264 P. Preetha and M. J.

Thomas: Partial Discharge Resistant Characteristics of Epoxy Nanocomposites

Partial Discharge Resistant Characteristics

of Epoxy Nanocomposites
P. Preetha and M. Joy Thomas
Nanodielectrics Laboratory
Department of Electrical Engineering
Indian Institute of Science
Bangalore, 560 012, India

ABSTRACT
Epoxy nanocomposite samples with a good dispersion of alumina nanoparticles in
epoxy matrix were prepared and experiments were performed to measure their partial
discharge resistant characteristics. Epoxy alumina nanocomposites with 0.1, 1, 5, 10
and 15 wt% nanofillers were prepared in the laboratory and partial discharge (PD)
experiments were conducted at a voltage of 10 kV for different durations using IEC (b)
type electrodes. The degradation of the sample surfaces were analyzed using SEM
techniques, surface profile studies, FTIR spectroscopy as well as PD studies. An
attempt was made to understand the interaction dynamics between the nanoparticle
and the epoxy chain by measuring the glass transition temperature of the
nanocomposites. The partial discharge resistance obtained for the nanocomposites are
compared with those of unfilled epoxy and epoxy microcomposites. It was observed that
even with 0.1 wt% of nanofiller added to the epoxy matrix, the partial discharge
resistance to degradation gets improved considerably. It was also observed that the
inter particle distance has a significant effect on the discharge resistance to
degradation. The improvement in the degradation resistance is attributed to the
interactions between the nanoparticle and the epoxy chain. A possible mechanism for
the surface degradation of nanocomposites has been proposed.
Index Terms — Epoxy, nanocomposites, nanofiller, partial discharge, surface
degradation.

suppress the partial discharge in high voltage windings of

1 INTRODUCTION rotating machines [5-7]. The ongoing research in the field of
ELECTRICAL discharges can occur in a gas, liquid or nanodielectrics has already reported that nanodielectric
vacuum in close vicinity to a solid dielectric surface. Such a material possess excellent dielectric properties [8, 9]. But only
discharge is known as a surface discharge. As a result of the few studies have been reported on the electrical discharge
proximity of the discharge plasma to the surface, considerable resistant characteristics of polymer nanocomposites. Kozako
degradation of the solid dielectric surface can occur. In et al [10, 11] performed experiments using the IEC (b)
insulating systems used in the windings of high voltage electrode to study the discharge resistance characteristics of
rotating machines, PD can occur as internal discharge, surface polyamide layered silicate nanocomposites and observed that
discharge, end-winding discharge, slot discharge, discharge with only 5 wt% fillers, the nanocomposite had superior
between bars of different phases, and/or copper conductor resistance to surface discharges when compared with the
interfaces, and inter-turn discharge [1, 2]. The phenomenon of unfilled polyamide and the microcomposites. The authors
surface partial discharge on high voltage stator winding end attribute this enhancement in the property to the presence of
turns can occur at several locations having high electric field. nanoparticles, the formation of high crystalline zones and
In high-voltage insulation systems, the occurrence of such formation of strong chemical bonds. Tanaka et al [12] also
discharges is highly undesirable as insulating materials and in observed an enhancement in the partial discharge degradation
particular polymers, degrade rapidly both physically and resistance in the epoxy clay nanocomposites as compared to
chemically when exposed to discharges [3]. This can the base epoxy systems. It has also been shown by Fuse et al
subsequently lead to premature failure of the insulation. [13] that the addition of mica nanofiller to polyamides can
Several studies have reported the different mechanisms of increase the surface degradation resistance of the
failure of rotating machines [4] and the remedial measures to nanocomposites when compared with the unfilled polymer.
The author claims that this is due to the reduction of oxidation
Manuscript received on 15 January 2010, in final form 25 August 2010. mechanisms and the formation of a layered nanofiller structure

1070-9878/11/$25.00 © 2011 IEEE

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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 1; February 2011 265

in a nanocomposite during exposure to electrical discharges. It Table 1. Interparticle distance in epoxy alumina nanocomposites.
was also shown that the resistance to partial discharges and to
Filler Inter particle distance
plasmas improve with increase in the nanofiller content.
concentration (wt%) (nm)
Investigations have been carried out on the effect of
electrical, chemical and radiation induced stresses on the 0.1 447
surface chemistry of unfilled epoxy and epoxy composites by 0.5 245
Hepburn et al. [14-16] and they suggest that the filler materials
affect the physico-chemical reactions occurring due to the 1 186
electrical discharges. 5 91
Although several possible reasons for the improvements in the
10 62
surface discharge resistance have been suggested and are still
being explored, a generalized inference cannot be made as yet 15 48
and focused studies are still desired to understand the influence of 20 39
nanofiller addition and the filler concentration on the degradation
mechanism of polymers exposed to electrical discharges.
In this paper, an attempt has been made to study the partial
discharge resistant characteristics of epoxy alumina 2.3 SAMPLE PREPARATION
nanocomposites with various nanofiller loadings. The filler As the nanoparticles are highly charged particles they
concentrations are so selected that the interparticle distance tend to agglomerate and form larger particles leading to a
between them becomes almost in the same range as that of the reduction in the surface area to volume ratio. Since most of
particle diameter itself. It was found that with the increase in the the promising dielectric properties are related to the surface
filler concentration, the average surface roughness reduces and area enhancement in the nanocomposites, proper processing
this is explained based on the physical model. An attempt is also techniques are to be adapted to uniformly disperse the
made to understand the chemical degradation taking place on the nanoparticles [18].
sample surface due to the electrical discharge and its effect on the The nanocomposites were prepared by the direct
degradation resistance of the epoxy alumina nanocomposites.
dispersion technique in the laboratory. Initially the epoxy
resin and the hardener were degassed for one hour to
2 EXPERIMENTAL DETAILS remove trapped air bubbles and moisture. The filler
2.1 MATERIALS USED particles were vacuum dried at 150 0C for 24 hours and are
Bisphenol-A epoxy resin (CY1300, density 1.16 g/cm3) kept at 150 oC for several days to maintain the dryness
along with a Triethylene Tetramine (TETA) hardener (HY956, before using it for processing. Then the epoxy resin and the
density 1.02 g/cm3) of Huntsman make were used for the nanofiller were mixed in a high shear mechanical mixer at a
investigations. The nanofiller material used was spherical speed of 700 rpm for 2 minutes. The mixture was then
aluminium oxide nanoparticle of average particle size (APS) subjected to ultrasonic agitation at a frequency of 24 kHz
40 nm and density 4 g/cm3 at 25 OC. Aluminium oxide particles for 1 hour. Then the hardener is added to the particle-resin
of average particle size 5 μm were used as microfillers. All the mixture in the ratio 1:4 and mixed thoroughly by hand
fillers were supplied by Sigma-Aldrich, USA. mixing. This mixture is then degassed to remove the
trapped air bubbles before casting it in a mould at 60 0C for
2.2 SPECIMENS PREPARED
4 hours to prepare samples of 3mm thickness and 75 mm
To understand the effect of filler concentration and the diameter. Proper care was taken to reduce the moisture
interface on the surface discharge degradation resistance, ingress in to the materials while processing. The epoxy
different filler concentrations were chosen based on the
micro composite sample was prepared by mechanical
interparticle distance. The inter particle distance in epoxy
mixing alone. The samples prepared are then kept in a
nanocomposites has been calculated using the expression
dessicator under vacuum for at least 24 hours to release
given by Tanaka et al [17].
residual stresses if any before carrying out the surface
ଵ
ߨ ߩ௡ ͳͲͲ ‫ݐݓ‬Ψ ߩ௠ ଼ discharge studies [19].
‫ ܦ‬ൌ ‫ۃ‬൜ ൬ ൰ ൤ͳ െ ൬ͳ െ ൰൨ൠ െ ͳ‫݀ ۄ‬ሺͳሻ The dispersion of fillers in the epoxy nanocomposites
͸ ߩ௠ ‫ݐݓ‬Ψ ͳͲͲ ߩ௡
were investigated by examining the cross section of the
ȡm and ȡn are the specific gravity of the matrix and that of the sample under a JEOL field emission scanning electron
filler respectively and ‘d’ is the diameter of the filler. The microscope (FESEM). Samples of approximately 2 mm × 2
interparticle distance for epoxy alumina nanocomposites are as mm × 3 mm are prepared by cutting the epoxy
shown in Table 1. It can be seen from Table 1 that above 5 nanocomposites at different locations on the specimen.
wt% filler concentration, the interparticle distance is less than Then the samples were coated with gold of 5 nm thickness
100 nm. Also it can be seen that the inter particle distance to prevent the specimen from charging when exposed to the
reaches a value almost equal to the filler diameter itself at a electron beam in the microscope. The images in Figure 1a
filler concentration of 15 wt%. So for the present study filler and 1b show uniform dispersion of alumina nanoparticles
concentrations of 0.1,1,5,10 and 15 wt% of nano alumina were in the epoxy matrix at a filler concentration of 5 wt% and
chosen. 15 wt% respectively.

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 266 P. Preetha and M. J. Thomas: Partial Discharge Resistant Characteristics of Epoxy Nanocomposites

Figure 3. Experimental setup for the surface discharge studies.

(a) 5 wt% nanoalumina,

(b) 15 wt% nanoalumina

Figure 4. Photograph of the test cell arrangement showing the surface
Figure 1. SEM images of epoxy alumina nanocomposites.
discharge on the sample.

2.4 SURFACE DISCHARGE STUDIES 2.5 CHARACTERISATION TECHNIQUES

The surface discharge studies were carried out on neat epoxy, The surfaces of the samples after exposure to surface
epoxy alumina microcomposite and epoxy alumina discharges were examined using a Scanning Electron
nanocomposite samples. The IEC (b) electrode system as shown Microscope (FEI make SEM Quanta). The EDAX analysis
in Figure 2 has been used for the surface discharge studies. This was also done to confirm the presence of filler on the surface
system consists of a rod-plane electrode arrangement. The exposed to discharges.
electrodes were made of stainless steel and the diameter of the The surfaces of the sample exposed to surface discharges
rod electrode was 6 mm with 1 mm end curvature radius. The were tested for surface roughness using an Optical Surface
surface discharge experiments were conducted in ambient air at Profilometer (OSP) of Veeco, USA make. The value of the
an ac (50 Hz) voltage of 10 kV for three different durations of 5 average surface roughness (Ra) is chosen as a measure of the
hours, 10 hours and 24 hours. The temperature of the ambient surface degradation on the discharge exposed region of the
air was 24 + 1 oC and the relative humidity was 62 + 5%. The sample. The average surface roughness (Ra) is the arithmetic
schematic diagram of the partial discharge test setup is shown in mean of the absolute values of the surface departures from the
Figure 3. The discharges take place in the small air gap around mean plane.
the periphery of the rod electrode as shown in Figure 4 and the To analyze the material characteristics of the
degradation is maximum in the region near to the electrode. nanocomposites, their glass transition temperatures (Tg) were
measured using a Differential Scanning Calorimetry (DSC)
  Rod Electrode (6mm) equipment of Mettler, USA make. The experiments were
(HV Electrode) performed at 10 0C/minute rate of rise of temperature and were
scanned up to 150 0C.
A Varian 600UMA Attenuated Total reflectance Fourier
End curvature radius
1mm
Transform Infra-Red (ATR-FTIR) microscope was used to
Specimen (75mm obtain the FTIR spectrum of the specimen before and after
and thickness 3mm) exposure to surface discharges. The equipment has a
resolution of 4 cm-1 and the spectrum was captured in the
range 400 cm-1 to 4000 cm-1 using a Ge ATR crystal in the
Plane Electrode (50mm) reflection mode. This set up was useful in getting the spectra
(Grounded Electrode) at the various discharge degraded regions around the periphery
Figure 2. IEC (b) Electrode system. of the rod electrode.

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IEE
EE Transaction
ns on Dielectricss and Electrical Insulation Vool. 18, No. 1; February 2011 267

The partial discharge

d charracteristics weere analyzed by comparred to epoxy nanocomposite
n es. Also it is evident
e from
cappturing the PD
D pulses using an
a Omicron, Germany
G make PD the SEM M images thaat 15 wt% epooxy nanocompposite is the
dettector. The PD
D pulses were acquired for a duration
d of 10 s.
s least deegraded as coompared to thhe other nanoo and micro
compossites.
In thhe case of epooxy microcom mposites, the SEM
S images
3 RESULTS AN
ND DISCUSSIONS show ana increase in the low lyingg areas indicatting that the
O
One of the sppecimens exposed to surfaace dischargess is degradaation is maxim mum. But wiith just SEM analysis, a
shoown in Figure 5. The faint innner circular reegion corresponnds quantitaative analysis is
i not possible. So to quantifyy the amount
to the region directly
d under the rod electtrode, where the of deggradation, the average surrface roughneess of each
surrface is not degraded.
d It caan be seen thhat there are twot specimeen was measurred.
cirrcular ring typpe eroded regions (A and B) B on the surfa face
aroound the high voltage electrode. The innerrmost ring (A)) is
thee region arounnd the peripheery of the elecctrode where the 3.2 OSP
O MEASUR REMENTS
maaterial has beeen eroded moree. The discharrge propagatess in
airr to some distaance along thee surface of thhe solid specimmen The average surfacee roughness waas measured forr the samples
exposedd to surface discharges ussing an Optical Surface
leaading to degraddation of a larrger circular reegion (B) arouund
Profilommeter and the vaalues are given in i Table 2. The Ra values for
thee rod electrodde. The level of degradationn decreases with w
inccreasing distannce from the periphery
p of thhe rod electroode. differentt samples at diffferent time duraations of the appplied voltages
are preseented in Table 2. 2 The values of Ra in Table 2 clearly show
Thhe region ‘C’ shown in Fig gure 5 has noot undergone any a
the depeendence of the time
t duration off the applied voltage and the
vissible degradatioon.
influencce of filler parrticles on the surface roughhness of the
specimeens. For pure epoxye as well as a for nanocom mposites, the
3.1 SEM STUDIES surface roughness inccreases with inncreasing durattions of the
10 mm applied voltage. The otther important observation
o fromm Table 2 is
that the values of Ra in various aluminna nanocomposittes are lower
than thaat of the unfilledd epoxy for all thhe exposure durrations. Even
a small percentage
p of fiiller (0.1 wt%) itself
i is sufficiennt to enhance
the resisstance to surfacce discharge deegradation. Thiss means that
nanocom mposites have enhanced
e resistaance to surfacee degradation
and thiss is most likelyy due to the sttrong bonding between the
nanoparrticles and the epoxy
e at the intterface region which
w causes
the polyymer material to t hold on to the nanoparticlle and resist
degradattion [9]. It is observed that with increase in the filler
concentrration there is a further enhanncement in the degradation
1 mm
10 10 mm resistancce. This enhanncement is moore pronouncedd for higher
Fiigure 5. Photogrraph showing the discharge
d exposedd region of the epoxy durationns of discharge exposure whenn filled and unnfilled epoxy
allumina nanocompoosite sample (0.1 wt%)
w
composiites performannces are compaared. The incrrease in the
T SEM imaage of the sam
The mple surface before and affter degradattion resistance with
w increase inn filler concentraation may be
thee exposure to surface disch harges, taken in the innerm most due to the reduction in i the interpartticle distances between the
deggraded ring (A A) is shown in n Figure 6. It can
c be seen from nanoparrticles at higher filler loadings. This reduction may lead to
Figgure 6 that thhe surface of thet unexposedd unfilled epooxy an increease in the tigghtly bound reegion at the innterface thus
sammple is veryy smooth whereas the surfaces s of the resistingg degradation. From
F Table 2, it is seen that there is not
disscharge expossed samples lo ook rough. Thhe roughness on much variation
v in the surface roughnness for lowerr duration of
thee sample surffaces indicate that the material has erodded exposure to discharges.
due to the electrrical dischargees. Two distincct regions cann be Thhe average surfaace roughness inncreases with inncrease in the
ideentified on thhe SEM imag ges - low lyiing areas where filler cooncentrations foor epoxy microocomposites. In the case of
maaterial erosionn has taken placep and isllands where the microcoomposites, the number
n of fillerss will be less thaan that of the
maaterial is still intact.
i The fraaction of islannd regions on the nanocom mposites for thhe same filler concentration and so the
SEEM image caan give an indication of the amount of interpartticle distance will
w be larger inn this case. Thiis causes the
maaterial degraddation. These island regionns will act ass a dischargge to penetrate through
t a largeer bulk of the polymer.
p The
barrrier against thhe electron annd ion impact on the specim men surface SEM of epoxy micrococmposiites also shows the presence
andd resists furthher degradation. The EDAX X analysis on the of moree low lying areeas than islandds which indicaates a higher
nannocomposite sample
s surface before and after
a exposuree to degradattion of the bulkk material. Oncee the bulk epoxxy material is
disscharges is shoown in Figuree 7. It shows an a increase in the degradedd, the micropartticles get exposed to discharges. So there is
aluumina filler concentration
c and oxygen content on the a possibbility of field enhhancement at thhese particle extr tremes which
surrface of the saamples exposeed to dischargees. It can be seeen can leadd to enhanced discharges resuulting in an inccrease in the
froom Figure 6 thhat neat epoxy y sample is higghly degradedd as roughneess on the surfacce.

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 268 P. Preetha and M. J. Thomas: Partial Discharge Resistant Characteristics of Epoxy Nanocomposites

(a) Unexposed unfilled epoxy (b) Exposed unfilled epoxy (c) Exposed 0.1 wt% epoxy-alumina
nanocomposite

(d) Exposed 1 wt% epoxy alumina (e) Exposed 10 wt% epoxy alumina (f) Exposed 15 wt% epoxy alumina
nanocomposite nanocomposite nanocomposite

(g) Exposed 1 wt% epoxy alumina (h) Exposed 10 wt% epoxy alumina (i) Exposed 15 wt% epoxy alumina
microcomposite microcomposite microcomposite

Figure 6. SEM images of the discharge exposed regions of epoxy composites aged for 24 h at 10 kV.

Table 2. Average surface roughness of epoxy nano/microcomposites.

Average Surface Roughness Ra (nm)

Voltage
and time
duration Unfilled Epoxy-Al2O3 nanocomposite Epoxy-Al2O3 microcomposite
Epoxy
0.1 wt% 1 wt% 5 wt% 10 wt% 15 wt% 1 wt% 10 wt% 15 wt%

10 kV 484 330 322 327 315 201 421 656 982

5 hours
10 kV 621 534 518 354 429 357 650 798 1200
10 hours
10 kV 910 706 694 539 602 405 869 1024 1270
24 hours

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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 1; February 2011 269

The FTIR spectrum of alumina nanoparticles shows two

bands around 3400 cm-1 and 1630 cm-1. The band at 3400 cm-1
corresponds to the stretching vibration of hydroxyl (OH)
groups attached to the nanoparticle surface and the band at
1630 cm-1 corresponds to the bending vibrations of absorbed
Counts

Counts
H2O molecules [20]. The hydroxyl groups can be present as
free OH groups attached to the nanoparticle surface or as OH
groups attached to the absorbed water (H2O) molecules or
both. When these nanoparticles are introduced into the epoxy,
Binding energy( keV) Binding energy (keV) the chemical reaction between the nanoparticles and the epoxy
(a) Before discharge (b) After discharge if any, will introduce chemical changes in the bulk of the
nanocomposite leading to formation of new chemical bonds.
Figure 7. EDAX analysis of epoxy alumina nanocomposite (10 wt%)
But the FTIR spectrum of neat epoxy and epoxy alumina
nanocomposite does not indicate the presence of new chemical
3.3 FTIR SPECTROSCOPY MEASUREMENTS bonds. So the possible interaction between the epoxy and the
In order to understand the interactions happening at the nanoparticle is through the hydrogen bonding that can happen
interface between the nanofiller and the epoxy polymer, the between the –OH group on the fillers and the electrophilic
FTIR spectrum of alumina filler, neat epoxy and epoxy oxygen of the epoxide group [21]. The –OH group is highly
alumina nanocomposites were studied and are as shown in polar because of the large electronegativity difference between
Figure 8. oxygen and hydrogen. The oxygen atom has a partial negative
charge and the hydrogen atom has a partial positive charge.
The positively charged hydrogen on one –OH can weakly
interact with the negatively charged oxygen of a second –OH.
This interaction results in a weak chemical bond known as
hydrogen bonding. These hydrogen bonds do not indicate as a
new peak in the spectrum. So no difference is observed
between the spectrum of neat epoxy and epoxy
nanocomposites. But it has been reported by Smith [22] that
the number and strength of hydrogen bonds varies from place
to place in a collection of molecules depending upon the
chemical environment in which it is present. The number of
chemical environments in a sample contributes to the width of
the peak. Because of the large number of chemical
environments caused by hydrogen bonding, the infrared bands
are usually broad. The peak width, intensity and position of –
OH infrared bands are all affected by the extent of hydrogen
bonding in a sample. It is observed that the peak width and
(a) FTIR spectrum of alumina nanofiller intensity of –OH bands are increased with the addition of
nanofillers to epoxy and so this may be considered as an
indication of the increase of the hydrogen bonding in the
nanocomposite sample.
The FTIR spectrum of the specimens exposed to surface
discharges were taken around the periphery where the
degradation is maximum. The FTIR spectrum of the eroded
region just near to the high voltage rod electrode for neat
epoxy and epoxy nanocomposites aged for 24 h are as shown
in Figure 9. Table 3 gives the wavebands and their
assignments for unstressed and stressed epoxy/epoxy
nanocomposites. It is observed that there is a degradation of
the –OH groups and a sharp peak has formed in the region of
the –OH stretching bands in the case of unfilled epoxy. It has
also been reported by Smith [22] that, where little or no
hydrogen bonding takes place the –OH stretching band would
appear sharper, weaker and at a higher wave number. So this
may be considered as an indication of the degradation leading
(b) FTIR spectra of neat epoxy and epoxy alumina nanocomposite to the breakage of hydrogen bonds in the sample exposed to
(15 wt%) surface discharges. In the case of epoxy alumina
Figure 8. FTIR spectra of alumina filler, neat epoxy and epoxy alumina
nanocomposites, the degradation of –OH bands is not as
nanocomposite. intense as with neat epoxy. This may be due to the large

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 270 P. Preetha and M. J. Thomas: Partial Discharge Resistant Characteristics of Epoxy Nanocomposites

surface conductivity of epoxy when exposed to discharges

have been reported by Hudon et al [24]. This can also enhance
the degradation of the unfilled epoxy samples.

3.4 PD DISTRIBUTION STUDIES

When polymers are exposed to PD, their surfaces will suffer
physical damage by the impact of charged species on it. Also
the reactive oxygen species produced by the discharge will
oxidize the surface thus enhancing the degradation on the
surface. To have an understanding of the PD occurring on the
surface, the partial discharge distribution of the samples
exposed to surface discharge was acquired for a duration of
10 s at every one hour interval. The ij-q-n distribution of the
PD pulses for unfilled epoxy and 0.1 wt% epoxy alumina
nanocomposite obtained are as shown in Figure 10. There is a
reduction in the number and magnitude of pulses in both the

(a) Unfilled epoxy

Figure 9. FTIR spectrum of unfilled epoxy and epoxy alumina (b) Epoxy alumina nanocomposite (0.1 wt%)
nanocomposites aged for 24 hours. Voltage applied is 10 kV.
Figure 10. ij-q-n distribution of unfilled epoxy and epoxy alumina
nanocomposite aged for 20 hours with 10 kV applied voltage.
number of hydrogen bonds that are formed between the filler
and the polymer resulting in a tightly bound region around the
filler. So the energy required for the discharge to penetrate in
to the material is more once the discharge encounters the
tightly bound region in the nanocomposites. It has also been
reported by Stephanie et al [23] that the increased bond
energies in the interphase enhance the material resistance to
degradation.
The other important observations from the FTIR spectrum
of aged epoxy samples are the formation of the carboxyl
groups and peracids which can lead to a change in the surface
conductivity with discharge. The carboxyl bands are shown
merged with C-C stretching vibration in the case of aged Figure 11. Average discharge magnitude at different durations of exposure
epoxy nanocomposites. Similar observations of enhanced for unfilled epoxy and 0.1 wt% epoxy alumina nanocomposite

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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 1; February 2011 271

cycles for epoxy nanocomposites when compared with that of discharge extends over a substantial portion of the ac half
unfilled epoxy. It has also been observed that the number of cycle and visually appears as a diffuse glow. Also it is
pulses in the positive half cycle is very less in the case of reported that larger discharge pulses dominate when the time
epoxy nanocomposites when compared to that of unfilled of exposure is less than 200 h [25]. It has been observed that
epoxy. Figure 11 shows the average discharge magnitude for in the case of unfilled epoxy, the ij-q-n distribution shows
unfilled epoxy and 0.1 wt% epoxy alumina nanocomposite discharge pulses of larger magnitude and extending over
samples at various discharge durations. It is seen from the substantial portion of the ac half cycles. This may be an
figure that the average discharge magnitude which is indication of the presence of both pulse type and glow type
maximum at the start of the aging drops to a very low value discharges when unfilled epoxy is exposed to surface
and then increases with aging duration and then decreases. discharges for a duration of 20 h.
The decrease is more prominent in the case of nanocomposite The lesser number of PD pulses in the case of epoxy
for longer duration of discharge exposure. nanocomposite may be due to the reduction in the oxidation
The FTIR spectra of aged epoxy samples show the presence reactions happening on the surface due to the presence of
of -C=O of intra molecularly hydrogen bonded acids and - nanofillers and the polymer regions which are tightly bound to
CO-OOH bands of the peracids. This suggests an the nanofillers. The FTIR spectrum of epoxy nanocomposite
enhancement in the surface conductivity when unfilled epoxy shows overlapping of the carboxylic acid band with the C-C
is exposed to surface discharges. This change in the surface stretching vibration. So the surface conductivity of epoxy
conductivity may be due to the oxidation on the surface in the nanocomposites may be less when compared to unfilled epoxy
presence of reactive species in the atmospheric air formed by to induce a transition to glow type discharge. From the
the discharges. Hudon et al [24] has reported an increase in the average surface roughness measurements it was seen that the
surface conductivity for unfilled epoxy which modifies the Ra value was very much lower for nanocomposites at longer
electric field distribution and thereby inducing a transition of durations of discharge exposure. So in the case of
the spark type discharge to a glow type discharge. Spark nanocomposites, the reduction in the average PD magnitude
discharges are characterized by duration of the order of 10 to may be one of the reasons for the reduction in the average
100 ns, forming narrow luminous channels. The glow type of surface roughness.

Table 3. Infrared bands and assignments for unstressed and stressed epoxy nanocomposites.
Wave bands
Corresponding group assignments Unstressed Stressed for 24 h
(cm-1)
Moisture, acid and peracid indicated by
~3500 Hydroxyl Groups (–OH) Present
number of peaks
~3280 -CO-OOH peracids Not seen Present
~ 3043 &
C – H stretch in aromatic Present Depleted
3050
Methyl groups depleted, overlapping with
~2970 Asymmetrical C – H stretch of –CH3 group Present
–OH
~ 2930 Asymmetrical C–H stretch of –CH2 group Present Methylene groups depleted
~2875 Symmetrical C-H stretch of –CH2 Group Present Depleted
~1720 Carboxylic acid (C=O stretching vibration) Present Overlapping with other new bands
C=O in intra molecularly hydrogen bonded Not
~1659 Seen
acids present
~1605
~ 1580 Doublet of medium bands corresponding to
Seen
~ 1511 C–C stretching vibration in aromatics
~ 1460
~1347 N–O in nitrates and nitrites Not seen Strong Intensities
~ 1297 Asymmetrical – CH2 deformation Present
~ 1246 Asymmetrical aromatic C – O– C stretch Present
~ 1186 Asymmetrical aliphatic C – O stretch Present
~ 1032- Increase in number of bands implies new
Symmetrical aromatic C – O– C stretch Present
1100 bonds
~ 919 Epoxide ring vibrations Present
~ 828 – CH out of plane deformation in aromatic Present

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 2
272 P. Preettha and M. J. Thomas:
Th Partial Discharge
D Resisstant Characteriistics of Epoxy N
Nanocompositess

3.5. DSC ME EASUREMEN NTS Tg vaalues would have decreased beyondb 0.5 wt%% filler loadingg
Differential Sccanning Calorrimetry (DSC) experiments were w also which
w is not thhe case in the present
p results.
connducted to meeasure the glasss transition teemperature (Tg) of In the
t present studdy, at 0.1 wt% nano-filler conncentration, thee
diffferent epoxy alumina
a nanocomposites in order
o to undersstand inter--particle distannces in the nanocomposites
n s are large ass
thee interface pheenomena. The glass transitioon temperaturees of show wn in Table 2 and the larrge loosely boound extendedd
epooxy alumina nanocomposiite with resppect to the filler f polym mer nanolayer may lead to an increase inn the mobilityy
conncentration aree shown in Figu ure 12. resultting in a reduuction in the nanocomposite
n Tg. When thee
The Tg of unffilled epoxy is 73 oC. It caan be seen thaat in filler concentration increases to 0.55 wt%, the voluume fraction off
nannocomposites, Tg decreases up u to 0.5% filleer loading and then looseely bound polym mer chains alsoo increases resuulting in the Tg
shoows an increasse when the filller concentratiion is increaseed up valuees to decrease further.
f As the filler concentrration increasess
to 15 wt%. A similar
s variation was reportted in a studyy by further, the inter-paarticle distancees start to reduuce which cann
Sanntanu et al [9].. This variation
n could be expplained on the basis
b resultt in an overlapp of the mobilee polymer regions around thee
of the dual layeer model for the nanocompposites, a picttorial nanopparticles [23]. This will lead to an increasee in the volumee
reppresentation off which is showwn in Figure 133. of immmobile polym mer regions in thet nanocompoosite leading too
A per the duaal layer model when the nanoofiller particles are
As an inncrease in the glass transitionn temperature as observed inn
the present study at higher filler looadings.

3.6
6. PHYSICAL
L MODEL TO
O EXPLAIN TH
HE SURFACE
DEGRADATION
N MECHANISSM
The enhancement in the degrradation resistance can bee
explaained on the basis
b of the physical
p model as shown inn

0.1 wt% 1 wt%

Figure 12. Glass

G transition temperature of epoxy aluminaa
nanocomposites as a function of filler
f concentrationn.

5 wt% 10 wt%

Figgure 13. Dual layer model of the inteerface.

uniformly disperrsed in the epo oxy matrix, eaach of the partticles 15 wt%
will hold the epoxye materiaal around it. The first eppoxy
Fiigure 14. Physical model to explain thhe surface degradatiion mechanism.
nannolayer on thhe nanoparticle is tightly bound b due too the
hydrogen bondinng and it is hig ghly immobile. Then there iss the Figurre 14. Considering the dual layer model m of thee
looosely bound seecond layer wh hich contains polymer
p chainss that nanoccomposites, inn addition to thhe two epoxy regions at thee
aree loosely bounnd to the nanop particle. It has also been receently interfface which intteract with thee nanoparticless, a significantt
repported that therre is a significcant influence of
o humidity onn the volumme of loose epooxy is present in the nanocom mposite. This iss
Tg of nanocompoosites and the presence
p of a water
w nanolayeer on held together betweeen the nanoparrticles and do not
n interact withh
thee surface of thee nanoparticless can lead to a reduction in thhe Tg the nanoparticles.
n The volume of o this loose epoxy
e materiall
vallues [26]. Evven though there t are manny factors which
w depennds upon the filler concenntration. Whenn subjected too
inffluences the Tg, reports suggests that it is thhe interfacial layer
l electrrical dischargess, the epoxy regions which arre loose tend too
bettween the nannoparticle and the polymer thhat determiness the degraade faster than the material which
w is tightlyy bound to thee
glaass transition temperature of o the nanocoomposites [27-29]. nanopparticles. With a longer duratiion of dischargge exposure, thee
Also great care has
h been exercised while prepparing the sam mples degraadation begins tot expand eitheer along the deppth or the widthh
so that the influeence of humid dity is minimizzed. In additioon, if of thhe sample, whichever way thhere is least ressistance for thee
theere is a water nanolayer
n on the
t nanoparticlle surface, thenn the dischharge to propagate. Once the discharge encounters a

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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 18, No. 1; February 2011 273

nanoparticle, the progress is restricted and then the degradation Manufacturing and Coil Winding Conf., Cincinnati, OH , USA, pp.
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Epoxy alumina nanocomposites of various filler loadings have Nanocomposites”, IEEE Trans. Dielectr. Electr. Insul., Vol.15,
pp. 12-23, 2008.
improved resistance to surface discharge degradation. It was
[10] M. Kozako, N.Fuse, Y. Ohki, T.Okamoto, T.Tanaka, “Surface
observed that even at low filler concentration, epoxy Degradation of Polyamide Nanocomposites Caused by Partial
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epoxy. This may be due to the difference in the surface Mechanisms of Superior Resistance of Polyamide
conductivity of epoxy and epoxy nanocomposites when exposed Nanocomposites to Partial Discharges and Plasmas”, IEEE
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[16] D.M. Hepburn, I.J. Kemp, R.T. Richardson, “Partial Discharge
ACKNOWLEDGMENT Stressing of Filled Epoxy Resin Surfaces”, 7th Intern. Conf.
The authors would like to thank IRIS, IPC department, IISc Dielectric Materials, Measurements & Applications, University
Bangalore for the help in conducting the FTIR studies, Nanoscience of Bath, UK, pp. 330-333,1996.
centre, IISc for the support in conducting the SEM studies and the [17] T. Tanaka, M. Kozako, N. Fuse and Y. Ohki, “Proposal of a
Multi-core Model for Polymer Nanocomposite Dielectrics”,
Nanotribology laboratory, Dept. of Mechanical Engineering for IEEE Trans. Dielectr. Electr. Insul., Vol.12, pp. 669-681, 2005.
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 2
274 P. Preettha and M. J. Thomas:
Th Partial Discharge
D Resisstant Characteriistics of Epoxy N
Nanocompositess

[222] B. Smith. Inffrared Spectral Interpretation

I A Systematic
S Appr oach, P. Preetha was born in Kerala, India
I in 1973. Shee
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[244] C. Hudon, R. R Bartnikas and d M.R. Wertheim mer, “Spark to Glow Bangalore, Indiaa in 2003. Presenttly she is doing herr
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1993. areas of interestt are Aging and discharge
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[266] C. Zou, J. C. Fothergill
F and S. W. Rowe, “A Water
W Shell Modeel for M. Joy Thomass (S’85-M’95) waas born in Keralaa,
the India in 1961. HeH received the B.Tech.
B degree inn
Dielectric Pr operties of Hy ydrated Silica-ffilled Epoxy Nano-
N electrical enginneering from the t Institute off
composites”, IEEE
I onf. Solid Dielecctr. (ICSD), pp. 389-
Intern. Co Technology, BH HU, Varanasi, India,
I the M.Scc.
392, 2007. (Engg.) and thee Ph.D. degrees from the Indiann
[277] G. Tsagaropooulos and A. Eissenberg, “Dynam mic Mechanical Study
S Institute of Sciennce, Bangalore, Inndia. Presently, hee
of the Factor s Affecting the Two Glass Tr ansition Behavioor of is working as an Assistant Professor at thee
Filled Polym mers. Similaritiees and Differeences with Ranndom Department off Electrical Enggineering, Indiann
Ionomers”, Maacromolecules, Vol.
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pp. 651-652, 2005.
2 are EHHV/UHV power trransmission, high voltage engineering, dielectrics andd
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Polymer Melt and the Relation nship to Ultrathiin Films”, Phys. Rev. engineeering, plasma science and tecchnology, EMC and engineeringg
E, Vol. 64, pp . 021802 (1) –02 1802 (5), 2001. pedagogy.

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