IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No.

3; June 2009 853

High Density Polyethylene (HDPE) Clay Nanocomposite

for Dielectric Applications
K. S. Shah, R. C. Jain, V. Shrinet, A. K. Singh
Material Research Cell, Electrical Research & Development Association,
ERDA Road, Makarpura, Vadodara 390010, India

and D. P. Bharambe
Applied Chemistry Department, Faculty of Technology and Engineering,
Maharaja Sayajirao University of Baroda, P. O. Box 51, Kalabhavan,
Vadodara-390001, India

ABSTRACT
Indigenous Montmorillonite clay available from Kutchh region in western part of India
was modified by Hexadecyl trimethyl ammonium bromide, a quaternary ammonium
compound to make it organophilic. It was blended with high density polyethylene
(HDPE) in a Brabender Plasticoder. The condition for blending was optimized and
sheets were prepared for evaluating mechanical, electrical and thermal properties.
Mechanical property such as tensile was improved. The electrical properties such as
dielectric strength, volume resistivity and surface resistivity were measured as per
ASTM D149 and ASTM D257 standards. It was observed that electrical properties of
nanoclay composite improved significantly when organoclay was treated with silane
and titanate compounds. Thermal characterization of the HDPE and HDPE clay
nanocomposite had been carried out by thermogravimetric analysis (TGA). It has been
observed that the thermal stability of the nanocomposite increases significantly when
the silane and titanate coupling agents are used.

Index Terms - Dielectric, nanocomposite, silane coupling agent, titanate coupling

agent, montmorillonite clay, quaternary ammonium compound.

1 INTRODUCTION a need for charge compensation which is accomplished by an

external positive ion such as calcium ion or sodium ion. [10,
11, 12]. Generally layered silicate is modified with quaternary
POLYMERIC nanocomposites have gained importance
ammonium or phosphonium compounds to make them
in the manufacture of products of high performance properties
organophilic from hydrophilic by cation exchange reaction
like light weight, material transparency, enhanced stiffness
between quaternary compound and cations between the clay
and toughness, increased barrier properties, decreased thermal
galleries. The molecules of quaternary ammonium compound
expansion, decreased flammability and increase in dielectric
between the clay galleries act as pillars to increase the layer
properties for different industries such as automobiles,
spacing of the clay. Quaternary compound lower the surface
electrical and electronics, packaging, coatings etc [1-7].
energy of the clay surface so the wetting between the organic
Polyolefin based nanocomposites are very important because
and inorganic phase improves and it facilitates the polymer
of the formation of intercalated structure with layered silicate
molecules to penetrate between the clay galleries [12, 13].
using conventional processing technology [8, 9]. Clay has
When a thermoplastic polymer is mixed with an
layered structure in which rings of six tetrahedral silicons
organoclay, it either intercalates or exfoliates the layer silicate
surrounded by oxygen at its vertices sharing vertices with the
aggregates [2]. High density polyethylene (HDPE) is one of
octahedral aluminums sharing alternate edges. The sharing of
the widely used polymers, but it does not have any polar group
alternate edges leads to rings of six octahedral aluminums in a
on its backbone to interact with the polar clay surface.
ring or an alternative description being that two out of three
Quaternary ammonium or phosphonium compound improves
octahedral sites being occupied by aluminum with the third
the wetting to some extent. Use of silane and titanate coupling
octahedral site being vacant. The sheets of six-membered
agents is another method to form strong bonds between the
silicon tetrahedra are located on both sides of the octahedral
organic and inorganic phase. Silane and titanate coupling
aluminum sheet. The gap between two of these triple sheets is
agents first condense on the clay surface forming a chemical
called interlayer spacing. Substitution of Al3+ for Si4+ results in
covalent bond and their other organic part diffuse into organic
phase improving the miscibility of the inorganic phase with
Manuscript received on 28 October 2008, in final form 27 January 2008. the organic phase. The anchoring effect between the organic

1070-9878/09/$25.00 © 2009 IEEE

854 K. S. Shah et al.: High Density Polyethylene (HDPE) Clay Nanocomposite for Dielectric Applications
part of the silane or titanate coupling agents and HDPE
molecules further strengthen the inorganic-organic bonds.
HDPE is very good insulation material. Use of organoclay and
silane and titanate coupling agents further improves its
insulation properties.
Here, the work on modification of clay and preparation of
HDPE clay nanocomposite and its evaluation for mechanical,
electrical and thermal properties has been reported. Effect of
the concentration of silane and titanate coupling agents on
electrical, mechanical and thermal properties has been studied.
2 EXPERIMENTAL
2.1 MATERIALS
Clay: - Montmorillonite clay from Suraiya Clay Pvt. Ltd,
Mandvi, Kutchh, India.
Physical properties
Swelling in water – 18 times
Colour - Creamish
Moisture - 7-12 %
PH (6%) - 9 – 10.5
Quaternary Ammonium compound: -
Hexadecyl trimethyl ammonium bromide AR grade from
Sulab Chemicals.
Coupling Agents: -
- Amino propyl triethoxy Silane, (Silane 6011) from
Dow corning Ltd.
- Titanium Acetylacetonate from Dupont India Ltd,
- clay, silane treated clay and organoclay treated with a
Polymer Matrix: HDPE Grade B56003, Reliance Industries
Ltd.
2.2 MODIFICATION OF CLAY
50 gm indigenous montmorillonite clay was dispersed in
the 2 liter 0.03 M solution of Hexadecyl trimethyl
ammonium bromide and stirred at 500 rpm using a
mechanical stirrer at 80 0C for 5 h. Then clay was filtered
and washed with distilled water. Filtered clay was dried at
room temperature for 24 h in open air. Dried clay was
crushed to convert big agglomerated lumps of clay in small
particles. Crushed clay was further made fine by mixer
grinder and sieved through ASTM 270 grade sieve to get
very fine powder of the organically modified clay [14]. It
was used for the preparation of the HDPE clay
nanocomposite with different organoclay content.
2.2.1 SILANE TREATMENT TO ORGANOCLAY
Hexadecyl trimethyl ammonium bromide modified clay was
treated with Aminopropyl triethoxy silane (z 6011) obtained
from Dow Corning Private Ltd in 1, 3 and 5 wt % of clay.
Benzene was used as solvent. Silane solution in benzene was
added to organoclay in beaker and stirred. Benzene was
evaporated by heating the clay slurry in oven at 80 0C. Silane
treated clay was crushed. The crushed clay was sieved from
ASTM 270 grade sieve to get fine powder. It was used to
prepare HDPE clay nanocomposite.
2.2.2 TREATMENT OF COMBINATION OF SILANE
AND TITANATE COUPLING AGENTS TO
ORGANOCLAY
Hexadecyl trimethyl ammonium bromide modified clay was
treated first with Titanium Acetylacetonate in 0.5, 1.5 and 2.5
wt % concentration. The solution of Titanium Acetylacetonate
was prepared in acetone. The solution of Titanium
Acetylacetonate was mixed with clay in beaker and stirred.
The slurry was dried in oven. The dried clay lumps were
crushed. The fine crushed powder of titanate treated clay was
used for the silane treatment. The titanate treated clay was
treated by Aminopropyl triethoxy silane in 0.5, 1.5 and 2.5 wt
% concentration. The silane solution was prepared in benzene.
The silane solution was mixed with titanate treated clay
powder in beaker and stirred. The benzene was evaporated by
heating in oven at 80 0C. The clay lumps were crushed and
sieved in ASTM 270 grade sieve to get fine powder. It was
used for preparation of HDPE clay nanocomposite. Titanates
help in reducing the melt viscosity for better dispersion of
filler in polymer matrix and silane compounds provide
compatibility and better cosmetics of products.
2.3 PREPARATION OF HDPE CLAY
NANOCOMPOSITE
Organo-clay and silane and titanate treated organoclay were
dried at 100 oC in oven for 12 h before use. Raw clay, organo
combination of silane and titanate was mixed with HDPE in
Brabender Plasticoder at 180 0C at 80 rpm for 10 minutes.
Various compositions having different organoclay content and
concentration of coupling agents have been prepared. Lumps
obtained from the Brabender were cut into small pellets in a
pelletiser. Pellets were dried at 80 0C for overnight and test
specimens were prepared in an Injection Moulding machine of
Polymechplast manufacture. The temperatures of the mixing
zones were 180 – 205 0C with injection pressure of 80%. Test
specimens for electrical tests were prepared by compression
moulding of the injection moulded sheet at 200 0C and 1x106
Pa (10 Kg) pressure. The composite prepared with HDPE and
5 wt % raw clay was designated as H5C. The HDPE
organoclay nanocomposites were designated as HnmC, where
H refers HDPE, n is wt % of organoclay (i.e. 1, 3, 5, 7 and 10)
and mC refers organically modified clay. The 5 wt %
organoclay was treated by 1%, 3% and 5% silane coupling
agent. Nanocomposites prepared with silane treated clay were
designated as H5mc1S, H5mc3S and H5mc5S (5mc is 5 wt %
of organoclay and 1S refers 1% concentration of silane). The 5
wt % organoclay was treated with combination of silane and
titanate coupling agents and nanocomposites prepared from
this clay were designated as H5mc0.5S0.5T, where 5mC refers
5 wt % organoclay, 0.5S refers 0.5 % concentration of silane
and 0.5T refers 0.5% of titanate. Figure 1 and Figure 2 shows
Brabender mixing zone and Brabender Plastograph.
IEEE Transactions on Dielectrics and Electrical Insulation
Figure 1. Mixing zone of the Brabender Plasticoder
Figure 2. Brabender Plasticoder
2.4 EVALUATION OF CLAY, ORGANOCLAY AND
HDPE CLAY NANOCOMPOSITE
The raw clay and organoclay were characterized with
Fourier Transform Infrared (FTIR). FTIR showed the
evidences of the absorption of the quaternary ammonium
compound between the clay galleries. The IR spectra of the
powder samples dispersed in KBr discs were recorded on
Perkin Elmer spectrometer with scanning range 400-4000
cm-1.
2.4.1 MECHANICAL PROPERTIES
2.4.1.1 TENSILE STRENGTH AND ELONGATION
Tensile strength and elongation at break of the
nanocomposites were measured according to ASTM D638
(type 4) using universal testing machine, Hounsfield, U.K. at a
crosshead speed 100 mm/minute with 5kN load cell keeping
gauge length 25 mm. The average value of five samples was
reported.
2.4.1.2 IMPACT STRENGTH
Impact strength of the HDPE clay nanocomposites was
measured on Impact tester make by CIPET as per ASTM
D256. The notched samples for the Izod impact strength were
prepared using special notch cutting tool. The two-joule
energy hammer was used and the striking velocity was 3.46
m/sec. The average of five readings was reported.
2.4.1.3 HARDNESS
Hardness was measured as per ASTM D224 using Blue
Steel digital durometer. (Shore D tester).
Vol. 16, No. 3; June 2009 855
2.4.2 ELECTRICAL PROPERTIES
2.4.2.1 DIELECTRIC STRENGTH
Dielectric Strength was measured as per ASTM D149
standard. The average of three readings was reported. The brass
electrode faces were kept parallel and held exactly opposite to
one another. Each sample was kept between two electrodes, and
applied voltage method was used to measure the voltage at 28 +
2 0C. According to standard, the voltage was raised from 0 at a
uniform rate of 500 volts/sec, so the breakdown would occure
on average between 10 and 20 sec. The dielectric strength was
calculated using the following equation
Dielectric Strength = Breakdown Strength (kV)
Thickness of specimen (mm)
2.4.2.2 VOLUME RESISTIVITY
Volume Resistivity was measured as per ASTM D257
standard. Volume Resistance was measured with a high
resistance meter from Hewlett-Packard (model 4329A) (USA).
Compression moulded sheet having diameter 100mm was
inserted into the sample holder (cell) and charged for 1 min at
500 V (direct current). The volume resistance measurements
were carried out at 27 + 2 0C.
Volume Resistivity (ohm. Cm) = 19.6 (Rv/t)
where Rv is the volume resistance (ohm) and t is the thickness
(cm) of the sheet.
2.4.2.3 SURFACE RESISTIVITY
Surface Resistivity was measured as per ASTM D257
standard. Surface Resistance was measured with a high
resistance meter from Hewlett-Packard (model 4329A) (USA).
Compression moulded sheet having diameter 100mm was
inserted into the sample holder (cell) and charged for 1 min at
500 V (direct current). The surface resistance measurements
were carried out at 27 + 2 0 C.
Surface Resistivity (ohm) = 18.8 x Rs
Where Rs is the surface resistance
2.4.3 THERMAL PROPERTIES
2.4.3.1 THERMOGRAVIMETRIC ANALYSIS (TGA)
Thermo-gravimetric analysis of HDPE nanocomposite
samples was carried out on a Mettler Toledo TGA SDTA 851
thermogravimetric analyzer. The nanocomposite samples were
kept on an alumina pan in air. Thremograms of nano-
composites samples were recorded from room temperature to
6000 C at heating rate of 100 C per minute.
2.4.4 GLOW WIRE TEST
Glow wire tests on the HDPE, HDPE raw clay composite and
HDPE clay nanocomposites were carried out at 650 0 C and
850 0 C according to IEC – 695 -2 – 1 standard.
3 RESULTS AND DISCUSSION
3.1 MODIFICATION OF CLAY
The swellability of indigenous untreated clay was found to
be 18 times in water. Its swellability is reduced to 5 times after
treatment with Hexadecyl trimethyl ammonium bromide
856 K. S. Shah et al.: High Density Polyethylene (HDPE) Clay Nanocomposite for Dielectric Applications
because of change in hydrophilicity to hydrophobicity of clay.
After filtering, a wet cake was obtained. The pieces of cake
after drying at room temperature shrink into hard lumps.
Lumps are broken by a mixture grinder to convert it into
powder form. The IR spectra of the modified clay confirm the
absorption of quaternary ammonium compound between the
clay galleries. For the organically modified montmorillonite,
the characteristic absorption bands include CH2 asymmetric
stretching (2926.07 cm-1), CH2 symmetric stretching
(2853.32cm 1), CH2 plane scissoring (1489.43 cm-1) and CH
out of plane bending (791.91cm-1). In addition, the absorption
bands related to silicate are also found, such as OH stretching
of lattice water (3621.34cm–1), H-O-H bending (1636.85cm–
1
), Si-O-Si stretching (1030.05cm–1), Si-O stretching and Si- O
bending (600-400cm –1). The IR spectra of the raw
montmorillonite clay and organically modified
montmorillonite clay are given in the Figures 3 and 4.
Figure 3. IR Spectra of the raw MMT
Figure 4. IR spectra of the Modified clay
3.2 PREPARATION OF NANOCOMPOSITE
The torque vs. time graph of the HDPE nanocomposites
obtained during preparation in the Brabender mixture has been
studied. It has been observed that torque increases with the
increase in the clay content indicating the increase in the
viscosity of the melt. The effect of the modification of clay by
quaternary ammonium compound, silane and combination of
silane and titanate coupling agents on the torque during the
mixing in Brabender can be seen in Figures 5 to 8. For the 5
wt % of raw clay, the torque is highest at 83.2 N. For the 5 wt
% organo clay torque reduces to 72.2 N. As the concentration
of the silane increase in the clay, torque and consequently
viscosity of the nanocomposite reduces. For the 5 %
concentration of the silane, torque reduces to 63.8 N. For the
clay treated with combination of silane and titanate coupling
agents, a larger reduction in torque is observed compared to
the nanocomposite treated with silane alone. For the
nanocomposite having 2.5 % silane and 2.5 % titanate the
torque reduces to 62.5 N. The torque vs. time curves of the
nanocomposites confirms that as the silane concentration
increases the viscosity of the nanocomposite reduces that in
turn reduces energy require to disperse the clay in the HDPE
matrix. Silane coupling agent improves the dispersion of the
clay in the HDPE and strengthen the interface of the clay and
HDPE molecules. The torque vs. time curves of the HDPE
clay nanocomposite, which contain clay treated with
combination of silane and titanate coupling agents, shows
much reduction in the torque with respect to the same
concentration of the silane. These curves confirm that use of
the combination of coupling agents gives improved effect in
dispersion of clay and reduction in viscosity. Use of the
combination of coupling agents much reduces the energy
require for the dispersion of the clay in the HDPE matrix than
silane alone. These results confirm that the use of silane and
titanate coupling agents improves the dispersion and
processing conditions.
Figure 5. Torque vs. time curve of the HDPE – 5 wt % raw clay
Nanocomposite
Figure 6. Torque vs. time curve of the HDPE – 5 wt % organo clay
Nanocomposite
Figure 7. Torque vs. time curve of the HDPE 5 wt % clay nanocomposite
having Clay treated with 5 % concentration of silane.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No. 3; June 2009
Figure 8. Torque vs. time curve of the HDPE 5 wt % clay nanocomposite
having Clay treated with 2.5 % concentration of silane and 2.5 %
concentration of titanate
Figure 9. Photographs of the HDPE clay nanocomposites with silane and
titanate treatment.
The photographs of the HDPE raw clay composite and
nanocomposites prepared with organoclay, silane treated
organoclay and silane and titanate treated organoclay are
shown in Figure 9. There is significant improvement in
apparent properties of the nanocomposite. On increasing the
concentration of coupling agents, colour and gloss of the
nanoclay composite specimen improves significantly. It
indicates the homogenization and proper dispersion of the clay
in polymer matrix. It is evident from the gloss improvement of
nanocomposite moulded coupons.
3.3 ELECTRICAL PROPERTIES
The electrical properties including Dielectric Strength,
Volume Resistivity and Surface Resistivity of the HDPE and
all the nanocomposite compositions prepared are plotted in the
Figures 11 to 16. Values are also summarized in Table 1 and
Table 2. The dielectric strength of the nanocomposite
increases significantly with increasing the clay content up to
5wt %. Upon further addition of clay, improvement stabilizes
and slightly reduces. The dielectric strength of HDPE, HDPE
unmodified clay composite with 5 weight percent and HDPE
nanocomposite with 5 weight percentage organoclay are 30,
48 and 54 kV/mm respectively. Exfoliated and intercalated
structure might be responsible for the improvement.
Exfoliated and intercalated clay platelets distribute the electric
stress and increase the path length for the break down. They
857
act as the barrier for the break down. The modification of clay
with quaternary ammonium compound reduces the surface
energy of the clay platelets and the intercalation of polymer
molecules becomes feasible. On 7 and 10 wt % of addition of
modified organoclay, dielectric strength decreases compared
to 5 wt % addition of modified organoclay because, on higher
loading, exfoliated structure decreases and intercalated and
flocculated platelets of clay increases. Flocculated clay stacks
provide weak interface sites which are responsible for the
decrease in the dielectric strength. Break down of the
nanocomposite with higher clay loading might be happening
through such weak interface sites of the flocculated clay
stacks. Further the treatment of organoclay with silane
strengthens the interface by chemical linkages which
consequently increase the dielectric strength. The treatment of
organoclay with the combination of silane and titanate
coupling agents strengthen the interface by chemical linkages
and anchoring effects of the organic groups of the silane and
titanate with HDPE molecules.
Clay particles act as barrier for breakdown by electrical
stress. Therefore, the strength of particle polymer bonding is
important factor for the improvement of the dielectric
properties of the nanocomposite. Figure 10 shows the treeing
effect due to clay platelets which increases the path length for
breakdown.
Surface resistivity increases as clay content increases. For
silane treated clay, surface resistivity increases as the
concentration of silane increases. High concentration of silane
gives higher chemical linkages, which strengthen the interface,
and reduces the surface roughness. For the clay treated with
the combination of silane and titanate coupling agents, the
surface resistivity increases with concentration and the
improvement is higher than the use of silane alone. The
anchoring effect and chemical linkages of silane and titanate
coupling agents gives synergetic effects.
Figure 10. Treeing effect due to clay platelets.
Volume resistivity increases as the organoclay content
increases. For the nano-composite treated with the coupling
agents, volume resistivity increases as the concentration of
coupling agent increases. At 5 % concentration, combination
of coupling agents gives high volume resistivity compare to 5
% silane alone. At higher concentration, dispersion of clay
improves and homogeneity of the system increases because of
chemical linkages and anchoring effect of organic parts of the
coupling agents with polymer molecules.
858 K. S. Shah et al.: High Density Polyethylene (HDPE) Clay Nanocomposite for Dielectric Applications
Table 1. Electrical properties of HDPE clay nanocomposite
HDPE clay nanocomposite clay content

Electrical Properties 12
Clay

Volume Resistivity
Dielectric Volume Surface

x 10 (Ohm.cm)
10
Content Strength Resistivity Resistivity 8

(KV/mm) (ohm.cm) (ohm) 6

12
4
HDPE 31.3 2.6 x 10 12
5.1 x 10 11
2
H5C 48.9 4.9 x 10 12
9.4 x 10 11 0
HDPE H1mc H3mc H5mc H7mc H10mc
H1mc 40.6 3.2 x 1012 8.5 x 1011 Composition

H3mc 52.8 6.8 x 1012 9.4 x 1011 Figure 13. Volume resistivity of HDPE clay nanocomposites.
Silane
H5mc 55.7 9.6 x 1012 16.9 x 1011
HDPE clay nanocomposite
Combination of silane and titanate

H7mc 49.7 9.6 x 10 12

18.8 x 10 11 2000

13
Volume Resistivity x 10
1500
H10mc 48.9 10.8 x 1012 18.8 x 1011

(ohm.cm)
1000
Table 2. Electrical Properties of HDPE clay nanocomposites.
500
Electrical Properties
0
Concentration
of Coupling Dielectric Volume Surface 0 2 4 6
Concentration
agent Strength Resistivity Resistivity
(KV/mm) (ohm.cm) (ohm) Figure 14. Volume Resistivity of HDPE clay nanocomposites treated
with silane and titanate
H5mc 55.7 1x 1013 1.7 x 1012 HDPE clay nanocomposite Clay content

H5mc1S 56.3 1.7 x 1014 9.4 x 1012 2

12
Surface Resistivity x 10

H5mc3S 60.5 15 x 1015 1.3 x 1014 1.5

H5mc5S 66.5 3.7 x 1015 8.5 x 1014

(ohm)

1
H5mc0.5S0.5T 56.4 1.7 x 1014 1.5 x 1013
0.5
H5mc1.5S1.5T 64.5 3.8 x 1015 2.2 x 1014
0
H5mc2.5S2.5T 68.7 19.6x 1015 9.9 x 1014 HDPE H1mc H3mc H5mc H7mc H10mc
Composition
HDPE clay nanocomposite Clay content
Figure 15. Surface Resistivity of HDPE Clay nanocomposites.
60 Silane
HDPE clay nanocomposite
Combination of silane and titanate
55
Dielectric Strength

50 1000
(KV/mm)

45
Surface Resistivity

800
x 10 (Ohm)

40
600
35
12

30 400
HDPE H1mc H3mc H5mc H7mc H10mc 200
Composition 0
0 1 2 3 4 5 6
Figure 11. Dielectric strength of HDPE clay nanocomposites.
concentration
Silane
HDPE clay nanocomposite Figure 16. Surface Resistivity of HDPE clay nanocomposites treated
70 Combinatrin of silane with silane and titanate.
and titanate
Dielectric Strength

65
3.4 MECHANICAL PROPERTIES
(KV/mm)

60
The mechanical properties, including Tensile strength,
55
Elongation at Break, Impact Strength and Hardness of HDPE
50 and all the nanocomposites prepared in this study have been
0 2 4 6 plotted in Figures 17 to 22. Values are also summarized in
Concentration Table 3 and Table 4. The tensile strength of the
nanocomposite prepared by organically modified clay
Figure 12. Dielectric Strength of HDPE clay nanocomposites treated with
silane and titanate. increases up to 5 weight % of clay. On further addition of
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No. 3; June 2009 859

clay, Tensile strength decreases. The increase in tensile Table 4. Mechanical properties of HDPE clay nanocomposite.
strength up to 5 wt % of clay may be due to an increase of
intercalated and exfoliated structure of the clay platelets in the Mechanical Properties
Concentration
nanocomposite. On higher loading exfoliated structure of Coupling Tensile Impact
Elong. Shore D
decreases whereas intercalated and flocculated structure of agent Strength Strength
(%) Hardness
clay stacks increases. This is probably because the free energy (N/mm2) (J/cm2)
of mixing of two heterogeneous phases is still high. So on H 5C 27.0 78 60 1.0
higher loading, to separate the clay platelets and to overcome H5mc 28.5 78 61 1.16
the attraction forces between the clay platelets, the
H5mc1S 28.9 78 61 1.23
environment between the clay galleries must be made which
balance the entropy loss of the intercalation of polymer H5mc3S 29.1 78 61 1.05
molecules by increase in the freedom of the organically H5mc5S 29.5 72 61.6 1.03
modifying agents absorbed between the clay galleries. Further H5mc0.5S0.5T 29.0 70 61 0.95
treatment of clay or compatibilisation of heterogeneous phase
H5mc1.5S1.5T 31.2 68 61.25 0.83
are needed to reduce the surface energy of the clay platelets.
Tensile strength of the silane treated clay nanocomposite H5mc2.5S2.5T 32.0 66.8 62 0.84
increases as the concentration of silane increases. Tensile
strength of the nanocomposites prepared using clay treated
with both silane and titanate coupling agents shows highest 29 HDPE clay nanocomposite Clay content
improvements. Use of coupling agents as compatibilizer 28.5

T e n sile Stre n g th (M P a )
between the inorganic and organic phase reduce the surface 28
energy of the clay platelets and reduce the free energy of 27.5
mixing. Chemical linkages between the clay and polymer
27
molecules by coupling agent and anchoring effect of the
26.5
organic part of the coupling agents in the polymer matrix
increase the strength of the interface which is also responsible 26
for the improvement in the tensile strength of the 25.5
nanocomposites treated with coupling agents. 25
Elongation at break of the nanocomposites shows the HDPE H5C H1mc H3mc H5mc H7mc H10mc
reverse behavior of the tensile strength. It decreases with Composition
increase in tensile strength. Figure 17. Tensile strength of the HDPE clay nanocomposites.
Impact strength of the nanocomposite decreases as the clay
content increases. Clay platelets increase the stiffness in the HDPE clay nanocomposite Silane
matrix which reduces the mobility of the polymer molecules. Combination of silane and titanate
For the nanocomposite treated with coupling agent, impact 32.5
strength decreases with increase in concentration of coupling 32
Tensile Strength (M Pa)

31.5
agent. Chemical linkages of coupling agents with clay 31
platelets and anchoring effect of the organic part of the 30.5
coupling agents reduce the mobility of polymer molecules and 30
reduce the flexibility in the system. 29.5
Hardness of the nanocomposite increases as the clay content 29
increases. Hardness of the nanocomposite treated with 28.5
28
coupling agents increases with increase in concentration. Clay
0 1 2 3 4 5 6
platelets increase the stiffness in the system Concentration
Figure 18. Tensile strength of the HDPE clay nanocomposites treated
Table 3. Mechanical properties of HDPE clay nanocomposite.
with silane and titanate.

Mechanical Properties HDPE clay nanocomposite Clay content

Clay Tensile Impact
Content Elongation Shore (D) 5
Strength Strength
(%) Hardness
Im pact Strength

(N/mm2) (J/cm2) 4
(J/cm 2)

HDPE 25.8 79.8 60 4.64 3

2
H1mc 28.0 78 60 1.49
1
H3mc 28.6 78.4 61 1.52
0
H5mc 28.5 78 61 1.16 HDPE H5C H1mc H3mc H5mc H7mc H10mc
H7mc 26.8 81.6 63 1.19 composition
H10mc 26.7 83.2 63 1.33
Figure 19. Impact strength of the HDPE clay nanocomposites.
860 K. S. Shah et al.: High Density Polyethylene (HDPE) Clay Nanocomposite for Dielectric Applications
Table 5. % weight loss against temperature.
HDPE clay nanocomposite Silane
1.3 Combination of silane and titanate % Weight HDPE H5C H5mc H5mc5S H5mc-
1.2 Loss (0C) (0C) (0C) (0C) 2.5S2.5T
Impact Strength

1.1 (0C)
(J/cm )
2

1 05 377.3 353.6 364.6 404.6 370.0

0.9 10 394.0 396.3 404.0 419.5 418.7
0.8 15 406.0 406.0 414.2 425.7 424.1
0.7 20 415.9 413.5 421.6 431.1 428.7
0 2 4 6 25 424.5 420.0 428.0 436.1 432.8
Concentration
30 432.2 425.6 434.1 440.7 436.7
Figure 20. Impact strength of the HDPE clay nanocomposites treated 35 439.2 430.8 439.5 445.0 440.3
with silane and titanate.
40 445.3 435.9 444.5 449.0 443.7
HDPE clay nanocomposite Clay Content 45 450.8 440.7 448.9 452.8 446.9
64
50 455.7 445.4 453.0 456.4 450.0
Shore (D) Hardness

63
62
61
60
59
58
HDPE H5C H1mc H3mc H5mc H7mc H10mc
Composition

Figure 21. Hardness of the HDPE clay nanocomposites.

Silane
HDPE clay nanocomposite
Combination of silane
62.2 and Titanate
Shore (D) Hardness

Figure 23. Thremograms of the HDPE, HDPE raw clay composite and
62 HDPE clay nanocomposites
61.8
61.6 3.6 GLOW WIRE TEST
61.4
61.2 All the sample passed the test at 650 0C. No flame was
61 observed and no dripping was observed during the contact
60.8 time of the tip. At 850 0C temperature, the flame was observed
0 1 2 3 4 5 6
above 25 mm height and extinguishes withing 30 s for all the
Concentration samples. No dripping is observed during the contact time. All
Figure 22. Hardness of the HDPE clay nanocomposites treated with nanocomposites sample confirm the test as per IEC - 695 – 2 -
silane and titanate. 1 standard.

3.5 THERMAL PROPERTIES

4 CONCLUSIONS
Thermal degradation of the HDPE and HDPE clay
nanocomposites were measured by thermogravimetric Indigenous clay from Mandvi, Kutchh (western part of
analysis. TGA graphs of the HDPE, 5 % raw clay composite India) was modified by Quaternary Ammonium Compound
(H5C), 5% organoclay nanocomposite (H5mC), clay such as Hexadecyl Trimethyl Ammonium Bromide. HDPE
nanocomposites with silane and combination of silane and clay nanocomposites were prepared by varying the modified
titanate (H5mC5S and H5mC2.5S2.5T) with HDPE are shown organoclay content and concentration of silane and titanate
in Figure 23 and data for the weight loss (%) at different coupling agents in the ratio of 1, 3 and 5%. Addition of organo
temperature is given in Table 5. From the Figure 23 and Table clay along with coupling agents improves the electrical,
5, it is clear that the thermal stability of the nanocomposite mechanical and thermal properties significantly. Optimum
increases as increase in the concentration of coupling agents in values were achieved by adding 5% of organoclay in HDPE
clay. Clay particle act as a superior insulator and mass with a combination of silane and titanate coupling agents. The
transport barrier to the volatile products generated during coupling agents form chemical linkages between the organic
decomposition. The data presented in the Table - 5 show that and inorganic phases. An anchoring effect due to coupling
the thermal stability of the nanocomposite treated with silane agent strengthens the matrix filler interface. The use of
and titanate coupling agents is improved and are more stable coupling agents, silane and titanate gives synergistic effect in
than virgin HDPE particularly at initial weight loss range. improving the strength of interface. The thermal stability of
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 16, No. 3; June 2009
nanocomposite was also improved by addition of coupling
agents. The glow wire test was also carried out on HDPE clay
nanocomposites with an objective to use this material for
wiring accessories. It confirms the IEC 695–2–1 standard.
ACKNOWLEDGMENT
The authors gratefully acknowledge Dr. M. Ramamurthy for
his motivation and suggestions to carry out this work. The help
rendered by Dr. P A. Krishnamoorthy, his group and TDC
department is thankfully acknowledged. The authors are grateful
to Electrical Research and Development Association for financial
help and providing a research fellowship to Mr. Ketan Shah.
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K. S. Shah was born on 30 June 1981 at Dhuvaran,
India. He received the M.Sc. degree in industrial
polymer chemistry in 2004 from the Sardar Patel
University, Vallabh Vidhyanagar. After 1 year with
GSECL power station, Dhuvaran he joined Electrical
Research & Development Association, Vadodara in
2006 and started research work for the Ph.D. degree.
His field of research includes the preparation of nano
dielectric particles, synthesis of coupling agents, preparation of
nanocomposite with thermoplastic and thermosetting polymers and
characterization of these nanocomposite materials for their electrical,
mechanical, thermal and morphological properties. His research work
concerns the study of the effects of various coupling agents on the electrical
properties of the nanocomposite.
861
Dr. Ramesh Chand Jain was born on 29 April 1942
in Tehra, India. He received the B.Sc and M.Sc
degrees in 1962 and 1964, respectively. He obtained
his Ph.D. degree in polymer science from Agra
University in 1978. He worked as a scientist at Shri
Ram Institute at Delhi and lecturer in chemistry at
IIT Delhi. He served as Head, Polymer and Material
Science at Research Center of Indian Petrochemical
Corporation Limited, Vadodara for 29 years and held
different positions during this period. Presently he is a consulting scientist at
Electrical Research and Development Association, Vadodara and guiding
research students for Ph.D. and developing insulating material for power
industries. He has guided about a dozen M.Tech. and Ph.D. students. He has
published over 100 research papers in national and international journals and
has many patents. He is recipient of several awards for academic and
industrial research. His areas of interest are process, products and new
polymer development for industrial applications.
Dr. Vagish Shrinet was born on 16 February 1958
in Uttar Pradesh, India. He received the M.Sc.
(physics) degree in 1978 from Gorakhpur University.
He received the Ph.D. degree from Banaras Hindu
University, Varanasi in 1985 and then he joined
Electrical Research and Development Association,
Vadodara. He has six patents and more than eighty
research publications in national/international
journals/seminars. Twice he got national NRDC
technology awards in 2004 and 2007. He is also selected for WIPO (World
Intellectual Property Organization, Geneva) gold medal for innovation in year
2008. He has worked with CSIRO, Melbourne, Australia and Corporate R &
D of General Electric, Bangalore. At present he is working as Sr. Manager and
Head (TDCC) at ERDA, Vadodara. His areas of interest are condition
monitoring, residual life assessment, smart materials and renewable energy.
Dr. Dinakar P. Bharambe was born on 19 may 1957
in Maharashtra, India. He received the M.Sc. degree. in
inorganic chemistry in 1982 from the Department of
Chemistry, Sardar Patel University and the Ph.D.
degree in polymer chemistry in 1988 from M. S.
university. He is presently working as Reader in the
Department of Applied Chemistry, M. S. University.
He has published twelve research papers in national and international journals.
His area of research is pour point depressing polymeric flow improvers for
crude petroleum and preparation of nanocomposite materials for industrial
applications.
Shri Awadhesh Kumar Singh was born on 9
November 1951 in Uttar Pradesh, India. He is
presently working as Director with
Electrical Research & Development Association,
Vadodara. He obtained his B.E. degree in
mechanical engineering. with Honours in 1974 from
the University of Gorakhpur. . He received the
M.Tech. Degree in turbo machines from IIT, Delhi in 1979. He has three
decades of experience as a power sector professional and two years of
academic experience as a Professor of mechanical engineering. His field of
expertise includes turbo-machines, fluid mechanics & fluid power, RLA &
LE, condition monitoring, quality management and energy management. He is
a Fellow of Institution of Engineers (India), Fellow of Society of Power
Engineers (India), Member of Indian Institute of Welding, Member of
International Association on Electricity Generation, Transmission &
Distribution (Afro-Asian Region), Member of the Research Advisory
Committee of National Innovation Foundation, India, Member of the
Advisory Board for Aerial Ropeways constituted by Government of Gujarat
and Member of the Refrigeration and Air Conditioning Sectional Committee
of the Bureau of Indian Standards. He has contributed more than five dozen
of technical papers to journals, conferences and seminars.