2010 Annual Report Conference on Electrical Insulation and Dielectric Phenomena
Hydrothermal aging of XLPE/silica nanocomposites
L. Hui, J.K. Nelson and L.S. Schadler
Rensselaer Polytechnic Institute
110 Eighth Street
Troy, NY 12180-3590, USA
Abstract- This paper examines the hydrothermal aging of
XLPE/silica nanocomposites. Nanocomposites are exposed to
humid environment with a relative humidity of 100 % at 50 oC
and the changes in moisture diffusion and electrical strength are
investigated. In addition to moisture decreasing the electrical
performance of nanocomposites somewhat, there is evidence that
moisture can permanently damage the nanocomposites.
I. INTRODUCTION
Nanocomposites have been widely studied to determine their
ability to improve the electrical and mechanical performance
of polymers [1,2]. For XLPE/silica nanocomposites, which are
a class of composite material with a promising future for
power cable insulation, outstanding increases in breakdown
strength, voltage endurance and water treeing performance
have been reported [3-5]. However, due to the presence of a
large amount of moisture in the XLPE/silica nanocomposites
when exposed to humid environment, the electrical
performance can be greatly reduced [6]. Moisture molecules
are believed to exist around the surface of nanoparticles [7]. In
epoxy/silica nanocomposites, percolation has been observed in
wet samples [8]. Meanwhile, it is widely documented that the
saturated moisture content is dependent on the particulate
loading. This confirms the hypothesis that moisture molecules
reside around particles [7,8]. The achievement of water
percolation at particle loading below particle percolation
suggests that water also resides in the interfacial regions. The
presence of water has been found to debond the filler and the
polymer chains likely because the particle surfaces are
hydrophilic [9]. Micro composites have been investigated for
this damage [10]. However, interfacial damage in
nanocomposites has rarely been investigated. Therefore, this
paper is aimed at understanding the damage due to moisture
absorption and desorption in nanocomposites.
II. EXPERIMENTAL
A. Sample preparation
LDPE and nano silica with a nominal particle radius of 12 nm
were melt mixed using a Haake thermal mixer at 165 oC for 20
minutes. Melted dicumyl peroxide (DCP) was added at the
end of the mixing procedure. Samples of appropriate
geometry were press molded at 165 oC for 15 min and cooled
in the mold for 30 min. Planar samples with a thickness of 1.5
mm were used for moisture diffusion tests. Planar samples
with a thickness of 0.1 mm were prepared for dielectric
spectroscopy, and multi-recess samples were prepared
similarly for AC breakdown tests.
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B. Hydrothermal aging conditioning
De-ionized water was used to achieve the 100% rh condition.
Samples were immersed in de-ionized water with a sealed cap,
and then heated up to 50 oC for various times.
C. Moisture uptake measurement
Planar samples were used to study moisture diffusion in
nanocomposite materials. The first group was immersed in
water for 1 year and vacuum dried for 2 days at 80oC. Then
this group was immersed in water again to see if there was any
increase of moisture uptake. The second group was immersed
in water for 1 week and vacuum dried similarly, then
immersed in water, again. The increase in weight was
determined using a digital balance (Mettler Toledo XS105)
with an accuracy of 0.1 mg. The weighing of the samples was
completed as soon as possible to avoid any impact of the
laboratory environment on the water uptake.
D. Determination of water status
The status of the water was analyzed using Differential
Scanning Calorimetry (DSC) [11]. Modulated DSC (MDSC)
was adopted to take advantage of its capability to track weak
signals. Samples immersed in deionized water at 50oC were
measured by MDSC. A ramp rate of 5 oC/min was used and
the tests were run from 40oC to -80oC.
E. Electrical characterization
Samples, after being fully saturated in water at elevated
temperature, were vacuum dried for 48 hours to remove
residual moisture molecules. Multi-recess samples were
conditioned in hot water for over 1 month with 2 immersion-
dry cycles. Planar dielectric spectroscopy samples were in hot
water for over 3 months and dried once. After drying,
dielectric spectroscopy samples were sputter coated with
Pt/Au alloy on both sides to create intimate contact.
III. RESULTS AND DISCUSSION
A. 2nd moisture uptake
Fig.1 shows the moisture uptake profile when 12.5wt%
samples with untreated filler (12.5wt% UN nano) and vinyl-
silane treated filler (12.wt% VS nano) were exposed to a
temperature of 50 oC and 100% rh. One set of samples
(12.5wt% UN nano and VS nano) were exposed to a humid
environment for 1 year. Another set of samples were exposed
to the same humid environment for two weeks (12.5wt% UN
nano – 1st short, 12.5wt% VS nano – 1st short) and the 2nd
moisture uptake after driving the moisture out (12.5wt% UN
 nano -2nd short, 12.5wt% VS nano – 2nd short) was tested. improvement of nanocomposites with surface treatment is
The 2nd moisture uptake profile after 1 year of aging and only effective for a comparatively short time. For long time
vacuum drying (12.5wt% UN and VS nano 2nd long) was also aging, surface treatment can be ineffective. Fig.2 illustrates the
tested. 2nd moisture uptake for 5wt% nanocomposites with vinyl
1.60 silane treated fillers. The acceleration of diffusion and
1.40 increased moisture content can be observed.
1.20
Weight Gain (wt%)

1.00
B. Status of water
Water is usually divided into bound water and free water. Free
0.80
water has properties similar bulk water. Bound water can
0.60
further be divided into freezing bound water and non-freezing
0.40 bound water. Water that is well dispersed in the polymer will
0.20 not freeze, whereas water phase separated from the polymer
0.00
can freeze. From DSC tests, these two kinds of water can be
0.00 1,000.00 2,000.00 3,000.00 4,000.00 5,000.00 6,000.00 7,000.00 clearly distinguished by different locations of the peaks. Free
sqrt(t)/thickness water has the same peaks as those found in bulk water.
12.5 wt% UN nano 12.5 wt% VS nano Freezing bound water still show crystallization and melting
12.5 wt% UN nano -1st short 12.5 wt% VS nano -1st short peaks similar to pure water but the locations of these peaks are
12.5 wt% UN nano - 2nd short 12.5 wt% VS nano - 2nd short
different. Freezing bound water freezes at a much lower
12.5 wt% UN nano -2nd long 12.5 wt% VS nano - 2nd long
temperature and melts at lower temperatures [11,12]. The
anomalous behavior of water in polymer materials can be
Fig.1 Moisture uptake of 12.5 wt% nanocomposites at 100% rh 50oC attributed to the effect of capillary condensation, the
confinement of water clusters by polymer chains, or the strong
It can be observed that for 12.5wt% nanocomposites after both
interactions of the water molecules with polar groups [12].
short exposure and long exposure, the moisture uptake
Bound water that is well dispersed (non-freezing) will not
increased and diffusion was accelerated. It has been
contribute to the DSC signal.
documented that, for micro composite materials, damage can
happen in the interface between fillers and polymer matrix,
From MDSC measurement, the amount of freezing water can
which results in increased moisture diffusion and absorption
be calculated [11]. Fig.3 shows the original measurement
for a 2nd exposure cycle [10]. For nanocomposites, dielectric
results from MDSC. The peaks indicate the crystallization of
spectroscopy has suggested that conventional Maxwell-
water. Instead of having a peak close to 0oC , the freezing
Wagner-Sillars (MWS) interfacial polarization (which has
temperature for bulk water, the delayed peaks indicate the
been largely associated with micro composite systems) was
water in nanocomposites is bound water.
not observed in nanocomposites suggesting a more compatible
interfacial region. However, Fig.1 suggests that interfacial
damage can still occur.
0.50

0.40
Weight Gain (wt%)

0.30

0.20

0.10

0.00
0.00 1,000.00 2,000.00 3,000.00 4,000.00 5,000.00 6,000.00
Sqrt(t)/Thickness

5 wt% VS nano 5 wt% VS nano -2nd long

5 wt% VS nano -1st short 5 wt% VS nano - 2nd short
Fig.3 Crystallization of water in XLPE, 5wt% and 12.5wt% nanocomposites
Fig.2 Moisture uptake of 5 wt% nanocomposites at 100%rh 50oC detected by MDSC

For samples aged for 1 year, the 2nd moisture uptake profiles
of nanocomposites with and without surface treatment behave
similarly. However, for a short term aged sample, surface
treatment can restrict the moisture uptake compared to the
nanocomposites with untreated fillers. This suggests the
Since the total amount of water is known, the non-freezing
water can be obtained by subtracting the two values. Fig.4
illustrates the buildup of the moisture versus time.

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 1.4
250

1.2

Breakdown Strength (kV/mm)

200
1.0
water content wt%

0.8 150

0.6 100

0.4
T50-unfreezing 50
0.2 T50 - freezing
T50 total
0
0.0
0 1000 2000 3000 4000 5000 6000 7000

no

no

no
no
LP

na
na

na

na
X

N
S
sqrt(s)/l

V
U

U
t%

t%

t%
t%
w

w
w

w
5

.5
5

.5
12

Fig.4 Dynamic analysis of water status of 12.5 wt% VS nanocomposite
From Fig.4 it can be noticed that the non-freezing bound water
builds up quickly at the initial region of the moisture diffusion.
The freezing bound water increases linearly versus time. The
non-freezing bound water could be hydrogen bonded to
hydroxyl groups at the surface of silica or dispersed within the
polymer. As water molecules build up layer by layer, they
reach a critical size and become freezable. However, because
the crystallization temperature is much lower than that of bulk
water, it suggests that the water is confined. However, the
presence of polymer chains or bonding between these chains
to the silica surface can hinder the water molecules from
forming bulk-like structure.
From the perspective of aging, the build-up of more and more
bound freezing water indicates the loose structure of the
interfacial region, and also there can be swelling of the
interfacial region due to the presence of thick water layers that
can contribute to the damage.
C. Reduction of AC breakdown strength
In order to evaluate the influence of the damage due to
hydrothermal aging, AC breakdown tests were performed on
materials with different moisture contents. In addition,
samples aged in a humid environment and elevated
temperature were vacuum dried and then AC tested with a
ramp rate of 0.5 kV/s. Comparing fresh samples with redried
moisture laden samples, there was no damage to XLPE (base
resin) after hydrothermal aging. For nanocomposites, a lighter
loading of 5wt% nanocomposites were still able to maintain
higher breakdown strength compared to 12.5wt%
nanocomposites. However, the decrease of breakdown
strength at the higher loadings suggests the presence of
damage to the material system.
12
Materials
Dry 75% rh aged 100% rh aged 100% rh aged - vacumm dried
Fig.5 AC breakdown strength of XLPE and nanocomposites with 5wt% and
12.5wt% nano silica
D. Dielectric spectroscopy results indicating the change in
the interfacial region
Dielectric spectroscopy was employed to provide some
understanding of the damage after hydrothermal aging. Fig. 6
shows a comparison of the real and imaginary permittivities
between fresh 12.5wt% UN nanocomposites and the 12.5wt%
UN sample after 6 month aging (vacuum dried afterwards).
Similarly, Fig.7 compares the permittivities between fresh
12.5wt% VS nanocomposites and that of the sample after 6
months of aging. It can be observed that the aged samples
have more significant interfacial polarization, indicating
damage to the interfacial region.
E. Discussion of the aging mechanism
The analysis of absorption and desorption of water in
XLPE/silica nanocomposites indicates that permanent damage
exists for nanocomposites. A detailed analysis of the status of
water in nanocomposites indicates that water in
nanocomposites is mainly bound water. Both the surface
hydroxyl groups as well as adjacent imperfections act as sites
for the attachment of water molecules. The build-up of large
amounts of free water has a more serious influence on the
damage of nanocomposites likely attributable to swelling of
the interfacial region.
As a result, the 60 Hz AC breakdown strength is reduced in
nanocomposites. However there is no influence in unfilled
XLPE. For 5wt% nanocomposites, the damage is less severe
than that of 12.5wt% nanocomposites. Interfacial damage was
also confirmed by dielectric spectroscopy which showed
increased interfacial polarization after the absorption and
desorption cycle.

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 1.0E+01
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IV. CONCLUSION
After an absorption and desorption cycle, the diffusion and
absorption of water molecules were found to be increased
indicating permanent damage in XLPE/silica nanocomposites.
A detailed analysis of the status of water in nanocomposites
indicates the existence of large amounts of non-freezable
bound water and the freezable bound water (increasing versus
time). Vinyl silane treatment decreased the damage degree
when materials exposed to humid environment for a short time.
However there is no significant improvement after long time
immersion.

AC breakdown strength was found to be decreased in re-dried

samples suggesting the permanent damage can influence the
electrical strength of the materials. Dielectric spectroscopy
results indicated the increased interfacial polarization exists
after aging.

ACKNOWLEDGMENT

This work is a continuation of research started under the

auspices of EPRI to whom the authors are indebted.

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