2nd International Conference on Electrical Materials and Power Equipment - Guangzhou - China

Effect of Silica Modification on Charge Trapping

Behavior of PP blend/Silica Nanocomposites
Amirhossein Mahtabani1, Xiaozhen He1, Ilkka Rytöluoto2, Kari Lahti2, Mika Paajanen3, Eetta Saarimäki3
Rafał Anyszka1, Wilma Dierkes1, Anke Blume1
1
University of Twente, Faculty of Engineering Technology, Department of Mechanics of Solids, Surfaces & Systems (MS3),
Chair of Elastomer Technology and Engineering, Enschede, The Netherlands
2
Tampere University of Technology, Laboratory of Electrical Energy Engineering, Tampere, Finland
3
VTT Technical Research Centre of Finland Ltd, Tampere, Finland

Abstract- Various dielectric nanocomposite materials are containing filler particles of size lower than 100 nm in one
studied in the frame of the European Commission funded project dimension, may exhibit significant improvements in e.g.
GRIDABLE. This project has the aim to develop DC cable dielectric strength and voltage endurance [4]. These
extruded insulation and medium and low voltage DC capacitor improvements can be addressed to various phenomena, which
films exhibiting enhanced performance with respect to presently
mainly stem from the high interfacial area implemented by
used materials. The nanocomposites intended for cable
applications are based on polypropylene (PP) blends filled with nanofillers incorporated to a polymer matrix [5] as well as the
surface modified nano-silica particles. The surface modification is alteration of the features of the polymer/filler interphase [4].
carried out via the state-of-the-art solution method using a polar Upon changes of the type and surface characteristics of the
silane as the modifying agent. Thermally Stimulated filler, the polymer/filler interphase region can influence
Depolarization Current (TSDC) measurements were carried out crystallinity [6], molecular mobility [7] and entanglement
in order to study the charge trapping behavior of the density [8]. These changes in the nanoparticles’ surface
nanocomposite samples. TSDC results indicate that the addition of properties can contribute to further improvements of the
the treated nano-silica, for most cases, reduces the density of the dielectric properties of the nanocomposites filled with them.
deep traps significantly. While more detailed studies are
Changing the surface properties of the nanoparticles is possible
necessary, these results imply that the depth and the density of the
deep trap states is profoundly influenced by the level of the silica through surface modification that is substituting the existing
modification i.e. the amount of the grafted silane on the silica chemical structure on the particles’ surface with a certain
surface. functionality tailored for a specific application.
Surface modification of nanofillers may enhance the
Keywords: Silica surface modification, PP blend/Silica dielectric dielectric properties of the nanocomposites by improving their
nanocomposites, Charge trapping properties, TSDC, High voltage dispersion in a polymer matrix. Since the nanofiller particles act
cable insulation as electrical defect centers in polymers [9], they can distort and
enhance the local electric field in their vicinity, which causes a
decrease in the dielectric breakdown strength as compared to
I. INTRODUCTION the neat polymer. The extent of this local field distortion and
A European project called GRIDABLE (Polymer enhancement is not only a factor of the difference in
Nanocomposite Insulation Material Enabling Integration of permittivity or conductivity between the particles and the
Renewables and DC Storage Technologies in the AC Energy polymer matrix, but also of the size of the particles, their
Grid) was inaugurated under the HORIZON 2020 framework aggregation and agglomeration [1]. Therefore, improving the
co-funded by the European Community. Various partners, both dispersion of the nanofillers in a nanodielectric material can
academic and industrial, are working together within this result in improvement of the dielectric breakdown strength.
project, aiming to develop a new generation of nanostructured Another factor that can lead to early electrical breakdown of
polymer-based materials suitable for high voltage DC (HVDC) a nanocomposite, is poor adhesion between the particles and
cable insulators and capacitors. The goal of GRIDABLE is to polymer chains due to chemical incompatibility [10]. Chemical
develop polypropylene-based nanocomposites with proper incompatibility could result in formation of small voids at the
nanoparticle functionalization and dispersion quality. This polymer/filler interface and thus decrease the dielectric
novel material can introduce significant improvements to the breakdown strength. Hence, surface modification performed in
state of the art DC cable and film capacitor insulations. order to bond/bind the particle surface to the polymer matrix,
The incorporation of nanoparticles to dielectric materials, in can increase the breakdown strength and reduce the dielectric
order to improve their insulating properties, was studied losses [11].
extensively in the recent years [1-3]. Nanodielectric composites Another way in which surface modification of the
nanoparticles can influence the dielectric properties of the

978-1-5386-8434-4/19/$31.00 ©2019 IEEE 241

nanodielectrics is alteration of the electronic features at the on the ultimate insulation characteristics of the nanocomposite
interface between the coated particles and the polymer matrix materials.
[1]. Siddabattuni et al. [12], reported a significant reduction in TABLE I
Reaction conditions utilized for modification of the silica nanoparticles
leakage currents and dielectric losses and improvement in
Sample Temperature Time Added Water
dielectric breakdown strengths, when electropositive phenyl, Number (°C) (hour) (gram)
thus electron-withdrawing functional groups, were located at 0 Untreated Silica
the polymer−particle interface. Accordingly, it can be 1 80 24 1.8
speculated that introduction of polar functional groups to the 2 20 1 1.8
3 80 1 0.0
surface of the nanoparticles can induce this sort of electronic 4 20 24 1.8
behavior as the dipoles at the particle/polymer interface may 5 80 1 1.8
affect charge carrier transport and trapping [13].
Space charge distribution is a direct outcome of combined B. PREPARATION OF THE NANOCOMPOSITES
trapping/detrapping and transport behavior of charges in
insulating polymers and varies with trap density, trap depth The nanocomposites studied in this work are based on
distribution, and charge carrier mobility [14]. While the space polypropylene (PP) blends filled with surface modified nano-
charge phenomena can possibly be controlled by changing the silica particles. The specimens were prepared by addition of
morphology and crystallinity of the polymer, space charge 1 w% of different silica samples to the polymer matrix in a
distribution can be influenced by grafting functional groups twin-screw micro extruder, and subsequently, injected into a
onto the nanofiller particle surface, influencing charge mobility square mold using a mini-injection molding machine. The
through the introduction of shallow trap sites [15] or reducing dimensions of the mold were 260x260x0.5 mm. The resulting
the number of charges trapped in deep traps [1] in the nanocomposite (NC) samples were named according to the
filler/polymer interaction zones. silica sample used. For instance, NC_1 is nanocomposite filled
In this study, silica nanoparticles were modified with a polar with silica sample number 1.
modifying agent, and compounded with PP based polymer
blends. The aim of surface modification was to improve the C. THERMAL GRAVIMETRIC ANALYSIS (TGA)
trapping/detrapping behavior of the PP blend/silica
nanocomposites. Firstly, the modification was proven by using Thermal gravimetric analysis was performed on the modified
Thermogravimetric Analysis (TGA). Subsequently, the silica samples in order to quantify the level to which the
influence of silica modification on the charge trapping behavior modification process is successful. This method involves
of the aforementioned nanocomposites was studied via heating up the silica powder from room temperature to 850 °C
Thermally Stimulated Depolarization Current (TSDC). with a rate of 20 °C/min while measuring the weight loss of the
Nevertheless, this paper is based on preliminary results of the sample. The weight loss between 300–850 °C can be attributed
study, and further elaborations are planned to be done in future to the thermal decomposition of this silane coupling agent
publications. chemically bonded to the silica surface [16]. Fig. 1
demonstrates the results of this measurement as the weight loss
II. EXPERIMENTAL WORK
percentage over temperature.
A. SILICA MODIFICATION
D. THERMALLY STIMULATED DEPOLARIZATION CURRENT
A fumed silica grade with high purity and low moisture (TSDC)
content was selected for this study. The silica surface
modification was carried out via the state-of-the-art solution Thermally Stimulated Depolarization Current (TSDC)
method using a polar silane as the modifying agent under measurements were carried out in order to study the charge
different reaction conditions. Further specification of these trapping behavior of the nanocomposites. Circular Au
materials is at this moment not possible due to intellectual electrodes (100 nm in thickness) were deposited on both sides
property reasons. The details of each modification reaction for of the sample films by e-beam evaporation under high vacuum.
each modified silica sample is depicted in Table 1. The The samples were first heated up to 70 °C, and subjected to a 3
modification was carried out in a glass round bottom flask, kV/mm DC electric field for 20 minutes under isothermal
immersed in an oil heating bath, equipped with a mechanical conditions. The samples were then cooled down to −50 °C
stirrer, cooler and thermometer. The silica, silane and additional while the poling voltage was still on. Subsequently, the samples
water were mixed with toluene, which was the liquid medium were short-circuited and linearly heated up to 140 °C at 3
of the reaction. °C/min, while the depolarization current was monitored by a
The polar silane used in this study is prone to alter the silica- highly sensitive ammeter.
polymer interphase which, as a consequence, can change the
dielectric behavior of the nanocomposites. It is assumed that by III. RESULTS AND DISCUSSION
the introduction of this polar functionality to the silica surface,
TGA results, depicted in Fig. 1, show a higher weight loss for
charge trapping properties of the dielectric material undergo
the modified silicas compared to the untreated one, which is an
meaningful changes, which might induce beneficial influences

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indication of the successful modification of the silica surface. The results in Fig. 2 indicate that upon incorporation of the
Different reaction conditions were utilized to achieve different treated nanosilica the TSDC spectra become more complex and
levels of silane modification. The values of weight loss above a significant shift of the main TSDC peak towards higher
300 °C are listed in Table 2. It can be seen that a range of weight temperatures occurs, being indicative of the trap becoming
losses, from ca. 3% to 6%, is achieved by altering the reaction deeper. For the samples with the polar functionality on the filler
conditions. surface a new (deep) trap emerges in the 93–97 °C range, while
a smaller side peak is observed around the same temperature
(~78 °C) as the intrinsic TSDC peaks of the two reference
samples (UP and NC_0). Comparing NC_3 and NC_4 with the
lowest and the highest levels of silica modification,
respectively, it can be observed that the location of the new deep
trap peak is shifted to higher temperatures. Moreover, the
intensity of the TSDC peak is seen to vary significantly
depending on the type of treated silica, with some of the
samples exhibiting (apparent) reduction in the main peak
current intensity; this may be related to (i) reduction of the
density of the trap states or (ii) more uniform distribution of the
space charge in the specimen (hence leading to smaller
measurable external current in the TSDC experiment). While
more detailed studies are necessary, these results imply that the
depth and the density of the newly introduced trap is profoundly
influenced by the level of the modification i.e. the amount of
Fig. 1. TGA results for the modified silica samples compared to the untreated the grafted silane on the silica surface.
silica.

Nevertheless, altering the modification reaction conditions

can change not only the thickness of the deposited layer, but
also its morphology, wettability and extent of silane hydrolysis.
Each of the aforementioned factors can affect the interfacial
properties between the fillers and the polymer chains which can
lead to different dielectric behavior of the nanocomposites.
Table II
TGA Weight Loss Values at Temperatures above 300 °C.
Sample TGA Weight Loss
Number (%)
0 0.61
1 6.16 Fig. 2. TSDC spectra of injection molded PP blend samples.
2 4.52
3 3.21 The above trend is however not entirely dominant as there are
4 6.23 some repeatable exceptions. For instance, samples NC_1 and
5 4.55
NC_4 contain silica samples number 1 and 4, respectively,
which have more or less equal TGA weight losses. However,
Fig. 2 shows the TSDC plots of all the silica filled samples as
for NC_4, the deep trap peak is more suppressed compared to
well as of the unfilled polymer (UP) as a secondary reference.
NC_1. It is the same for samples NC_2 and NC_5. In other
In principle, the TSDC spectra are attributable to the relaxation
words, a possible explanation is that the depth and density of
of (dipolar) polarization and accumulated space charge formed
the traps are not only a function of the thickness of the silane
during the isothermal polarization phase. It is remarked that the
layer, but also of other parameters, such as filler dispersion,
short-circuit TSDC is a net sum of both homo- and heteropolar
silane layer morphology, micro-structure and crystallization
discharge current components, and hence, the integrated charge
characteristics of the compound.
represents the net charge. For most semi-crystalline and weakly
In order to gain more insight into the results above, the areas
polar polymers, such as PP, the high temperature TSDC
under current vs. time curves during polarization and
spectrum above the glass transition temperature is mainly
depolarization were calculated, providing an indication of how
associated with the relaxation of trapped space charge. It is also
much charge was injected into or released from the sample,
remarked that this high-temperature space charge relaxation can
respectively. Fig. 3 demonstrates the calculated amount of
be influenced by thermal transitions (such as softening/melting)
charges for each sample during isothermal polarization,
of a single phase in heterophase polymer blend systems. To a
isothermal polarization + freezing and depolarization. Fig. 3
first approximation, the TSDC peak temperature and intensity
can be interpreted from different points of view. Firstly, it can
can be attributed to the depth and density of charge traps,
be seen that for all cases the amount of charge injected during
respectively, as is done in the following analysis.

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the isothermal polarization period more or less remains in the deep traps. However, there are exceptions. Some of the samples
sample as a result of freezing. Secondly, the amount of charge with the same modification levels behave differently during the
released during the thermally stimulated depolarization phase is TSDC measurement. This could be due to the fact that altering
much lower than that injected during polarization. While the the modification reaction conditions changes not only the
latter is generally to be expected for TSDC experiments—in amount of grafted silane, but also the grafted layer morphology,
particular for relatively thick specimens for which the depth of accessible surface area, wettability and extent of silane
the injected charge layer is likely small in comparison to film hydrolysis, each of which can affect the interfacial properties
thickness[17]—it seems that the above effect is significantly between fillers and the polymer chains leading to different
reduced upon incorporation of modified nanosilica. Fig. 4 dielectric behavior of the nanocomposites. In order to get a
shows the values of released charges relative to the amount of clearer image of the functionalization of the silica and its effect
the injected charges for these samples. As it can be seen, for the on the charge trapping behavior of dielectric nanocomposites,
reference samples UP and NC_0, only %19 and %17 of the studying the aforementioned factors seems to be interesting for
injected charges are released during depolarization, whereas, in future studies.
case of samples with highly modified silica e.g. NC_1, this
value increases to %55. This can be an indication of lower ACKNOWLEDGMENT
remaining accumulated space charge for the samples with
modified silica. This project has received funding from the European Union’s
Horizon 2020 research and innovation program under grant
agreement No. 720858. The authors also would like to thank the
ECIU Researcher Mobility Fund for supporting this research
work.

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