Mechanical, Thermal and Dielectric Properties of Cross-

linked Polyethylene Nanocomposites

Manswini P.a, Rithika Reddya, Kavitha Db, Meera Balachandranc
a
Department of Chemical Engineering and Materials science, b Department of electrical
engineering, c Centre of Excellence in Advanced Materials and Green Technology,
Department of Chemical Engineering and Materials science, Amrita Vishwa
Vidyapeetham, Coimbatore, India

INTRODUCTION

Reinforcing polymer with nanosized fillers yield materials with enhanced

performance1-3. Nanaoclay modified with organo – modifiers have been widely used
in polymeric systems3-4. The amount of the nanoclay content in the matrix determines
the properties of the nanocomposites. Cross- linked polyethylene is widely used as
insulation material in high tension underground cables and submarine cables 5,6. The
long time exposure to moisture and electrical stress leading to partial discharge
cause treeing and breakdown in the insulation 5,6. It has been reported in literature
that addition of nanoclay in epoxy enhances the dielectric properties and reduce the
treeing phenomenon7. Incorporation of naoclay into the polymer matrix also
improves mechanical, thermal, barrier and ageing properties of polymer
nanocomposites3,4. In this paper, the effect of nanoclay content on the mechanical,
ageing, thermal and electrical properties of XLPE – nanoclay composites was
investigated.

EXPERIMENTAL

The cross linked polyethylene and cross – linking agent used in this work was KLJ-
XL-01 (KLJ Polymers& Chemicals Ltd.) and the nanoclay used was Nanomer 1.30E
(25-30 wt% of Octyldecyl amine salt and d 001: 20.29 nm, Sigma Aldrich). To prepare
XLPE – nanoclay composites polyethylene pellets, crosslinking agent and nanoclay
was mixed in Haake Rheocord 90 at 60 rpm and 190°C temperature for 20 minutes.
The nanocomposites were cured in a water bath at 90 ⁰C for three hours and molded
in hydraulic compression press at 175 kg/cm 2 and 200°C. Morphological studies
were performed on Bruker D8 ADVANCE X-ray diffractometer (Cu X-ray beam of
wavelength 1.5406 A°) at 3°/minute and Park system XE70 atomic force microscope.
Tensile properties were evaluated as per ASTM D638 (Type 5) method on a UTM at
crosshead speed of 50 mm/min. Samples were heat aged at 100 0C for 48 hours and
tested for mechanical properties. Perkin Elmer, Diamond TG/DTA and on Toledo
DSC 822e were used for thermal properties at heating rate of 10°C / min. The
dielectric constant (relative permittivity) and dissipation factor (tan δ) were evaluated
using ASTM D150 standards.

RESULTS AND DISCUSSIONS

Figure 1 shows the XRD pattern for XLPE nanocomposites. For the organomodified -
nanoclay the peak occurs at 2θ of 4.334 corresponding to d spacing of 20.41 nm.
For XLPE nanocomposites, absence of peaks indicated that the nanoclay was
exfoliated in the polymer8. The appearance of small peak at 2θ of 6.7 for 7.5 and
10% nanoclay indicated intercalation and slight agglomeration. AFM images of neat
XLPE showed relatively smooth surface. Figure 2 shows the AFM image of
XLPENC7.5 and it can be noted from the different colored peaks corresponing to
different heights that nanoclay was exfoliated with formation of few agglomerates 9.

Fig 1. XRD pattern for XLPE nanocomposites Fig 2. AFM image for XLPEN7.5
The mechanical properties of XLPE nanoclay composites before and after ageing
are tabulated in Table 1. In XLPE nanocomposites, the tensile strength increased
with increase in the nanoclay content from 0 to 5% after which there was a slight
decrease. There was significant increase in the modulus with the increasing
nanoclay loading confirming the reinforcing effect of nanoclay which can be
attributed to the exfoliation of nanoclay that resulted in larger surface area and better
interfacial interaction with XLPE matrix8,10. The reduction in tensile strength at higher
nanoclay content is due to the formation of intercalated structures and
agglomerates8. As nanoclay Restriction of polymer chain mobility by nanoclay
decreased elongation. It was observed after heat ageing the tensile strength and
modulus of the nanocomposites increased due to the continued curing while
elongation decreased making them more rigid and stiffer. As the percentage change
in properties after ageing decreased with increase in nanoclay content, it may be
concluded that nanoclay improved the ageing behavior of XLPE.

Table 1. Mechanical Properties of XLPE Nanocomposites

Sample Before Heat Ageing After Heat Ageing
Tensile Yield Break Modulus Tensile Yield Break Modulus
Strength Elong. Elong. MPa Strength Elong. Elong. MPa
MPa % % MPa % %
XLPENC0 9.40 154 235 1086 12.58 239 311 1114
XLPENC2.5 10.5 12.2 158 1501 12.54 14.7 163 1741
XLPENC5 14.3 17.3 155 1764 17.23 15.7 129 1815
XLPENC7.5 12.06 19.5 85.0 1789 10.75 14.4 83.2 1602
XLPENC10 12.5 11.3 114 2379 13.2 16.1 89.8 2118
The thermal properties of XLPE nanocomposites are tabulated in Table 2.
Table 2 Thermal Properties of XLPE nanocomposites
IDT Tmax Char Melting Crystallisation
Nanoclay
(°C) (°C) (%) Temperature (⁰C) Temperature (⁰C)
Sample Content (%)
XLPENC0 0 355 468 0 114 103
XLPENC2. 2.5 365 451 0 115 102
5
XLPENC5 5 375 419 4.14 115 102
The thermal stability of the composites was enhanced on addition of nanoclay. In
neat XLPE, the initial decomposition temperature (IDT), was around 355° C and
increased by 20⁰C on addition of 5% nanoclay, confirming that nanoclay enhances
the the thermal stability of XLPE. The temperature at which maximum rate of
decomposition occured (Tmax) decreased with increased nanoclay content, possibly
due to the decomposition of the alkyl chain modifications in the nanoclay. The char
content of the nanocomposites at 500°C increased with nanoclay content due to the
higher mineral content at higher percentages. . From the DSC scans it was seen that
the addition of nanofiller did not have a major effect on the crystallization
temperature and the melting point.

The variation of dielectric constant and tan δ of the XLPE nanocomposites are
shown in Figure 3. The dielectric constant and tan δ for all nanocomposites with
varying compositions of nanoclay show the same trend as shown in figure 3. The
tortuous path induced by nanoclay slows the propagation of electrical current and
hence the dielectric constant decreased with increase in the nanoclay content and
enhanced the insulating property of XLPE 11. The slight increase at 10% may be due
to possible agglomeration. Addition of nanoclay decreased the loss factor at
intermediate frequencies whereas it increased at low frequencies.

Fig. 3 Variation of relative permitivity and tan δ with frequency

CONCLUSION

The morphology of LPE nanoocomposites show exfoliation. The mechanical

properties improved with increasing content of nanoclay. Nanoclay decreased the
effect of heat ageing and improved the thermal stability in XLPE. The dielectric
constant and insulation properties of XLPE increased with increasing nanoclay
content.

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