this disadvantage of TPU. Beside this, PP has
4]. A complete understanding of the dielectric properties many excellent properties, such as maximum volume
such as volume resistivity, dielectric constant, and loss resistivity, minimum dielectric constant, easy processing,
factor as a function of frequency and temperature is often outstanding chemical and moisture resistance. and low
necessary for the proper selection of polymers as insulat- density, which make it favor for making blend of TPU/PP
material for electrical insulation application [22, 23].
Potschke et al. [24–26] have carried out mechanical,
Correspondence to: M. Kannan; e-mail: [email protected]
DOI 10.1002/pc.22820
viscosity, and morphological studies on TPU/PP blend
Published online in Wiley Online Library (wileyonlinelibrary.com). without compatibilizers. Lu and Macosko, and Lu et al.
C 2013 Society of Plastics Engineers
V have studied mechanical, morphological, and viscosity

POLYMER COMPOSITES—2014
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properties on TPU/PP-based blends in with compatibil- TABLE 1. Sequence I and II of blend compositions.
izers like maleic anhydride-g-PP (MA-g-PP) and primary/
Sequence I
secondary amine-g-PP [27, 28].
In this new study, the electrical properties of TPU/PP
TPU(nano)* PP MA-g-PP
blends were investigated with special reference to the Blend (wt%) (wt%) (wt%)
effect of type of polyurethane (ester- or ether-based),
blend ratio, compatibilizer, and sequence of nanoclay Ester-TPU(nano)/PP 70 30 —
addition. The nanocomposites were prepared by melt Ester-TPU(nano)/PP/MA-g-PP 70 25 5
Ether-TPU(nano)/PP 70 30 —
blending in a twin screw extruder. The electrical proper-
Ether-TPU(nano)/PP/MA-g-PP 70 25 5
ties measured were dielectric constant (e0 ), volume resis-
tivity (qt), loss factor (e00 ), and dissipation factor (tan d).
Sequence II
EXPERIMENTAL
TPU PP PP-nano MA-g-PP
Blend (wt%) (wt%) (wt%) (wt%)
Materials
Ester-TPU/PP/MA-g-PP 70 25 — 5
Ester-TPU (385S) and ether-TPU (KU2–8600) were Ester-TPU/PP-nano 70 30* —
supplied by Bayer (TPU) India Ltd., Chennai. The MFI Ester-TPU/PP-nano/MA-g-PP 70 25** 5
value of 385S and KU2–8600E is 10 g/10 min and 11 g/ Ether-TPU/PP/MA-g-PP 70 25 — 5
min, respectively, (190 C/2.16 kg). The hardness value of Ether-TPU/PP-nano 70 30* —
385S and KU2–8600E is Shore A 85 and 84, respectively. Ether-TPU/PP-nano/MA-g-PP 70 25** 5
PP (MA 1100) was supplied by Reliance Industries Ltd., TPU(nano)* 5 3 wt% nano content.
Jamnagar, India. The MFI value of PP (MA 1100) is 11 PP-nano** 5 8.4 wt% nano content; PP-nano* 5 7.0% nanocontent.
g/10 min (230 C/2.16 kg). MA-g-PP compatibilizer was
purchased from Pluss Polymers, New Delhi. The compati- Neat ester-TPU/PP blends were prepared in the ratio of
bilizer is a maleic anhydride functionalized PP (MA-g- 70/30.
PP), containing 1 wt% of maleic anhydride. The MFI
value of MA-g-PP compatibilizer is 12 g/10 min (190 C/ Sequence I: TPU/nanoclay nanocomposites were pre-
2.16 kg).The organoclay used in this study (Cloisite 10 A pared and subsequently blended with PP using MA-g-PP
[C 10A]) was obtained from Southern Clay Products, as compatibilizer. About 3 wt% of the nanoclay was
United States. It is a Na1 montmorillonite, chemically used. The ester-TPU pellets were dried at 100 C for 4 hr.
modified with dimethyl benzyl hydrogenated tallow qua- The nanoclay was dried at 100 C for 12 hr in a vacuum
ternary ammonium ions (N1 2MBHT), where N1 denotes oven. The dried pellets were fed into a co-rotating twin
quaternary ammonium ions, HT denotes hydrogenated tal- screw extruder and the temperature of the die zone was
low. HT is made of approximately 65% C18H37, 30% maintained at 190 C. The extrudate was received as
C16H33, and 5% C14H29. Cation exchange capacity is 125 strands, which were cut into small granules for melt
meq/100 g clay. blending with PP. The granules of nanocomposites, along
with pellets of PP and MA-g-PP were pre-dried at 100 C
for 4 hr in a vacuum oven. Blending was done in the
Preparation of Nanoclay Filled TPU/PP Blends
same co-rotating twin screw extruder with a die zone
Ester-TPU/nanoclay nanocomposites were prepared by temperature of 190 C and the extrudate was again
melt blending TPU and nanoclay using twin screw obtained in the form of strands. Neat TPU/PP blends
extruder. About 3 wt% of the nanoclay was used. The were prepared in the ratio of 70/30.
ester-TPU pellets were dried at 100 C for 4 hr. The nano- Sequence II: Nanoclay was added to PP by similar
clay was dried at 100 C for 12 hr in vacuum oven. The extruder melt blending and subsequently melt blended
dried pellets were fed into a co-rotating twin screw with TPU using MA-g-PP as compatibilizer (Table 1).
extruder (Berstrof ZE 25) and the temperature of the die
zone was maintained at 190 C. The extrudate was Ether-TPU based samples were also prepared by simi-
received as strands and cut into small granules for melt lar method.
blending with PP.
Later, the granules of nanocomposites, along with
Scanning Electron Microscopy (SEM)
pellets of PP and MA-g-PP were pre-dried at 100 C for
4 hr in a vacuum oven. Blending was done in the co- The phase morphology was studied using cryogenically
rotating twin screw extruder at a die zone temperature of fractured samples. By immersing the samples in liquid
190 C and the extrudate was again obtained in the form nitrogen, a brittle fracture is obtained avoiding large
of strands. Blends of different compositions shown in deformations in the surface to be examined. These sam-
Table 1 were prepared by the method described above. ples are immersed in xylene solutions to remove the PP

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from TPU base. This setup kept in oil bath at 80 C for 3 e00 5e0 tan d (3)
hr. Then the sample is taken out and dried in oven at
100 C under vacuum in order to remove excess of xylene. where tan d is the dissipation factor.
Thus, chemical etching of the sample is obtained. Morpho-
logical studies were performed on the chemically etched
RESULTS AND DISCUSSION
and gold sputtered samples using JOEL (JSM-5800) SEM.
Morphology
Transmission Electron Microscopy (TEM) Influence of Nanoclay Addition on Compatibilized
The samples for TEM analysis were prepared by ultra- Blend Phase Morphology. The equilibrium concentra-
cryomicrotomy with a Leica Ultracut UCT (Leica Mikro- tion at which the domain size levels off can be considered
systems GmbH, Vienna, Austria). Freshly sharpened glass as the so-called critical micelle concentration (CMC) of
knives with cutting edges of 45 C were used to obtain compatibilizer, that is, the concentration at which micelles
cryosections of 100–120 nm thickness. Because these are formed. The CMC has been estimated in separate
samples were elastomeric in nature, the sample and glass study by the intersection of the straight lines at the low
knife temperatures during ultra-cryomicrotomy were kept and high concentration regions, the CMC value for MA-
constant at 275 C and 285 C, respectively (these tem- g-PP is 5% for this TPU/PP blends [29].
peratures were well below the glass transition temperature SEM micrographs of chemically etched (PP material
[Tg’s] of PUs). The cryosections were collected individu- was removed by xylene at 80 C) nanoclay (1%, 3%, and
ally in a sucrose solution and directly supported on a cop- 5%) filled ester and ether based TPU/PP/MA-g-PP
per grid of 300 meshes in size. Microscopy was [70(nano)/25/5] blend system are shown in Figs. 1 and 2.
performed with a JEOL JEM 2000 TEM instrument It is observed that the size of dispersed PP particle is con-
(Japan), operating at an accelerating voltage of 120 kV. siderably reduced in the ester-TPU (3% nano)/PP/MA-g-
PP (Fig. 1b) system. For nanocomposite SEM sample
preparation, the PP portion was removed by chemical
Electrical Property Measurements etching method which gives very fine holes. In the case
The electrical measurements were carried out using of compatibilized blends addition of 3% nanoclay reduces
circular samples of diameter 10 mm and thickness of 3.2 the domain size to the maximum extent and attained max-
mm at room temperature using Novo control, Germany- imum interfacial area/unit volume. Beyond 3% concentra-
Alpha ATP. The test samples were coated with conduc- tion, increase of size of dispersed particle is due to
tive graphite paint on either side and copper wires were inefficiency of nanoclay dispersion, it cause miscelle.
fixed on both sides of the samples as electrodes. All As mentioned in the introduction, the high polarity dif-
measurements were done at the frequencies ranging from ference between TPU and PP limits the miscibility of
100 HZ to 1 MHz. The capacitance, impedance, and their blends. Nanoclay was used to reduce the surface
dielectric loss factor were measured directly. Electrical energy of the TPU hard segments and makes them more
properties such as volume resistivity, dielectric permittiv- compatible with the non-polar PP. More compatible
ity, loss factor, and dissipation factor were studied. blends have been obtained by using MA-g-PP as the com-
The volume resistance of the samples was calculated patibilizer. Better dispersion of organoclay may be attrib-
using the equation uted to the following reasons. Carbonyl groups (both in
the polyol soft segments and the TPU hard segments)
RA form hydrogen bonds with the hydroxyls groups of the
qv 5 Xcm (1) nanoclay silicates layers. Secondly, maleic anhydride
t
forms hydrogen bonds with the hydroxyls groups of the
where qv is the volume resistivity of the samples the ohm nanoclay silicates layers. Thirdly, ANH group of urethane
centimeter, R is the resistance in ohms, A is the area in linkage form hydrogen bonds with the oxygen groups of
centimeter square, and t is the thickness of the samples in the silicate layers of nanoclay and maleic anhydride group
centimeters. (R is obtained from the relation impedance, of compatibilizer. Besides hydrogen bonding, chemical
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Z5 R2 1 c21x2 where C is capacitance, x 5 2pF where F reaction between urethane linkage and compatibilizer is
possible. It is thus possible that a reaction of carbamate
is the frequency). The dielectric constant (e0 ) was calcu-
lated from the capacitance using the following relation and anhydride involves a mechanism, with elimination of
carbon dioxide and alcohol. Because the release of carbon
Ct dioxide is an irreversible process, the carbamate conver-
e0 5 (2) sion kept increasing over time and never tended to level
eo A
off. In the absence of any other factors the reaction
where C is the capacitance, t is the thickness, A is the area between carbamate and anhydride may not be fast enough
of electrode cross section, and eo is 8.85 3 10212 F/m. for reactive compatibilization in real polymer blends.
Loss factor is calculated as follows: Nonchemical interactions/bonding between anhydride

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FIG. 1. Ester-based TPU blend TPU (nano)/PP/MA-g-PP (70/25/5). (a) 1% nano, (b) 3% nano, and (c) 5%
nano (nano content in TPU).

groups and other species are usually strong that could Fig. 3d, where the degree of dispersion of clay is
compensate the relatively insufficient reactivity toward observed to be poorer than ester-TPU nanocomposites.
urethane linkages.

Uncompatibilized Blends
TEM Investigation. It is well known that the difficulty
in studying the nanocomposites is that no single charac- Effect of Blend Ratio on Volume Resistivity. Basi-
terization method can adequately describe the state of cally, polymers have high value of resistivity, owing to
clay dispersion in the nanocomposites. The supporting the non-availability of free electrons for conduction.
analyses are necessary and especially TEM is proved to Resistivity studies are important for insulating materials,
be quite effective. because the most desirable characteristic of an insulator is
When MA-g-PP is not introduced into the system, only its ability to resist the leakage of electrical current. Vol-
intercalated structure is obtained, and many larger aggre- ume resistivity is numerically equal to the direct current
gates exist in the matrix (Fig. 3a and c). When the com- resistance between opposite faces of a one centimeter
patibiliser is introduced in the system, the nanoclay cube of a material, expressed in ohm centimeters. Figure
dispersion improves. 4 shows the variation of volume resistivity (qv) of TPU/
The TEM image in Fig. 3b shows exfoliated and well PP blends as a function of TPU concentration. Polar poly-
dispersed nanoclay particles. In view of this, a true nano- mers have lower resistivity than non-polar polymers due
composites was produced in the case of ester-TPU(nano)/ to the polarization of polar polymers under the influence
PP/MA-g-PP and 3 wt% nanoclay loading. The TEM of electrical field, which promote the conducting process.
image of the composite supports this and shows that indi- From the Fig. 4 it is clear that PP is a good insulator
vidual clay layers were well dispersed in the polymer. with very high value of volume resistivity where as the
TEM images of nanocomposite of ether-TPUs shown in volume resistivity of TPU is very low. In the case of

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FIG. 2. Ether-based TPU blend TPU (nano)/PP/MA-g-PP (70/25/5). (a) 1% nano, (b) 3% nano, and (c) 5%
nano (nano content in TPU).

blends the volume resistivity values are in between that frequency further increases, the dipole polarization effect
that of TPU and PP. As the concentration of TPU will increase and leads for reduction of volume resistivity
increases the volume resistivity values decreases. values.
Volume resistivity of TPU, PP, and their blends as a
function of frequency is given in the Fig. 5. It can be Effect of Blend Ratio on Dielectric Constant (e0 ). The
seen from the Fig. 5 that, with incorporation of TPU, dielectric constant (e0 ) is an important parameter for an
which is comparatively a less insulating material, reduces insulating material. It is an expression of the extent to
the volume resistivity of the blends. In TPU/PP (30/70) which a material concentrates electric flux. The dielectric
blend where PP forms the matrix, the curve is very close material is a substance that is a poor conductor of elec-
to PP curve and in TPU/PP (70/30) the curve is very tricity, but an efficient supporter of electrostatic fields.
close to TPU. In all cases reduction in volume resistivity Materials with high dielectric constants are useful in the
is observed with increase in frequency. This can be attrib- manufacture of high value capacitors. The variation of
uted to the increase in molecular mobility at high fre- dielectric constants of TPU, PP, and their blends as a
quencies. Volume resistivity of the material is mainly function of frequency is shown in the Fig. 6. It is evident
dependent on the electronic polarization and dipole polar- from the figure that e0 values of pure TPU and their
ization of the material: whereas the former involves only blends decrease with increasing the applied frequency.
movement of electrons the latter entails movement of part Generally the dielectric constant of a polymer arises from
of or even the whole of the molecule. Molecular move- various polarization phenomena that come into play when
ments take a finite time and complete orientation as the polymer is subjected to an electric field. The dielec-
induced by frequency of an alternating current. As the tric constant increases with increase in polarizability. The

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FIG. 3. TEM images of TPU based blends. (a) Ester-TPU(3%nano)/PP (70/30); (b) ester-TPU(3%nano)/PP/
MA-g-PP(70/25/5); (c) ether-TPU(3%nano)/PP (70/30); and (d) ether-TPU(3%nano)/PP/MA-g-PP(70/25/5).

different types of polarization possible in a material are

(1) electronic polarization, (2) atomic polarization, and
(3) orientation polarization. The orientation polarization
contributes a major part of the total polarization for polar
polymers. In heterogeneous materials, there is a possibil-
ity for interfacial polarization, which arises due to the dif-
ference in conductivities of the two phases [30].
Therefore in the case of TPU, which is a polar polymer,
all the three types of polarization contribute toward the
dielectric constant. As a result, TPU exhibits high dielec-
tric constant, especially at low frequencies.
The time required for each type of polarization to
reach the equilibrium level varies with the nature of
polarization. The orientation polarization requires more
time compared with electronic and atomic polarization to
reach equilibrium value. The interfacial polarization
generally occurs at lower frequencies. In the figure high
values of dielectric constant in the low frequency region
can be attributed to the interfacial polarization effects.
But at higher frequency the interfacial polarization is less FIG. 4. Variation of volume resistivity of TPU/PP blends with TPU
prominent and hence the dielectric constant is due to the content at 30 C.

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PP shows lowest dielectric constant value, which is a
characteristic of a non-polar material and TPU shows the
highest value. The blends show intermediate values. In
the case of blends the values increase as the TPU content
increase. The increase with the incorporation of TPU is
due to the increase in dipoles, which increase the orienta-
tion polarization and also due to the presence of interfa-
cial polarization. The non-linearity of the curves observed
in the TPU/PP blend systems is due to the incompatibility
of the blends. This type of non-linearity in e0 values was
reported by the Saad and Sabbagh [35–37]. In the case of
TPU/PP (30/70), TPU is dispersed with poor bonding
with the matrix whereas; in TPU/PP (70/30) TPU is the
matrix. Thus relativity high value of e0 on the addition of
TPU can be correlated with the continuous nature of TPU
phase leads to a better orientation of dipoles. The dielec-
tric constant depends on resistivity according to equation

log R10 ð298K Þ52322e0 ð298K Þ (4)

that is, the electrical resistance of polymers decreases

exponentially with increasing dielectric constant. In TPU/
PP blends as the dielectric constant increases with the
increase in TPU content, the volume resistivity decreases.

Effect of Blend Ratio on Dissipation Factor and Loss

FIG. 5. (a) Volume resistivity of ester-TPU, PP, and their blends as a Factor (E00 ). The tangent of the dielectric phase angle or
function of frequency 30 C. (b) Volume resistivity of ether-TPU, PP, the tangent of the dielectric loss angle is represented by
and their blends as a function of frequency at 30 C.

orientation, electronic and atomic polarization. We can

explain the effect of high frequency in this way also.
Under the influence of an electric field, polar polymers
tend to form dipoles, and these dipoles under the influ-
ence of an external field, oscillate with the frequency of
the field. The effect is more pronounced at high fre-
quency. When the heat buildup is more, this results in the
deterioration of electrical properties. The orientation of
the dipoles depends on the crystallinity of the medium.
Since TPU is amorphous, dipoles can orient more easily.
Such increase in dielectric constant of polar polymers
was reported by various authors [31–33].
PP exhibits having low dielectric constant values charac-
teristic of non-polar materials. The higher the viscosity of
the polymer, the greater will be the hindrance to free dipo-
lar orientation polarization from the neighboring molecules,
and the lower will be the dielectric constant [34].
In the case of blends, due to the presence of two
phases TPU and PP with different conductivities, interfa-
cial polarization occurs leading to an increase in dielectric
constant. From the figure it can be seen that the dielectric
constant increase with in TPU content at all frequencies.
This is due to the increases in the dipoles by the addition
of the TPU. Since interfacial polarization decrease with
increase in frequency, the dielectric constant has contribu- FIG. 6. (a) Variation of dielectric constant of ester-TPU/PP blends
tion from orientation, atomic and electronic polarizations with frequency at 30 C. (b) Variation of dielectric constant of ether-
at higher frequencies. TPU/PP blends with frequency at 30 C.

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These values are used for the calculation of model stud-
ies. The logarithmic variation of dielectric constant can
be expressed by the equation,

log e0 c 5V1 log e0 1 1 ð12V1 Þ log e0 2 ðModel 2Þ (6)

The dielectric constant of two-phase mixtures based on

spherical particle, which consider all the possible interac-
tion, could be calculated using the following equation
[38]

1  1 
e0c 5 H1 H 2 18e01 e02 2 ðModel 3Þ (7)
4
where

H5ð3V 1 21Þe01 1ð223V 2 Þe02 (8)

The Maxwell–Wagner–Sillars equation [39] was also

used to predict the e0 values and is given as
 
2e02 1e01 12V1 e01 2e02
e0c 5e02   ðModel 4Þ (9)
2e02 1e01 1V1 e01 2e02
FIG. 7. (a) Variation of dissipation factor of ester-TPU/PP blends with
frequency at 30 C. (b) Variation of loss factor of ester-TPU/PP blends
Experimentally obtained dielectric constants (at a fre-
with frequency at 30 C.
quency 1 MHz) for the various blend compositions were
compared with theoretical models. The comparison is
the tan d. The measurement of dissipation factor (tan d)
depicted in the Fig. 9, which shows that experimental val-
and loss factor (e00 ) of an insulating material is important.
ues deviate from all the models. The experimental values
In electrical applications, it is desirable to keep the elec-
are much lower than that of various theoretical models,
trical 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 con-
verted into heat in an insulator. This heat raises the tem-
perature, leading to deterioration of the polymeric
materials. The variation of tan d and loss factor with fre-
quency for TPU, PP, and their blends is depicted in the
Figs. 7 and 8. Addition of TPU into PP increases dissipa-
tion and loss factor. The increase in the value is due to
orientation polarization of polar TPU followed by oscilla-
tion under electric fields.

Comparison with Theory

Experimental dielectric values can be compared with
theoretical predictions. The dielectric constant of a com-
posite containing two components can be expressed in the
general form.

e0c 5V1 e01 1e02 ð12V1 ÞðModel 1Þ (5)

where E01 and E02 are dielectric constants of components 1

and 2, and V1 and (1 2 V1) 5 V2 are the volume fractions
of components 1 and 2, respectively. Experimentally
obtained dielectric constant values of neat PP, neat ester-
TPU, neat-ether TPU at 1 MHz is 3.2, 4.5, and 4.3,
respectively. The blend TPU/PP weight ratios of 100/0, FIG. 8. (a) Variation of dissipation factor of ether-TPU/PP blends with
70/30, 50/50, 30/70, 0/100 are converted into volume frequency at 30 C. (b) Variation of loss factor of ether-TPU/PP blends
ratios of 100/0, 64/36, 43/57, 24/76, 0/100, respectively. with frequency at 30 C.

1678 POLYMER COMPOSITES—2014 DOI 10.1002/pc

 15480569, 2014, 9, Downloaded from https://4spepublications.onlinelibrary.wiley.com/doi/10.1002/pc.22820 by The Director National Institute Of Technology Calicut, Wiley Online Library on [06/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Compatibilized Blends
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 compatibi-
lization. Hence a reactive route was employed to compati-
bilize the system using MA-g-PP as the compatibilizer.
The urethane group of the TPU can react with the anhy-
dride group of the compatibilizer to form a graft polymer,
which can locate at the interface. Analysis of phase mor-
phology, mechanical, DMA, and thermal properties
proved that MA-g-PP could act as an effective compati-
bilizer in TPU/PP blend system. In this context we ana-
lyzed the effect of compatibilization on the dielectric
properties of 70/30 (TPU/PP) blends. Both ester- and
ether-based TPU was used for these studies because soft
segment of ester and ether TPU has different surface ten-
sion values. Further, nanoclay was incorporated in the
system to reduce the surface tension of TPU hard seg-
ment to make the blend more compatible.

Volume Resistivity. The effect of compatibilization on

the volume resistivity of the TPU/PP (70/30) blends is
given in the Figs. 10 and 11. It is quite evident from the
FIG. 9. (a) Comparison of experimental values obtained for dielectric figure that compatibilization resulted in the increase of
constant with theoretical predictions for ester-TPU based blends. (b)
Comparison of experimental values obtained for dielectric constant with
volume resistivity [40–44].The highest value of volume
theoretical predictions for ether-TPU based blends. resistivity is observed at 5% of compatibilizer concentra-
tion. With the incorporation of 3 wt% of MA-g-PP, the
resistivity becomes almost close to that of the uncompati-
which is attributed to the incompatible nature of the bilized blends. During the 3% addition of the compatibil-
blend. Maximum deviation is shown for the Maxwell– izer, the anhydride group will react with the urethane
Wagner–Sillars equation and model 3. groups of TPU, contributing toward the reduction in

FIG. 10. (a) Effect of compatibilizer concentration on the volume resistivity as a function of frequency at
30 C for ester-based TPU-based blends. (b) Effect of compatibilizer concentration on the volume resistivity
as a function of frequency at 30 C for ether based TPU based blends

DOI 10.1002/pc POLYMER COMPOSITES—2014 1679

 15480569, 2014, 9, Downloaded from https://4spepublications.onlinelibrary.wiley.com/doi/10.1002/pc.22820 by The Director National Institute Of Technology Calicut, Wiley Online Library on [06/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
FIG. 11. (a) Effect of nanoclay addition on the volume resistivity as a function of frequency at 30 C for
compatibilized ester-based TPU-based blends. (b) Effect of nanoclay addition on the volume resistivity as a
function of frequency at 30 C for compatibilized ether-based TPU-based blends.

overall polarity of the system. When the concentration of Dielectric Constant. The results of the effect of compa-
the compatibilizer increases above CMC level, the tibilization on the dielectric constant of TPU/PP (70/30)
amount of polar groups in the system increases. This is blends are given in Fig. 12. It can be observed from the
reflected in the volume resistivity at high compatibilizer figure that compatibilization resulted in a substantial
loading. The morphology of the compatibilized blends decrease of dielectric constant. The lowest value of
suggests that, by the incorporation of 5 wt% of the com- dielectric constant was observed at 5% of compatibilizer
patibilizer, CMC is reached. Therefore, further addition of addition. Further addition of the compatibilizer increased
the compatibilizer will lead to the formation of micelles. the dielectric constant. As discussed earlier, this observa-
It is expected that the micelles aggregates of the compati- tion may be due to the formation of aggregates of the
bilizer will result in the increase of polarity. compatibilizer beyond CMC.

FIG. 12. Effect of nanoclay addition on the dielectric constant as a function of frequency at 30 C for com-
patibilized (a) ester-TPU based and (b) ether-TPU based.

1680 POLYMER COMPOSITES—2014 DOI 10.1002/pc

 15480569, 2014, 9, Downloaded from https://4spepublications.onlinelibrary.wiley.com/doi/10.1002/pc.22820 by The Director National Institute Of Technology Calicut, Wiley Online Library on [06/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
FIG. 13. Effect of nanoclay addition on the dissipation factor as a function of frequency at 30 C for com-
patibilized (a) ester-TPU based and (b) ether-TPU based.

Dissipation Factor and Loss Factor. Figures 13 and CONCLUSION

14 show the variation of dissipation factor (tan d) and
loss factor (e00 ) on compatibilization. As the frequency In this article electrical properties of ester- and ether-
increases tandand loss factor decreases and then levels based TPU, PP, and their blends were analyzed in the fre-
off. The loss factor and dissipation factor reaches a mini- quency range 100 Hz to 1 MHz. Compared with polar
mum at 5% loading of the compatibilizer. Increase in loss TPU, PP exhibited good insulating properties. Among the
factor and dissipation factor at high concentration of MA- neat polymers, PP possessed the maximum volume resis-
g-PP can be attributed to the increase in the polarity of tivity and minimum dielectric constant. The volume resis-
the systems at high loadings. The lower values of tan d tivity values of the blends fall in between those of TPU
and e00 for TPU(nano)/PP/MA-g-PP (compatibilizer load- and PP. TPU has got high dielectric constant. With the
ing of 5%, nanoclay loading of 3%) implies that insulat- addition of PP, the dielectric constant decreased due to
ing property can be improved by using optimum the decrease in the overall polarity of the system. By
concentration of the compatibilizer and nanoclay. comparing the experimental dielectric constant values

FIG. 14. Effect of nanoclay addition on the loss factor as a function of frequency at 30 C for compatibi-
lized (a) ester-TPU based and (b) ether-TPU based.

DOI 10.1002/pc POLYMER COMPOSITES—2014 1681

 15480569, 2014, 9, Downloaded from https://4spepublications.onlinelibrary.wiley.com/doi/10.1002/pc.22820 by The Director National Institute Of Technology Calicut, Wiley Online Library on [06/10/2024]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
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1682 POLYMER COMPOSITES—2014 DOI 10.1002/pc