Proceedings of the XIVth International Symposium on High Voltage Engineering,

Tsinghua University, Beijing, China, August 25-29, 2005

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Erosion Behaviour of Nano Filled Silicone Elastomers

Stephanie Rätzke*, Josef Kindersberger

Lehrstuhl für Hochspannungs- und Anlagentechnik der Technischen Universität München, Deutschland;
*E-mail: stephanie.raetzke@tum.de

Abstract: The effect of nano sized particles compared
to micro sized particles is explained by the high surface
to volume ratio. The influence of different types and
concentrations of nano and micro sized fillers on the
erosion resistance, the thermal conductivity and the
dielectric properties of an unfilled silicone elastomer is
investigated. The dispersion of the filler particles in the
matrix material seems to play a decisive role.
Key Words: Nanodielectrics, nanometric fillers,
advanced insulation materials, erosion behaviour
Fraction of interfacial layers
To illustrate the highly increased fraction of interfacial
layers, one has to dwell on the consequences of the
smaller particle size. On the one hand a spherical
particle with a diameter of 1 µm has approximately the
same volume as one billon particles with a diameter of
1 nm (Fig. 1).

INTRODUCTION

In polymeric materials for outdoor insulation fillers are 1 nm

used for various reasons, e.g. to improve the mechanical
stiffness, the resistance to arcing, resistance to tracking
1 µm
and erosion, etc. The contact area between filler and
matrix material is called interfacial layer. The size of Fig. 1 Illustration of dielectrics with µ- and n-fillers
typical conventional filler particles is 1 - 150 µm. These
filler materials shall further be called µ-filler. One can see from this example that as a result of the
The potentials of new nano structured materials, in smaller particle size the absolute number of particles is
which the properties of the interface layers dominate the highly increased at the same volume fraction.
volume effect, which today is called interface effect, Furthermore, with decreasing particle diameter the
were already indicated in 1992 [1]. fraction of surface atoms is increased. In particles with a
It was illustrated in 2001 that the interface effect can be diameter of 20 nm already 10 % of the atoms in the
used for tailored materials [2], for instance by using particle are surface atoms (Table 1). At a particle size of
nanometric fillers. Nanometric fillers are defined as 1 nm nearly all atoms are located at the particle surface.
particles with a size between 1 – 100 nm. In this paper Therefore, nano particles have a highly increased
they are called n-fillers or nano particles and the fraction of surface atoms.
materials consisting of n-fillers in a dielectric medium
are called nanodielectrics. Particle Number of Fraction of
Several publications point out in past years the potential diameter atoms in a surface atoms in a
of n-fillers [3, 4, 5]. It is remarkable, that the published [nm] particle particle [%]
improvements already occur at a filler loading of 1 – 10 20 250 000 10
wt. %. By using conventional fillers usually a large 10 30 000 20
amount of filler material (55 – 65 wt. %) is necessary to 5 4 000 40
achieve the required properties [9]. 2 250 80
The present work investigates the influence on the 1 30 99
resistance to HV-arcing (according to IEC 61621) by
using n-fillers and µ-fillers in a silicone elastomer. Table 1 Relation of particle diameters to contained
Furthermore the dielectric properties were measured. atoms as well as to the fraction of surface atoms

FUNDAMENTALS OF THE NANO EFFECT
In materials with µ-fillers the volume effect is
dominating, i.e. due to the high volume fraction the
filler material contributes to the properties of the whole
material. Contrary to that the properties in
nanodielectrics are affected by the interfacial layer
between the filler and the matrix material. The reason
for that is the highly increased fraction of interfacial
layers in the material.
Thus, for a constant filler fraction in the material it is
found that with decreasing particle size
- the absolute number of atoms in the particle is
highly increasing and
- a larger fraction of the atoms in the filler particle
belong to the interfacial layer.
As a result the fraction of the interfacial layers is
increased enormously.

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Proceedings of the XIVth International Symposium on High Voltage Engineering,
Tsinghua University, Beijing, China, August 25-29, 2005
Physical Fundamentals of the Nano Effect
The binding structures in interfacial layers are very
different in comparison with the filler or matrix
material. Beside the classic physical effects quantum
physical effects are also possible. The interfacial layers
present a range between macroscopic and quantum
mechanical properties. This is evident if one compares
the size of a nano particle (1 – 100 nm) with the radius
of an aluminium atom (0.25 nm) or the single bond
length between two carbon atoms (0,154 nm) [2].
In a homogenous material, like the matrix material or
interior of a particle, the atomic constitution is also
homogenous. That means every atom is surrounded only
by atoms of the same type and therefore the interactions
are equal for all directions. But, atoms of the interfacial
layer interact with atoms of the matrix material and the
filler material likewise. This means that the forces
acting to the atoms of the interfacial layer are different
from those in a homogeneous material.
The interfacial layer can have a thickness of only 1 nm
if only strong interaction is acting or can be more than
10 nm thick if charge carriers are situated in the
interfacial layer [7, 15].
The effects in the interfacial layer may be explained by
a model [7]. The interfacial layer between two different
materials defines also a transition of an intensity of a
special property (for example concentration or energy)
in material A (IA) to another in material B (IB).
There must be a continuous transition between the two
intensities at the border (Fig. 2). This transition can have
different slopes (a) or even a maximum (b) is possible,
which is higher than the intensities of both materials IA
and IB [6, 7].
I MATERIALS
(b)
IB
(a)
IA
material A material B
Fig. 2 Transition of an intensity I of a property in
material A to material B with a continuous slope (a) or a
maximum (b)
An example for (a) is the electron-hole concentration in
a p-n-junction of a diode. For instance the characteristic
of (b) represents the potential barrier at the tip of the
electrode of a scanning electron microscope. It will be
tunnelled by electrons, which are needed to determine
the distance to the sample.
It is assumed, that a particle of material B is dispersed in
the matrix material A. If the particle diameter is small
enough no constant value IB is reached. The intensity of
the property is a value on the curve. If the fraction of the
2
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interfacial layers is large enough, the properties of the
whole material are neither the properties of the matrix
material A nor the properties of the particle B (Fig. 3).
I
IB d is reduced
IA
material A particle B material A
Fig. 3 Intensity I depending on the particle diameter d
(according to [7])
These changes are not limited only to the macroscopic
properties: The higher intensity in the area of the
particle B can for instance be a barrier for an electron
(in the tunnel effect), for a photon or a phonon. If
always just the energy quantity of an electron, photon or
phonon can be transported across the energy barrier, the
electrical conductivity, the light or the thermal
conductivity becomes quantised.
An example for this effect is the fluorescence behaviour
of CdTe nano particles. Dilutions with nano particles in
a range from 2 – 5 nm change their fluorescence with
increasing particle diameter from green to red [12].
Another example is the quantisation of the thermal
conductivity, which was detected by Schwab 2000 [13].
EROSION BEHAVIOR OF POLYMERIC
Degradations of insulations for outdoor application are
basically caused by high energy stresses. The most
important stresses are:
- Pollution initiated discharges,
- Arcs and
- UV-radiation.
Usually the stresses of the pollution initiated discharges
and arcs are dominating for polymeric materials for
outdoor insulation. They can lead to tracking and
erosion. Tracking can be presumed as a special form of
erosion. It is characterized by a continuous conductive
path, which is caused by local erosion on the surface of
the material [14].
The resistance to erosion and arcing of materials for
high voltage outdoor insulation is evaluated by two
standardized tests, the IEC 60587 and IEC 61621 [14,
21]. Within a material family a high resistance to
tracking and erosion usually corresponds to a long
duration of the arcing test [11]. Therefore the
considerably faster arcing test according to IEC 61621
suffices for exploratory analysis in terms of a screening.
Proceedings of the XIVth International Symposium on High Voltage Engineering,
Tsinghua University, Beijing, China, August 25-29, 2005
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There are different studies on the impact of the particle

size of silica in RTV silicone elastomers. Particle sizes
of 1.5 – 12 µm were investigated at filler loadings of
10 -50 % wt. The studies show a better resistance to
erosion and a higher thermal conductivity by using
smaller particles at the same filler fraction [8, 19]. It has
to be studied if this behaviour continues at nanometric
scale.

EXPERIMENTAL RESULTS

Investigated materials
Fig. 4 TEM picture of the matrix material with 4 wt. %
Unfilled HTV silicone rubber with a filler content of n-SiO2, 10 000-times magnified
(2), 4, 10, and 40 wt. % was investigated. Table 2 shows
medium primary particle diameter of the used filler
materials. Furthermore, samples without filler material
were investigated.
Primary particles are mostly spherical clusters of
amorphous filler material. The primary particles can not
be split up (sheared) at the dispersion process.
Aggregates are formed by chemical bonds between the
primary particles. Several aggregates can form
agglomerates by weaker surface forces. They are
sensible to shear at the dispersion process.

Filler Medium diameter of

primary particle Fig. 5 TEM picture of the matrix material with 4 wt. %
n-SiO2 7 nm µ-SiO2, 10 000-times magnified
µ-SiO2 212 nm
n-Al2O3 13 nm
µ-Al2O3 4100 nm
Table 2 medium diameter of primary particles of the
used filler materials

Fig. 4 to Fig. 7 show the TEM (Transmission Electron

Microscope) pictures of the investigated materials. All
samples were manufactured in the same way. To avoid
agglomeration strong shear forces were applied at the
dispersing process. As it can be seen from the TEM
pictures the agglomeration could not be avoided
completely, anyway.
The best dispersion was achieved with n-SiO2 (Fig. 4). Fig. 6 TEM picture of the matrix material with 4 wt. %
The filler particles are equally dispersed and partly form n-Al2O3, 10 000-times magnified
aggregates or agglomerates. Nevertheless the particles
mostly have a size of 10 – 50 nm, which are nano
particles by definition.
It can be seen in Fig. 6 that n-Al2O3 tend to form large
agglomerates, which are not nano particles. The particle
dispersion is well in some parts but not satisfying in
general. Due to their not sufficing dispersion the
particles and agglomerates are not interspersing the
matrix material contrary to the n-SiO2. Because of this it
is to be expected that the n-Al2O3 behave generally as µ-
particles.
Both types of µ-particles are obviously larger and do not
form aggregates or agglomerates (Fig. 5 and Fig. 7).
They have a medium diameter of approximately 250 nm Fig. 7 TEM pictures of the matrix material with 4 wt. %
and 4 µm, respectively. µ-Al2O3 8000-times magnified

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Proceedings of the XIVth International Symposium on High Voltage Engineering,
Tsinghua University, Beijing, China, August 25-29, 2005
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In general it is more difficult to achieve a good 0,23

dispersion of n-fillers than of µ-fillers because of their n-SiO2

thermal conductivity [W/mK]

0,22
high specific surface and their resulting affinity to form µ-SiO2
aggregates or agglomerates. Furthermore it is important 0,21 n-Al2O3
µ-Al2O3
to consider the combination of filler and matrix 0,20
material. If the binding structure of the filler material is
0,19
similar to the one of the material, the tendency to form
aggregates is less pronounced. It is assumed, that the 0,18

dispersion behaviour of the filler types is similar at 0,17

higher filler concentrations. Unfortunately the contrast
0,16
of the TEM pictures at higher filler concentrations is 0 5 10 15 20 25 30 35 40
insufficient.
filler concentration [wt. %]
Resistance to HV-Arcing
Fig. 9 Thermal conductivity of investigated materials
The resistance to arcing was tested according to IEC
61621. The size of the samples was 15x30x6 mm. For Dielectric Properties
each material a test series was made consisting of 12
measurements. Fig. 8 shows the mean values of the test The dielectric loss factor and the relative permittivity of
duration (arcing time) and the associated minimum and the investigated materials were measured at 3 kV and
maximum values in dependence on filler type and filler plotted in Fig. 10 and Fig. 11. For both SiO2-fillers and
concentration. The results show increasing test durations the n-Al2O3 filler there is no significant difference for
with increasing filler concentrations. The graph for both the loss factor at 10 and 40 wt %. The value of 10 wt %
µ-fillers and for the n-Al2O3 exhibit no significant µ-Al2O3 is smaller than the value of 40 wt %. The loss
differences. But the test duration of the n-SiO2 is factors of the SiO2-fillers are smaller than for the Al2O3-
significantly higher at 40 % wt. fillers.
There is a remarkably peak for three of the filler types at
a filler concentration of 4 wt %. Only the value of n-
300
n-SiO2
Al2O3 is smaller for 4 wt % than for 10 wt %.
250 µ-SiO2
14
n-Al2O3
test duration [s]

200
µ-Al2O3 n-SiO2
loss factor [10^-3] at 3 kV

12
µ-SiO2
150
10 n-Al2O3
100 µ-Al2O3
8

50
6

0
4
0 5 10 15 20 25 30 35 40
filler concentration [wt. %] 2

Fig. 8 Duration of the arcing according to IEC 61621 0

for different filler materials and filler concentrations 0 5 10 15 20 25 30 35 40

filler concentration [wt. %]

Thermal conductivity
To investigate the influence of the thermal conductivity
on the resistance to arcing, measurements of the thermal
conductivity were undertaken. Fig. 9 shows the thermal
conductivities of the investigated materials.
The values for all filler materials rise approximately
linear to the filler concentration. There is no significant
difference between the four filler materials.
Fig. 10 loss factor of the investigated materials
A similar but slighter peak is found for the relative
permittivity (Fig. 11) of n-SiO2 and µ-Al2O3. In general
the relative permittivity is raising slightly with higher
filler concentrations. All values lies between 2.8 and
3.2.

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Proceedings of the XIVth International Symposium on High Voltage Engineering,
Tsinghua University, Beijing, China, August 25-29, 2005
3,6
relative permittivity at 3 kV
3,4
3,2
3,0
2,8
2,6
0 5 10
filler concentration [w t. %]
Fig. 11 relative permittivity of the investigated materials
DISCUSSION
The erosion behaviour of filled silicone elastomers was
investigated with the HV arcing test according to
IEC 61621. The test durations increase approximately
linear with increasing filler content. This is in good
correlation with the thermal conductivity, which is
supposed to improve the resistance to erosion. An
influence of the particle size at lower filler
concentrations becomes not apparent. The graphs for
both Al2O3 fillers and the µ-SiO2 show also no
significant difference at higher filler concentrations.
Only the test duration of the n-SiO2 is remarkably
higher at 40 wt %.
This result is plausible considering the filler dispersion.
Only the particles of the n-SiO2 exist as nano particles
in the matrix material. The n-Al2O3 act as a µ-filler
because of its large aggregates. Therefore its behaviour
is similar to both µ-fillers.
Another fact to discuss is that the enhanced resistance to
arcing by using n-SiO2 is achieved only at high filler
concentrations. The published improvements of material
properties mostly deal with mechanical properties like
surface degradation caused by partial discharges and
they already occur at low filler concentrations (1 - 10
% wt). In this case the strong interfacial bonding and
small inter-filler spaces of the nanodielectrics are
supposed to constrain the material degradation. This is
relevant, if the upper layer of the matrix material is
degraded and the particles are now situated at the
surface [22].
The erosion of a material is caused by thermal
decomposition. It is supposed, that the stronger
interfacial bondings can mitigate the pyrolysis of the
polymer chains. This is relevant if the dielectric consists
mostly of interfacial layers. To achieve this a higher
filler concentration is necessary.
The n-SiO2 filler has also the lowest loss factor and the
lowest relative permittivity at 40 wt %. The values of
the corresponding µ-type are higher. This is in good
correlation with already published results where it is
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suggested that the nano particles restrict chain
n-SiO2 movement [3].
µ-SiO2 The behaviour can not be confirmed for the Al2O3
n-Al2O3 fillers. The reason is probably the unsatisfactory
µ-Al2O3 dispersion of the n-Al2O3. Here the agglomerates have a
similar size as conventional µ-particles.
An explanation for the peak of the SiO2-fillers at 4 wt %
can not be given at the moment.
CONCLUSION
- The interface effect is based on the high fraction of
15 20 25 30 35 40 interfacial layers in the dielectric. The fraction of
interfacial layers becomes dominant by using n-
fillers.
- Theoretically the properties of the interfacial layer
do neither match the properties of the matrix
material nor the properties of the filler. If the
fraction of interfacial layers is high enough, the
properties of the whole dielectric are changing.
- A good dispersion of the filler in the matrix material
is decisive for the fillers to make an impact, in
particular for n-fillers. Only if the whole matrix
material is interspersed with filler particles, one can
expect a change of the properties of the n-filled
dielectric contrary to the µ-filled dielectric.
- The necessary dispersion was only achieved with the
n-SiO2 filler, which improves the resistance to arcing
significantly at higher filler contents contrary to the
corresponding µ-filler. Also the loss factor and the
relative permittivity are decreasing slightly.
- n-Al2O3 acts as a µ-filler because of its large
aggregates. That is the reason why there is no
remarkable effect on the resistance to arcing or the
dielectric properties by using n-Al2O3 instead µ-
Al2O3.
ACKNOWLEDGEMENT
The authors thank to Dr. H.-J. Winter for his
cooperation in manufacturing samples and for valuable
discussions.
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Proceedings of the XIVth International Symposium on High Voltage Engineering,
Tsinghua University, Beijing, China, August 25-29, 2005
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