Received: 5 June 2022

DOI: 10.1049/hve2.12268

ORIGINAL RESEARCH
- -Revised: 10 August 2022 Accepted: 15 August 2022

- High Voltage

Effects of nanofiller and voltage stabilizer on partial discharge

resistance of polypropylene/elastomer blends: A comparison
study

Yu Gao1 | Jing Li1 | Xuri Xu2 | Jinjing Peng3 | Tao Han1 | Boxue Du1

1
School of Electrical and Information Engineering, Abstract
Tianjin University, Tianjin, China
This paper reports on the individual and synergistic influence mechanisms of nano‐silica
2
State Grid Yancheng Power Supply Company, (SiO2) and voltage stabilizers on partial discharge (PD) resistance of polypropylene
Yancheng, China
blended with ethylene‐octene copolymer elastomer. The SiO2 nanoparticles and three
3
Guangzhou Panyu Power Supply Bureau,
types of voltage stabilizers, that is, benzoin, 4,40 ‐dimethoxybenzil, and 3‐aminobenzoic
Guangzhou Power Grid Corporation, Guangzhou,
China acid are selected as fillers to prepare samples. PD is initiated in a rod‐to‐plane elec-
trode system with an alternating current voltage of 5 kVrms. PD characteristics are
Correspondence captured with multi‐sensors, and the erosion profile of the test sample is measured using
Tao Han, School of Electrical and Information a three‐dimensional (3D) optical profilometer. Carrier trap distribution is extracted with
Engineering, Tianjin University, Tianjin 300072,
isothermal surface potential decay measurement to assist the analysis of PD eroding
China.
Email: [email protected] material. Fourier transform infrared spectrum, scanning electron microscopy, X‐ray
diffraction spectrum, and differential scanning calorimetry analysis are performed to
Associate Editor: Xingyi Huang reveal the change in material structures caused by the fillers. Test results indicate that the
PD resistance of the blend can be improved by the addition of nano‐SiO2 and voltage
Funding information stabilizers individually and synergistically. The PD resistance of PO is increased by 71.2%
Natural Science Foundation of Tianjin City, Grant/ at most in the sample with 3 wt% nano‐SiO2 addition. The sample filled with SiO2
Award Number: 20JCYBJC00840; National Nature
Science Foundation of China, Grant/Award exhibits better PD resistance than that with the voltage stabilizer or co‐added, which
Number: 52077151 should be ascribed to the introduction of deep traps, the formation of the packaged layer,
the suppression of oxygen diffusion of the nanofillers, and the good compatibility be-
tween additives and the polymer matrix.

1 | INTRODUCTION polymer material used as cable insulation in the AC field, it is

very essential to understand the degradation behaviour caused
Polypropylene (PP) blending with elastomer has been consid- by the PD, thus proposing effective methods to improve the
ered a promising candidate for cable insulation with excellent PD resistance of the polymer.
electrical and mechanical properties in both alternating current Over the years, researchers introduced inorganic oxide
(AC) and direct current (DC) systems [1–3]. Studies concern- nanoparticles into polymer materials to improve insulation
ing the electrical properties of PP under the DC field have properties. A large volume fraction of the interface is formed
been widely performed [4, 5]; however, the focus on the in nanocomposites, which is the reason for the advantageous
properties under the AC field is rather limited. One important dielectric behaviours at low nanofiller loadings [8]. Properly
phenomenon that occurred within polymeric cable insulation dispersed nanoparticles can act as elementary barriers to pre-
that would lead to insulation deterioration is partial discharge vent electrical tree propagation and breakdown in nano-
(PD) [6]; such PD activity is easier to take place under an AC composite materials [9–11]. The evaluation of PD corrosion
field than that under a DC field [6, 7]. Therefore, for the resistance is helpful to understanding the generation,

-
This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is
properly cited.
© 2022 The Authors. High Voltage published by John Wiley & Sons Ltd on behalf of The Institution of Engineering and Technology and China Electric Power Research Institute.

High Voltage. 2022;1–11. wileyonlinelibrary.com/journal/hve2 1

2
- GAO ET AL.

development, and failure mechanism of electrical ageing of 2 | EXPERIMENTAL SETUP

insulating materials, hence a large number of studies about PD
erosion characteristics of polymers have been performed. 2.1 | Sample preparation
Abdel‐Gawad et al. pointed out that the surface functionali-
sation of nanoparticles improved the dispersion within poly- Isotactic PP (PPH‐T03, Sinopec Shanghai Company) and
vinyl chloride and the low‐density polyethylene (LDPE) EOC (DOW 8401, Dow Chemical Company) were selected as
matrix, and enhanced the PD resistance [12–15]. Ohki et al the base material and the filler. The weight average molecular
reported that the resistance to PDs for polyamide composites weight (Mw) of PP is 334,242, and that of EOC is 263,711,
was influenced by the size of fillers. The PD resistance of the measured by gel permeation chromatography with tri-
specimens with nanofillers was better than that of specimens chlorobenzene as the mobile phase. The PP and EOC mixture
without nanofillers or containing micro fillers [16, 17]. The was placed in an internal mixer at 180°C with a rotation speed
effect of nanoparticle type on the PD resistance of the epoxy of 30 r/min for 5 min. During the melting of the mixture, the
composite was also analysed [18, 19]. The PD resistance of additives, that is, 20 nm‐SiO2 and voltage stabilizers, were
epoxy could be improved remarkably while a proper nanofiller doped. The SiO2 (Dechuan Technology Co., Ltd.) particle was
was selected. Accordingly, in order to improve the PD resis- pretreated with 3‐Aminopropyltriethoxy Silane (KH550), and
tance properties of the PP/elastomer blend, the surface its content was controlled at 1, 3, and 5 wt%, respectively. The
functionalisation, size, and type of nanofillers should be care- voltage stabilizers were benzoic, 4,40 ‐dimethoxybenzil, and 3‐
fully considered. aminobenzoic acid, and the content was selected at 0.1 wt%.
On the other hand, studies have been conducted where Figure 1 shows the chemical structural formula of these
organic additives as voltage stabilizers are added into poly- voltage stabilizers; it can be seen that all the stabilizers contain
mers to improve the dielectric strength under high‐voltage aromatic rings. The extruded pellets then went through a hot‐
alternating current conditions [20]. Voltage stabilizers are pressing process under 16 MPa at 190°C for 5 min to produce
usually aromatic compounds. The high electron affinity of the blend samples. The sample thickness was 300 μm and was
voltage stabilizers is used to resist the impact of high‐energy tailored into 30 � 30 mm for testing. The samples containing
electrons and be excited or ionised. The destruction of mo- different types of fillers are listed in Table 1. PO is the
lecular chains by high‐energy electrons is inhibited because abbreviation of the PP/EOC blend. POS, POV, and POSV
that part of the energy is absorbed, which significantly im- represent PP/EOC/SiO2, PP/EOC/voltage stabilizer, and
proves the electrical treeing resistance of the material [21]. PP/EOC/SiO2/voltage stabilizer composites, respectively. In
Roseen et al pointed out that the PD resistance of cross‐ POS, one, three, and five are the contents of nanoparticles,
linked polyethylene (XLPE) was improved by adding vinyl while B, four, and A are the types of voltage stabilizers in POV
naphthalene; however, anthracene, fluoranthene, naphthalene, and POSV. wt% is the weight percent of fillers in samples. The
pyrene, and o‐terphenyl had little influence on the PD resis- abbreviations of the samples are used in the following sections
tance [22]. Yamano et al reported that the electrical tree for discussion.
initiation voltage for LDPE with anthracene is about 3.5
times higher than that for pure LDPE, while the TIVs for
naphthalene, tetracene, and pentacene are not significantly 2.2 | PD resistance measurement
increased [23]. It can be expected that the selection of the
voltage stabilizer is also very important to improve the PD The PD erosion test was carried out with the rod‐to‐plane
resistance of polymers. Therefore, attempts are worth carrying electrode system, as shown in Figure 2. The rod electrode
out to tailor the PD resistance of the PP‐based blend used for was designed to form strong tangential and normal electric
AC cable insulation by adding nanoparticles and voltage sta- field components on the surface where the charges were
bilizers, respectively, or together. A comparative study is
performed concerning the analysis of the individual and
synergistic influence mechanisms.
In this work, the surface‐treated nano‐silica (SiO2) and
three types of voltage stabilizers were selected as fillers to
modify the PD resistance of the PP/ethylene‐octane copol-
ymer (EOC) blend. The PD erosion test was carried out with
an AC voltage of 50 Hz through a rod‐to‐plane electrode
system. Multi‐sensors were employed to capture the PD be-
haviours, and the erosion feature was estimated by a 3D optical
profilometer. Carrier trap distribution, as well as material
structures, were measured to assist the analysis of PD‐induced
degradation of test samples. The mechanisms of PD resistance
improvement by nanoparticle and voltage stabilizers individu- F I G U R E 1 Chemical structural formula of the voltage stabilizers.
ally and synergistically have been demonstrated. (a) Benzoin, (b) 4,40 ‐Dimethoxybenzil, (c) 3‐Aminobenzoic acid
GAO ET AL.
- 3

TABLE 1 The abbreviations of samples

Weight percent of fillers (wt%)
Category Name POE SiO2 Benzoin 4,4′‐Dimethoxybenzil 3‐Aminobenzoiic acid
PO PO 20

POS PO1 20 1
PO3 20 3
PO5 20 5

POV POB 20 0.1

PO4 20 0.1
POA 20 0.1

POSV POSB 20 3 0.1

POS4 20 3 0.1
POSA 20 3 0.1

The PD erosion process was performed for 2 h at ambient

temperature and the relative humidity was kept at 20%. The
erosion depth and the surface roughness, as quantitative pa-
rameters to directly reflect the PD resistance, were extracted by
using a 3D optical profilometer (Sneox). The erosion depth
and the calculated surface roughness were used to show the
erosion conditions of samples, while the average apparent PD
intensity, the average pulse number, the average light intensity,
and the ozone concentration are employed to analyse the PD
behaviours. The test was repeated at least three times for each
sample to ensure repeatability.

FIGURE 2 Rod‐to‐plane electrode system for PD erosion. PD, partial

discharge 2.3 | Trap characteristics measurement
Trap characteristics are considered to be highly associated with
deposited during PD. Accordingly, charge migration along the charge transport behaviours in polymer materials. The trap
surface and into the bulk of the sample would be both facili- characteristics can be derived from the isothermal surface
tated. In such a case, the charge transport behaviour that was potential decay (ISPD) measurement. Electrode arrangement
associated with the material structure on the resistance of PD and test circuit for ISPD test could be found in our early
could be easily evaluated among various samples. The length of publication [1]. The experiment was conducted in an enclosed
the tungsten rod electrode was 12 cm and the radius was chamber with a temperature of 40°C, and the humidity
0.5 mm. The grounded plane electrode made of brass was remained at 20%. The sample was charged by negative DC
placed at the bottom of the sample with a thickness of 300 μm. corona with a needle and grid electrodes at −5.5 and −3 kV,
The air gap between the rod tip and the sample surface was set respectively.
to 0.4 mm. The discharge pulse signal, the optical signal, and
the concentration of the ozone produced by PD were acquired
by a high‐frequency current transformer (HFCT), a CH253 2.4 | Material structure characterisation
photomultiplier tube (PMT), and the ozone gas sensor
(IGM200‐03), respectively. Detailed methods for measuring The sample structures have been characterised using Fourier
the PD signals with the multi‐sensors have been presented in transform infrared (FTIR), scanning electron microscopy
our previous publication [24]. Regarding the PD test, it was (SEM), X‐ray diffraction (XRD), and differential scanning
reported in accordance with the IEC standard 60,270 [12–15]; calorimetry (DSC). The chemical structure of the sample could
however, HFCT was employed in this work in order to adapt be measured through the FTIR spectrum, which was achieved
the requirements of polymers for wider bandwidth. The gas by a Bruker FTIR spectrometer with an attenuated total
sensor was placed in an enclosed test chamber to avoid the reflection accessory. The microscopic morphology of the PP/
influence of airflow, and the sensor was 15 cm away from EOC blends was observed using the SEM measurement. The
the rod tip. An AC voltage of 5 kVrms at 50 Hz was applied samples were fractured in liquid nitrogen and the cross‐section
between the rod electrode and the plane electrode for each test. was sputtered with a thin layer of Au in a vacuum before
4
- GAO ET AL.

observation. The accelerating voltage of the FEI Apreo scan-

ning electron microscope was 10 kV. XRD and DSC tests were
carried out to exhibit the crystalline structure of the sample.
The wide‐angle XRD measurement was conducted by the
MinFlex600 diffractometer, and the crystalline structures of
the samples were obtained by the test at room temperature
with Cu target Kα radiation (Kα = 1.54 Å). The XRD pattern
was recorded over angles varying from 10 to 35° with a scan
rate of 2°/min. The DSC measurement was attained by using a
NETZSCH DSC214 polyma. The heating or cooling rate was
10°C with a temperature between 45 and 180°C under a ni-
trogen atmosphere. The sample was firstly heated up from 45
to 180°C and held for 5 min to remove the thermal history, and
then a heating–cooling cycle was made to get the melting and
crystalline behaviours. The melting temperature Tm, the crys-
tallisation temperature Tc, and melting enthalpy ΔHm could be
obtained from DSC curves. The crystallinity of the sample
was calculated using Equation (1), and ΔHm0 was selected as
209 J/g [3]:

ΔHm
Xc ¼ � 100% ð1Þ
ΔHm0

F I G U R E 3 Erosion morphology and 2D erosion profile for PO3.

(a) Erosion morphology, (b) 2D erosion profile
3 | TEST RESULTS
3.1 | PD behaviour

For the rod electrode used in this work, the un‐eroded area
appears beneath the electrode whereas the area face to the edge
of the electrode is eroded due to the impact of PD [24]. The
erosion of the test sample is non‐uniform, and the 3D optical
profilometer is used to position the deepest erosion pit. The
morphology of the deepest erosion pit observed by the 3D
optical profilometer for PO3 has been taken as an example and
is shown in Figure 3a. The erosion pit is featured in a crater‐
like shape, and the roughness is enhanced as well. A 2D
erosion profile is exacted from Figure 3a and is depicted in
Figure 3b. It can be observed from Figure 3b that the
measured erosion depth for PO3 has a max value of 5.18 μm.
Since PD occurs with different magnitudes for various sam-
ples, the calculated erosion depth under the unit PD quantity is
used to estimate the PD resistance of the sample, which is
defined as the ratio of the measured max erosion depth to the
average apparent PD intensity [24]. Similarly, the calculated
surface roughness is calculated using this method. The calcu-
lated erosion depth and the calculated surface roughness for
the test samples, which reflect the PD resistance of the ma-
terial, are shown in Figure 4. It is found in Figure 4a that the
erosion depth for POS, POV, and POSV is shallower than that
of PO, which means the improvement of the PD resistance by
the addition of the additives. The erosion depth for POS is the
shallowest among the test samples, which indicates the best
resistance to PD. It can be seen that the erosion depth for POS F I G U R E 4 The calculated erosion depth and surface roughness for
initially decreases and then increases with the increase of the the test samples. (a) Erosion depth, (b) surface roughness
GAO ET AL.
- 5

content. The shallowest erosion depth for POS, that is,

0.34 μm/pC, appears at the content of 3 wt%. POV exhibits
inferior PD resistance than that of POS, whereas it is superior
to POSV. In addition, POA exhibits the best performance in
improving PD resistance compared with PO4 and POB, as
shown in Figure 4a. The surface roughness depicted in
Figure 4b exhibits a similar trend to the erosion depth, which
proves again that the PD resistance of the sample follows
POS > POV > POSV > PO.
In order to understand the PD activity during the discharge
process, multi‐sensors have been employed to reveal the
behaviour from electrical, optical, and chemical aspects,
respectively. It has been reported that PD magnitude and activity
rates were analysed using the phase‐resolved PD method [13]. In
this work, the PD intensity and pulse number are used to reveal
the PD level and how often the erosion occurs, respectively,
which reflects the evolving process during the degradation. The
PD pulse number refers to the number of PD pulses acquired
within 0.1 s. The average pulse number can be calculated by
averaging 24 PD pulse numbers in the test [24]. The results of
the average apparent PD intensity, the average PD number, and
the average light intensity acquired by HFCT and PMT are
shown in Figure 5. It is seen that the average PD number and the
average light intensity have similar trends to that of the average
apparent PD intensity. PO exhibits the highest average apparent
PD intensity among the test samples whereas the intensity for
POS is the lowest. The intensity for PO1 is 10.71 pC, which
reduces to 9.08 pC with the SiO2 content of 3 wt%, then the
value rises to 10 pC when 5 wt%‐SiO2 is added into the blends.
The concentration of the ozone for the test samples, which is
produced by PD, is shown in Figure 6. It can be found that the
ozone concentration for PO is the smallest, that is, 12.6 ppm.
Except for PO, POSV has the lowest gas concentration, POV
follows, and the ozone concentration for POS is the highest.
The concentration for PO1 is 22.8 ppm, which increases to
28.1 ppm and then decreases to 24.2 ppm when the nano
content increases to 3 and 5 wt%, respectively. For POV, the
F I G U R E 5 The average (a) apparent PD intensity, (b) pulse number,
ozone concentration follows POA > PO4 > POB. By adding and (c) light intensity for the test samples. PD, partial discharge
different voltage stabilizers into POS, the ozone concentration
of POSA is the highest, whereas that is the lowest for POSB. It
has been reported that the concentration of ozone is correlated
with the generation process induced by PD and the consump-
tion process due to the oxidation reactions of the test sample
[24]. For PO3, the least ozone is consumed during the PD
erosion process, which results in the highest ozone concentra-
tion. Meanwhile, the average intensity and number of PD are the
lowest in PO3, as shown in Figure 5. Therefore, the PD erosion
of the sample would be the shallowest. It is considered that the
results of the ozone concentration for other samples can be
understood in this way.

3.2 | Trap distribution

An ISPD test is carried out to assist in analysing the PD
development behaviour during the PD erosion process. The FIGURE 6 Ozone concentration for the test samples
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density of the deep trap is 10 times higher than that of the

shallow trap, the charge transport behaviour is considered to
be mainly affected by the deep trap. As mentioned above, the
deep trap level of POS is the deepest among the test sample,
and most charges will be accumulated, thus weakening the
electric field between the rod electrode and the sample surface.
As a result, the PD intensity for POS is the lowest. Such an
effect can be also employed to analyse the average PD number
and the light intensity of other samples.

3.3 | Material structure characteristics

The structures of samples were characterised with the purpose

of better understanding the erosion mechanism because the PD
erosion process is highly related to the material structure [7]. The
FTIR spectra of PO, POS, POV, and POSV are shown in
Figure 8. It can be observed that the main infrared absorption
peaks of PO are asymmetric stretching vibration peaks of
(‐CH3) at 2953 cm−1, (‐CH2) at 2917 cm−1, (‐CH2‐) at 2845 and
1459 cm−1, (‐CH3) at 1377 cm−1. For PP/EOC blends with
SiO2, the bending vibration peak of (HOH) at 1638 cm−1 ap-
pears, which is due to the introduction of hydroxyl groups on the
surface of the nanoparticle. The absorption peak at 1087 cm−1
represents the (Si‐O‐Si) antisymmetric stretching vibration.
Hence, the nanoparticle treated by a silane coupling agent is
successfully introduced into PO. It can be noticed from
Figure 8b that the vibration peak at 1600 cm−1 and (C=O)
FIGURE 7 The electron (a) trap level and (b) density for the test absorption peak at 1720 cm−1 appears in infrared spectra, which
samples originate from the common structure of the benzene ring and
the carbonyl group of the voltage stabilizers. Similarly, the
variation in the FTIR spectra can be recognised as the addition
trap energy level and the trap density derived from the ISPD of of both SiO2 and voltage stabilizer, as depicted in Figure 8c.
the test samples are shown in Figure 7a,b, respectively. Among It is known that the electrical property of polymer‐based
the three categories, POS has the deepest level of both shallow nanocomposites is dependent upon the material morphology
and deep traps. In addition, the deep trap density for POS is [25]. The morphology of the test samples is shown by the SEM
the largest. Another interesting feature for POS is that the trap images in Figure 9. It can be seen that a number of the isolated
level as well as the deep trap density initially increases and then spots appear in PO, as indicated by the red dotted square in
decreases with the increasing addition of SiO2, whereas the Figure 9a. Such a phenomenon is a result of the bad
shallow trap density increases continually. The deep trap depth compatibility between PP and EOC [1]. It is found in
for POV is shallower than that of POS. It is noted that the trap Figure 9b–d that the size of the isolated spots is smaller than
level and the deep trap density for POSV are slightly changed that of PO, which infers that the compatibility of PP/EOC
compared with POV. For the deep trap, the level of POA is the blends is improved. The nanofiller is well‐dispersed in the PP
deepest, PO4 follows, and POB has the shallowest trap energy. matrix when the filler content is 1 and 3 wt%, as shown in
In general, both the shallow trap level and the deep trap level Figure 9b,c. As the content increases to 5 wt%, nanoparticle
for POS, POV, and POSV are deeper than that of PO. agglomerations appear as indicated by the red dotted circle in
Moreover, the deep trap density for the modified blends is PO5. In POV, the size of the separated spots is larger than that
more enhanced than that of PO. An interesting feature can be in POS, as depicted by the example of PO4 in Figure 9e. The
concluded, which is that the trend of deep trap energy for tiny prisms with a size of 2–5 μm are marked by red rectangles,
various samples is consistent with the variation of erosion which are correlative with the shape of the introduced voltage
depth and surface roughness. Considering the results of the stabilizer. For POSV, taking the POS4 as an example, the
trap characteristics and the results of the PD intensity, it is nanoparticle agglomerations and the micro‐sized prisms are
proposed that the sample with deeper trap energy exhibits observed in Figure 9f, and it indicates the worst compatibility
smaller PD intensity compared with that having shallower trap status among the test samples.
depth. It is known that the carrier captured by the deep trap is Figure 10 shows the results of normalised XRD spectra of
more difficult to de‐trap, whereas the charge localised by the test samples. It is observed that the characteristic diffraction
the shallow trap is easier to go over the barrier [4]. Since the peaks of PO are at 2θ = 14.1°, 16.9°, 18.5°, 21.4°, and 21.8°,
GAO ET AL.
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FIGURE 8 FTIR spectra for the test samples. (a) PO and POS, (b) POV, and (c) POSV

FIGURE 9 Typical SEM images for the test samples. (a) PO, (b) PO1, (c) PO3, (d) PO5, (e) PO4, and (f) POS4

corresponding to the α(110), α(040), α(130), α(111), and α(131), Figure 11 shows the melting and crystallisation parameters
respectively. Such features mean the presence of the monoclinic for the test samples extracted from the DSC measurement. As
(α) crystal morphology in the PP/EOC blends. The diffraction shown in Figure 11a, the melting temperature Tm of the PO is
peak at 16.1° corresponding to β (300) appears in POS but is not 162.6°C. With the addition of the nano‐SiO2, the Tm of POS
observed in POV. It means that the crystal form is changed with decreases slightly and the PO3 holds the lowest Tm of 161.3°C
the inclusion of nano‐SiO2 but is not altered with the addition of among the POS samples. It infers that the inclusion of the
the voltage stabilizers. In addition, the diffraction peaks of β nanoparticle doesn't change the melting process of PO
(300) are more obvious for PO1 and PO3 than for PO5, which remarkably. Similar behaviour is observed for the crystalline
may indicate that the nanoparticle agglomeration in PO5 re- process as well; the Tc varies between (118 � 1)°C for PO and
stricts the formation of the β‐crystal. As for POSV, the β‐crystal POS samples. The crystallinity keeps almost unchanged as the
peak appears again and the intensity of the β‐crystal diffraction nanofiller content grows from 0 to 3 wt%; however, an
peak is weaker compared with that of POS. It proves that the obvious reduction occurs as the filler content is 5 wt%. The Xc
nanoparticle would lead to the formation of the β‐crystal of PO5 is 28%, much lower than that of PO with 39.7%. It
whereas the voltage stabilizer would not. means that the doping of high content nano‐SiO2 seriously
8
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FIGURE 10 X‐ray diffraction spectra for the test samples

affects the crystallinity of PO. For the POV samples, as shown

in Figure 11b, the Tm, Tc, and Xc are in the range of
(162.5 � 1.5), (118.5 � 2.5)°C, and (38 � 1)%, respectively,
which are very close to the parameters of PO. It reveals that
the voltage stabilizers don't result in a noticeable change in the
melting and crystalline processes of PO. For the POSV sam-
ples, as depicted in Figure 11c, the above parameters again
hold close to those of PO; since all POSV samples contain the
nano‐SiO2 of 3 wt%, the pronounced reduction in Xc is not
observed for POSV.

4 | DISCUSSION
F I G U R E 1 1 Melting and crystallisation parameters of the test
PP is a typical semi‐crystal polymer that consists of crystalline samples. (a) PO and POS, (b) POV, and (c) POSV
and amorphous regions in its volume. As the EOC elastomer is
blended into the PP, the PO blends could be prepared with
acceptable mechanical properties for cable insulation [26].
When additives are further included in the PO, the change in eroding the composite. Another effect facilitating the degra-
PO structure may result in the variation of PD resistance. The dation of polymer is the local heating due to the high‐
general process of PD erosion to polymer with the rod‐to‐ temperature gas induced by PD [24]. Accordingly, the resis-
plane electrode system has been stated in our previous works tance of PO tailored by the nano‐SiO2 or the voltage stabilizers
[24]. As the material is exposed to the PD, it would be sub- to PD should be analysed by taking into account the charge
jected to a couple of effects caused by the discharge, which can bombardment, UV radiation, oxidation, and local heating ef-
result in the erosion of the sample. One of the most important fects. In order to clearly analyse the individual and synergistic
effects is the bombardment of ions and electrons accelerated influence mechanisms of nanoparticles and voltage stabilizers
by the high electric field [7]. These charges with energy higher on PD resistance, the schematic diagrams of the PD erosion
than 8 eV are sufficient to rupture the molecular chains [27]. mechanisms of POS and POV are shown in Figure 12.
Ultraviolet (UV) radiation has been also considered an For POS samples, deep traps are formed due to the
important reason for molecular chain rupture. Due to the interface between the base matrix and the inorganic particle,
rupture of the molecular chain and the activated free radicals when SiO2 nanoparticles are well‐dispersed with a low content
generated by the charge impact, the material would be as shown in Figure 9b,c. Shallow traps are introduced by ag-
degraded [27]. Moreover, the chemical reaction between acti- glomerations, which act as physical defects in PO5, as shown in
vated free radicals and the oxidative species can produce acids Figure 9d. In addition, β‐crystal is observed, which should be
GAO ET AL.
- 9

deep traps are introduced, the lateral charge motion as well as

the charge transport through the bulk is limited, and charges
could be captured and stay at the traps for a longer period.
These charges generated a reversed field to the applied field,
thus reducing the PD activity. Accordingly, the apparent
average PD intensity, the average PD number, and the average
light intensity decrease, as shown in Figure 5. Therefore, the
PD becomes less harmful than the case of the PO. In addition,
the nano‐SiO2, as a type of inorganic filler, is more tolerant to
the charge bombardment than the organic molecular chains
due to the higher Si‐O bond energy [29], and the degradation
would mainly occur in the polymer part of POS and the SiO2
particles will reside on the eroded surface to pile up a thin layer
as depicted in Figure 12a. The high‐energy charge bombard-
ment will be reduced by the nanofiller, which helps to improve
the PD resistance. Since the nano‐SiO2 is treated with KH550,
it is expected to have a tight bonding with the polymer matrix.
The vibration of molecular chains that bond with the nano-
particle is restricted when the material is exposed to UV ra-
diation, and thus the rupture of the chains becomes difficult.
The packaged nano‐SiO2 layer also retards the diffusion of
oxygen, resulting in the suppression of oxidation degradation,
which could be supported by the high concentration of ozone
measured with the POS. The melting temperature of POS is
very close to that of PO, which means that the local heating‐
induced deformation of the material structure is comparable
between the two cases. To sum up, the superior PD resistance
of POS to PO is proposed to be attributed to the nano‐SiO2‐
induced deep traps, packaged layer, and oxygen diffusion
suppression.
With regard to POV, the addition of the voltage stabilizers
does not lead to a noticeable change in crystal form or crys-
tallinity of the PO; however, the carrier trap energy becomes
deeper than that of the PO. The possible reason for such a
behaviour is that the voltage stabilizers have aromatic struc-
tures in their molecular framework, which exhibit a high
buffering ability and high electron affinity [21]. When the hot
electrons with high energy attack the voltage stabilizer, the
energy of the charge could be absorbed to form a cold elec-
tron, which is much easier to be captured by the trap. Such a
buffering effect to the hot electron is depicted in Figure 12b.
Since the ionisation energy of the voltage stabilizer is usually
lower than the covalent bond energy of the polymer, the
voltage stabilizer will be ionised or excited by the electrons
prior to the polymer under the high electric field, hence leaving
F I G U R E 1 2 Schematic diagrams of the PD erosion mechanisms of
the low energy electrons behind. The high electron affinity of
(a) POS and (b) POV the voltage stabilizer makes it easy to capture electrons, hence
acting as deep trap centres. The co‐works of the above effects
contribute to the presence of deeper traps in the PO. Since the
ascribed to the heterogeneous nucleation with the nano‐SiO2 hot electrons are buffered by the voltage stabilizers and are
as the nucleating agent. Such β‐crystal contributes to the for- captured by the deep trap, their impact on the molecular chain
mation of deep traps as well [28]. That is the reason why the is alleviated, thus reducing the possibility of molecular chain
deep trap level and deep trap density of POS are obviously rupture caused by the bombardment of charges with high
higher than that of PO. When the PD erosion occurs to the energy, by which the PD resistance of the PO is improved. The
POS, as is depicted in Figure 12a, the charges in the discharge appearance of the deeper traps is responsible for the more
channel have two main ways to release, that is, surface dissi- weakened PD activity, such as the way stated for the POS.
pation and migration into the sample bulk. Since numerous Considering the presence of aromatic rings in the voltage
10
- GAO ET AL.

stabilizers, their addition to the PO should be beneficial for 3. When nano‐SiO2 and voltage stabilizers are co‐added into
UV radiation endurance. However, the oxygen diffusion sup- PO, the PD resistance of POSV is better than that of PO but
pression effect of the voltage stabilizer is lower than that of the worse than that of POS and POV. This is the result of the
nano‐SiO2, as the organic fillers are with a loose structure poor compatibility between additives and the PO matrix. The
(shown in Figure 9e) and are difficult to pile up for the low agglomerations introduce shallow traps and the charge
concentration (0.1 wt%). Accordingly, the oxidation‐induced transport is accelerated, leading to more serious PD erosion.
degradation in POV is more obvious than in POS, which
could be supported by the results of ozone concentration in In summary, the addition of nanoparticles and voltage
Figure 6. Again, the melting temperature of the POV is similar stabilizers both have a positive impact on improving the PD
to that of PO or POS, hence the difference in PD resistance resistance of PP‐based material through different mechanisms.
between POS and POV caused by local heating could be However, the insulation performances are closely related to the
neglected. In short, the most effective way for the voltage compatibility between additives and the polymer matrix.
stabilizer to improve the PD resistance of PO may be attrib- Therefore, attentions should be paid to the modification of
uted to the energy buffering and electron affinity nature of the inorganic and organic additives to further improve the PD
aromatic rings, and the difference in PD resistance of POV is resistance of polymer materials in future research. Moreover,
related to the types and functional groups, such as O‐H or nanoparticles and voltage stabilizers with better PD resistance
C=O, in the voltage stabilizers [30, 31]. should be considered.
When the nano‐SiO2 and the voltage stabilizer are co‐
added to the PO, their positive effects of improving the PD A C K N OW LE D G E M E N T S
resistance are not simply added. As shown in Figure 4, the PD This work is financially supported by Natural Science Foun-
resistance of POSV is even lower than that of POS or POV. It dation of Tianjin (20JCYBJC00840) and National Nature Sci-
is proposed that since the nanoparticle and the voltage stabi- ence Foundation of China (52077151).
lizer are both in powder status, their co‐addition will increase
the possibility of agglomeration because of the poor compat- C O N F L I CT O F I N T E R ES T
ibility with the polymer matrix, as shown in Figure 9f. The The author declares that there is no conflict of interest that
shallow trap density of POSV is thereby higher than that of could be perceived as prejudicing the impartiality of the
POS and POV, as shown in Figure 7b, and the PD activity for research reported.
POSV is more serious with high discharge intensity. Further-
more, the oxygen consumption for POSV is higher than that DA TA AVAI LA B I LI T Y S TAT EM E N T
for POS and POV, indicating severe oxidation degradation in The data that support the findings of this study are available
POSV. For the reasons stated above, it is possible to under- from the corresponding author upon reasonable request.
stand the reduced PD resistance of POSV compared with
POV or POS. O R CI D
Yu Gao https://orcid.org/0000-0002-0493-8421
Jing Li https://orcid.org/0000-0002-7046-0753
5 | CONCLUSIONS Tao Han https://orcid.org/0000-0003-3602-4859
Boxue Du https://orcid.org/0000-0002-7500-1134
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