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Electr Eng
DOI 10.1007/s00202-016-0498-7
ORIGINAL PAPER
Accelerated aging investigation of silicone rubber/silica composites
for coating of high-voltage insulators
Muhammad Amin1 · Abraiz Khattak2,3 · Muhammad Ali4
Received: 26 January 2016 / Accepted: 25 November 2016
© Springer-Verlag Berlin Heidelberg 2016
Abstract Room temperature vulcanized silicone rubber
(RTV-SiR) is a prominent polymeric material for coating
of high-voltage insulators. Like other polymeric materials,
silicone rubber also exhibits aging in outdoor applications.
Silica is one of the most effective additives for properties’
enhancement of polymeric materials. To analyze the effect
of silica on the aging behavior of RTV-SiR, we prepared
its two silica-based composites with 10% micro +5% nano
and 15% microsilica. Prepared samples are subjected to
accelerated stresses such as ultraviolet radiation, acid rain,
heat, and fog for 9000 h in a specially fabricated cham-
ber. For timely analysis of the samples, scanning electron
microscopy (SEM), Fourier transform infrared spectroscopy
(FTIR), leakage current monitoring and Swedish Transmis-
sion Research Institute hydrophobicity analyses are used
along with continuous visual inspection. In the course of
time, all samples showed gradual decrease in transparency.
Increase in leakage current was highest in case of the neat SiR
(SiR-0) and lowest in case of the hybrid composite (SiR-2).
Initial values of leakage current for SiR-0, SiR-1 and SiR-2
B Abraiz Khattak
abraiz.ktk@gmail.com
1 time, advancements in its various aspects for instance shape,
Department of Electrical Engineering, Ghulam Ishaq Khan
Institute (GIKI) of Engineering Sciences and Technology,
Topi, Pakistan
2 Department of Electrical Engineering, COMSATS Institute
of Information Technology (CIIT), Wah, Pakistan
3 Department of Electrical Engineering, City University
of Science and IT (CUSIT), Peshawar, Pakistan
4 Department of Electrical Engineering, University
of Engineering and Technology (UET), Taxila, Pakistan
were 0.5, 0.5 and 0.3 µA, respectively, and after aging the
increased leakage current values were 0.9, 0.8 and 0.6 µA.
From FTIR, the lowest decrease in the intensities of absorp-
tion peaks of important groups in SiR-2 were recorded. In
SiR-0, the peaks of symmetric C–H stretching of CH3 and Si–
CH3 symmetric bending after 9000 h were 91.7 and 94.6%
of virgin, respectively. In SiR-1 and SiR-2, symmetric C–
H stretching of CH3 exhibited an increase which was 120
and 110%, respectively, while Si–CH3 symmetric bending
remained 95% of virgin in SiR-1 and nearly 97% in SiR-2
after 9000 h. Final hydrophobicities of SiR-0 and SiR-1 were
HC-2, while comparatively SiR-1 had higher hydrophobicity
class of HC-1. SEM results also exposed least changes in the
surface of hybrid composite. Silica revealed great impact on
the aging behavior of silicone rubber which was highest in
the case of the hybrid composite.
Keywords Composites · Coating · Aging · SEM · FTIR ·
STRI · Leakage current
1 Introduction
Usage of ceramic insulators dates back to 1880s, while
they were implemented and commercially accessible dur-
ing the last decade of nineteenth century [1,2]. Since the
design, dielectric strength, resistance against flashover, cost
and improvements in other properties were made possible
[2,3]. However, for improvement of surface hydrophobicity
and to minimize leakage current, these insulators are coated
with polymeric material [4].
Due to their organic nature, polymeric materials have the
issue of aging specifically in outdoor environment. Ultra-
violet (UV) radiations, heat, humidity, acid rain and fog
123

are some of the examples of environmental stresses [5–10].
These stresses affect physical, chemical, electrical, thermal
and mechanical properties of polymers [9,11–15].
Room temperature vulcanized silicone rubber (RTV-SiR)
is a frequently recommended material for outdoor HV insu-
lators’ coatings in comparison to other polymeric materials
due to its excellent weathering and heat resistance. It is an
elastomeric organo-siloxane polymer which mainly consists
of silicon with carbon, oxygen and hydrogen. The presence
of hydrocarbon groups makes it an acceptable rubber, while
the Si–O bond imparts its inorganic properties [16–18]. Due
to this hybrid nature, it has excellent insulating properties and
unique hydrophobic behavior [19,20]. RTV-SiR has differ-
ent applications in many fields, e.g., bio-medical engineering,
industrials rolls and coatings of high-voltage insulators, etc.
[21–24]. As the name indicates, RTV-SiR is cured at room
temperature. It is specifically fabricated to obtain SiR with
special features such as flame retardancy. RTV-SiR is pre-
pared by two components, i.e., base and curator [25] and it is
an important class of SiR used for coatings of ceramic insula-
tors to minimize leakage current and enhance hydrophobicity
of overall insulator [26]. RTV-SiR is known for its better
weather resistance in comparison to other polymers and has
good insulating properties. However, it also degrades after
some period in outdoor applications [27,28]. Weathering
resistance of RTV-SiR is needed to be improved to attain
it with extended service life. One of the most efficient ways
to improve the life expectancy of silicone rubber is to obtain
its composites using nano- and micro-fillers.
To obtain polymeric composites with their precise char-
acteristics, they need careful preparation according to the
standard procedures [29]. Moreover, for exploration of envi-
ronmental aging these prepared composites need to be
evaluated under uniform stresses along with neat SiR. In a
review [8], contributions of many authors on aging of silicone
rubber were highlighted; also aging techniques for polymeric
insulators were described. Accelerated multistress weather-
ing (AMW) is an efficient way for assessment of polymeric
materials. AMW is an artificial weathering procedure and is
performed in the laboratory. In comparison to field/natural
aging, AMW not only reduces operation time and cost but
it is also helpful to readily examine the insulators through
different analysis techniques in the laboratory [30].
Few contributions were made on study characteristics
and their improvements for RTV-SiR. However, there are
still gaps in refining performance of RTV-SiR. In [31], only
improvement of hydrophobic behavior for RTV-SiR was dis-
cussed by adding aluminium-tri-hydrate (ATH), and also
stresses other than UV were not taken into account. While in
[32] hydrophobicity, surface charge and flashover character-
istics for only neat RTV-SiR were reported.
There are many types of nano- and micro-fillers that can be
used for properties’ enhancements of silicone rubber [33]. In
123
Electr Eng
some cases, nano/micro-fillers can bring superior enhance-
ments in the required properties of polymers. Different types
of reinforcing fillers can be used for this purpose. By many
researchers, nanocomposites and hybrid composites were
studied [34,35]. Improvements of properties of polymers
depend on size, type and loading of filler. Therefore, further
studies on type and concentration of fillers for SiR are still
required. Among wide range of these fillers, silica (SiO2 ) is
an inorganic filler that provides resistance against thermal,
mechanical and electrical stresses and, thus, can slow the
aging time and enhance the performance of SiR [12,36,37].
The authors of [38] used up to 2 wt% nanosilica and electri-
cal treeing characteristics of RTV-SiR were focused. Other
studies such as [39–41] were conducted on RTV-SiR and
its composites. However, they were specific to particular
property, and also lacked the realistic practical conditions.
Although the previous work done by many authors on RTV-
SiR is a contribution towards its durability, still long-term
study of the silicone rubber in a multistress environment has
not been done. The long-term study is important because
degradation and recovery of polymers are random and unpre-
dictable, and the results may not be reliable on the basis of
short time explorations. Therefore, silicone rubber should
be investigated under multi-stress weathering environment
along with its composites for adequate long time.
Keeping in view the above motivations, we prepared
silica-based micro and micro/nanocomposites of RTV-SiR.
The composites and neat sample are degraded all together
through multiple environmental stresses for 9000 h in a spe-
cially fabricated environmental chamber with reference to the
neat RTV-SiR. Furthermore, leakage current analysis, STRI
hydrophobicity classification, FTIR and SEM are used along
with critical visual inspection to analyze different variations
in the samples.
2 Experimental details
2.1 Preparation of samples
RTV silicone rubber (RTV-615) was procured from Lanxess
Chemicals Co., Germany, microsilica was purchased from
Wuhan Newreach chemicals Co., China and nanosilica
(12nm) was procured from Degussa Chemicals Co., USA.
Composites were prepared according to the percentage
weight (% wt.) of the fillers and polymer. For example, 5%
wt. microsilica composites refer to samples that are made by
mixing 5g of microsilica and 95g of RTV 615 silicone rubber
(having 86.36 g RTV 615-A base polymer) and 8.64 g RTV
615-B curator. The ratio of the base polymer to curator was
kept 10:1 in a sample. The maximum amount of nano-fumed
silica loading was restricted to 5% wt. in hybrid composite.
Electr Eng
Fig. 1 Prepared SiR-0, SiR-1
and SiR-2 samples
Table 1 Samples and their codes
Sample name Sample code Filler concentration (% wt.)
Neat silicone rubber SiR-0 0%
Silicone rubber SiR-1 15% microsilica
microcomposite
Silicone rubber nano/ SiR-2 10% microsilica and
microcomposite 5% nanosilica
A high shear laboratory mixer with a sonicator was used for
the preparation of the silicone rubber composites [42].
The silicone rubber composite samples were prepared in
three steps. In first step, dry fillers were gently added to RTV
615-A, while keeping the mixing speed low to wet out the
fillers. After the fillers got properly wet, the mixing speeds
were gradually increased to the maximum revolution per
minute (rpm) and were kept at the same maximum speed
until the mixture did not show any visible signs of lumps. In
second step, after 2–3 min of cooling, RTV 615-B was added
to the mixture and mixed at low speed for 2 min by a sonicator
and then the mixture was degassed in a vacuum at 27 inHg
until the bubbles were completely removed. In third step,
the silicon rubber mixture was discharged into molds and
allowed to cure at room temperature for 24 h. Subsequently,
the samples were post-cured for 4 h in an oven at 90 ◦ C. List
of the prepared samples is given in Table 1. Photographs of
prepared samples are given in Fig. 1. All the prepared sam-
ples had 80 mm diameter and 3 mm thickness.
2.2 Accelerated aging setup
An environmental chamber with dimensions of 1 m × 2 m ×
1 m was fabricated in which the neat SiR and its composites
were energized with 2.5 kV voltage through 220V/2.5kV
transformer having output current capacity of nearly 100
mA. Schematic diagram of accelerated weathering cham-
ber is shown in Fig. 2a and b shows picture of chamber in
operating conditions.
Different environmental stresses such as controlled ultra-
violet (UV) radiations, temperature, humidity, acid rain and
salt fog were applied timely along with the electrical stress.
To include variable heating stress, 1500 W (max.) heater was
used. For ultraviolet radiations, two UV lights (xenon lamps)
were used, each of 15 W i.e., 15 × 2 = 30 W to make lumi-
nous intensity 1 mW/cm2 as per IEC 61109. The samples
position can be seen in Fig. 2. HCl dilute solution with pH
4.5 was used for acid rain purpose. Two accelerated weather
cycles based on weather data of Hattar were followed during
the experiment, i.e., summer cycle which was of 11 days and
winter cycle which was of 17 days. During summer cycle,
temperature was kept 47.3 ◦ C and in winter cycle it was 35.2
◦ C. The temperature was calculated by taking average of
maximum temperature of a months’ cycle (May–October and
April–September) and adding 11 ◦ C as explained in [43,44].
Summer cycle (11 days) temperature
= 24.3 ◦ C + 11 ◦ C = 35.3 ◦ C
Winter cycle (17 days) temperature
= 36.2 ◦ C + 11 ◦ C = 47.2 ◦ C
Specifications of accelerated weather cycles are shown in
Table 2. Values for other stresses such as pH for acid rain,
salt fog and humidity were applied by finding the appropriate
effect of these stresses in actual environment. Furthermore,
for preparation of this experimental setup, ASTM D2865M-
06, IEC 62217 ed2.0 and IEC-61109 standards were used as
guides.
2.3 Instruments and analysis techniques
2.3.1 Visual inspection
To check the insulators for major degradation or cracking,
each sample was analyzed through a lens under lamp. To
record the surface condition of samples, their photographs
were taken in daylight using a high-resolution digital camera.
2.3.2 Hydrophobicity classification
To measure the degree of water repellency after every
weather cycle, each sample was examined using Swedish
Transmission Research Institute (STRI) hydrophobicity clas-
sification method. A total of 28 hydrophobicity tests were
123
 Electr Eng

Fig. 2 Accelerated multistress

environmental chamber. a
Schematic. b Photographs of
experimental setup

performed. Each sample was sprayed for 20 s with tap
water and then its hydrophobicity was evaluated within 10 s
according to the STRI guide by comparing images of the
samples with the standard images (HC1–HC7). The photos
of sprayed samples were taken with a high-resolution digital
camera.
2.3.3 Leakage current measurement
Alternating leakage current was measured directly using pre-
cision micro-ammeter (UT-70B) after each weather cycle.
Thus, a total of 28 leakage current measurements were
recorded during 9000 h period.

123
Electr Eng

Table 2 Weathering cycles

Applied stress Summer Winter

Test voltage 2.5 kV 2.5 kV

Length of cycle (days) 11 17
Temperature (◦ C) 47.2 35.3
UV-A (h/day) 10 8
Acid rain (4.5 pH) 6 times 2 times
Salt fog (6000 µS/cm) 0 4 times
Relative humidity (%) 85 73

2.3.4 Fourier transform infrared (FTIR) spectroscopy

FTIR spectroscopy was performed to analyze structural

changes in the samples from 0 h (virgin) to 9000 h. For this Fig. 3 Samples’ photographs: a virgin, b 9000 h aged
purpose, spectrographs of samples in absorption form were
obtained through Perkin–Elmer Spectrum 2000 FTIR spec- Table 3 Hydrophobicity class of SiR-0, SiR-1 and SiR-2 from virgin
trometer after each 1000 h. A total of six were obtained for to 9000 h
each sample during 9000 h aging period. In all the tests, S. no. Aging period STRI hydrophobicity class
potassium bromide (KBr) powder was used as a transparent SiR-0 SiR-1 SiR-2
material.
1. 0 (virgin) HC-2 HC-1 HC-1
2.3.5 Scanning electron microscopy (SEM) 2. 264 HC-1 HC-2 HC-1
3. 672 HC-1 HC-1 HC-1
To investigate the surface morphology of virgin and aged 4. 936 HC-1 HC-2 HC-2
samples at micro-level, scanning electron microscopy (SEM) 5. 1344 HC-1 HC-2 HC-2
was used before and after aging. Before subjecting to SEM, 6. 1608 HC-2 HC-2 HC-1
the materials were gold coated. The images were taken at 7. 2016 HC-3 HC-3 HC-2
5 µm scale by applying 20 kV voltage. SEM-Hitachi (SU- 8. 2280 HC-2 HC-3 HC-2
1500) was used for SEM analysis. 9. 2688 HC-1 HC-2 HC-1
10. 2952 HC-2 HC-1 HC-2
11. 3360 HC-2 HC-1 HC-1
3 Results and discussion 12. 3624 HC-2 HC-3 HC-1
13. 4032 HC-2 HC-2 HC-1
3.1 Visual inspection 14. 4296 HC-2 HC-2 HC-1
15. 4704 HC-1 HC-1 HC-1
Major cracking or degradation was not recorded in any sam- 16. 4968 HC-1 HC-3 HC-1
ple during routine visual inspection. All three samples remain 17. 5376 HC-3 HC-3 HC-1
in acceptable condition and look adequate by examining 18. 5640 HC-1 HC-3 HC-1
them through lens under lamp. Opacity of samples increased 19. 6048 HC-3 HC-3 HC-2
gradually with aging as can be seen virgin and 9000 h aged 20. 6312 HC-2 HC-3 HC-1
samples of SiR-0, SiR-1, and SiR-2 from left to right in 21. 6720 HC-2 HC-2 HC-1
Fig. 3a and b respectively. However, color fading of this level 22. 6984 HC-2 HC-2 HC-1
is considered normal in polymeric materials [45,46]. 23. 7392 HC-2 HC-1 HC-2
24. 7656 HC-1 HC-1 HC-1
3.2 Hydrophobicity analysis 25. 8064 HC-1 HC-2 HC-1
26. 8328 HC-1 HC-1 HC-1
Hydrophobicity of each sample was recorded by matching 27. 8736 HC-2 HC-1 HC-1
the samples with standard images of STRI hydrophobicity 28. 9000 HC-2 HC-2 HC-1
guide [47], and recorded as given in Table 3. Images of only
virgin and 9000 h aged samples after hydrophobicity tests are

123

Fig. 4 Images of SiR-0, SiR-1 and SiR-2 for hydrophobicity test
Fig. 5 Images of SiR-0, SiR-1 and SiR-2 for hydrophobicity test
given in Figs. 4 and 5, respectively. Samples are arranged as
SiR-0, SiR-1 and SiR-2 from left to right, respectively. SiR-0
starting from HC-2 showed clear variation in its hydropho-
bicity in which recovery was observed at many points. This
nature of silicone rubber has been previously reported by
many authors and is attributed to the rotation of backbone
chain and transfer of low weight molecules to the surface
[19]. The maximum decrease in the hydrophobicity of SiR-0
was recorded at 6048 h of aging and then recovered to HC-2
while showed HC-1 at 7656 h and maintained this hydropho-
bicity till 8328 h. However, SiR-0 showed its initial value of
hydrophobicity in last two tests, i.e., HC-2. SiR-1 did not
show much variation in hydrophobicity from SiR-0 and it
ended with HC-2. During 4968 and 6048 h, SiR-1 maintained
its hydrophobicity at HC-3; this indicates that microsilica has
no significant influence on the improvement of hydrophobic
behavior. During hydrophobicity analysis, SiR-2 performed
differently than SiR-0 and SiR-1. SiR-2 started from HC-1
and touched HC-2 only 7 times during entire 9000 h aging.
During rest of the tests, it maintained minimum hydropho-
bicity class HC-1. Among all polymeric insulating materials,
silicone rubber has best hydrophobicity property. The loss of
hydrophobicity of SiR is comparatively less, but it also recov-
ers with time. The reasons for this are high bond energy of
siloxane which resist chain scission and also Si–CH3 bond
chain length is greater than hydrocarbon methyl chain of
other hydrocarbons. Furthermore, relatively higher mobil-
ity of backbone chain in SiR also contributes to this unique
behavior [48].
The SiR-2 sample’s improved hydrophobic behavior over
SiR-0 may be due to the strong interaction between silanol
123
Electr Eng
SiR-0
1.1 SiR-1
SiR-2
1.0
0.9
Leakage Current (µA)
0.8
0.7
0.6
0.5
0.4
0.3
0.2
0 1500 3000 4500 6000 7500 9000
Aging Period (Hours)
Fig. 6 Variation in leakage current with increasing aging period
groups present in nanosilica and SiR network, due to which
the main groups of SiR remain intact against stresses. How-
ever, this hydrophobicity may decrease with further increase
in silica loading [49].
3.3 Leakage current analysis
The trend in variations of leakage currents of the SiR-0, SiR-
1 and SiR-2 is given in Fig. 6. From Fig. 2, it can be observed
that like hydrophobicity leakage current for all the samples
varied in complex unpredictable manner. Although not linear
but all the three samples exhibited increase in leakage current
with the decrease in hydrophobicity.
Among all three samples, SiR-0 showed highest values
of LC followed by SiR-1. SiR-2 relatively had overall least
leakage current and at some points it also touched the initial
value of leakage current, i.e 0.3 µA. The maximum values of
leakage current were recorded in all samples nearly 4000 h.
SiR-2 with both nano and microsilica ended with least value
of 0.6 µA.
Although SiR-1 showed little higher values of leakage
current as compared to SiR-2, it performed better than SiR-0
during leakage current analysis. The suppression of leakage
current in composites may be due to the increase in over-
all resistance imparted by silica. Decrease in hydrophobicity
causes higher surface resistivity and, thereby, lowers leakage
current. Like hydrophobicity, the same reasons of changes at
molecular level are responsible for reduced leakage currents
in nanocomposites which are clear from hydrophobicity and
leakage current relation explained in [50].
3.4 Fourier transform infrared spectroscopy
Variation in all wavenumbers occurred which shows continu-
ous chemical changes in both composites and SiR-0. In all the
tests, potassium bromide (KBr) powder was used as a trans-
Electr Eng

Fig. 7 Spectrographs of SiR-0: a virgin, b 1000 h, c 2000 h, d 3000 h, e 4000 h, f 5000 h, g 6000 h, h 7000 h, i 8000 h, j 9000 h

123
 Electr Eng

Fig. 8 Spectrographs of SiR-1. a Virgin, b 1000 h, c 2000 h, d 3000 h, e 4000 h, f 5000 h, g 6000 h, h 7000 h, i 8000 h, j 9000 h

123
Electr Eng

Fig. 9 Spectrographs of SiR-2: a virgin, b 1000 h, c 2000 h, d 3000 h, e 4000 h, f 5000 h, g 6000 h, h 7000 h, i 8000 h, j 9000 h

123
 Electr Eng

virgin after 9000 h

Table 4 Important groups in SiR and relevant absorption bands

Percentage of
Group Wave number (cm−1 )

Symmetric C–H stretching of CH3 ∼2963–2960

91.6
94.5
74.5
Si–CH3 symmetric bending ∼1280–1255

75
70
70
56
Si–O–C stretching ∼1110–1050

9000 h
∼1130–1000

0.055
Si–O–Si asymmetric stretching

0.35
0.35

0.14

0.14
0.6

0.7
Si–O of O–Si(CH3 )3 ∼870–850
Si–O of O–Si(CH3 )2 –O ∼840–790

8000 h

0.055
0.35
0.47

0.15
Si- of Si-(CH3 )3 ∼700

0.6

0.2
1
7000 h

0.05
0.35
0.45
0.65
0.17

0.2
1
parent material. Spectrographs of SiR-0, SiR-2 are given in

6000 h
Figs. 7, 8 and 9, respectively. Important groups in SiR and

0.05

0.75
0.18
0.3
0.4

0.9
0.2
relevant wavenumbers are given in Table 4.
In SiR-0, loss in absorption peaks of symmetric C–

virgin after 5000 h

H stretching of CH3 and symmetric bending of Si–CH3
occurred at ∼2963–2960 and ∼1280–1255 cm−1 , respec-

Percentage of
tively, till 5000 h of aging, but afterwards increases in

81.25
absorption peaks at these wavenumbers were recorded.

83.3
86.5
85.1

75
75
60
The peaks of symmetric C–H stretching of CH3 and Si–
CH3 symmetric bending after 9000 h were 91.7 and 94.6% of

5000 h

0.05
0.32

0.65
0.15
0.75
0.15
virgin, respectively. The increase in C–H bonds on the surface

0.4
is the indication of hydrophobicity recovery which is also
evident from hydrophobicity analysis. The Si–O–C stretch-
ing at ∼1110–1050 cm−1 exhibited decrease in absorption 4000 h

0.05
0.32

0.18
0.82
0.22
0.4
0.7
peak and remained 74.5% of the virgin sample. Similarly,
Si–O–Si asymmetric stretching at ∼1130–1000 cm−1 , Si–O
3000 h

0.325
0.05

0.45
0.82
of O–Si(CH3 )3 at ∼1130–1000 cm−1 , Si–O of O–Si(CH3 )2 –

0.2

0.2
Table 5 Absorption peaks in SiR-0 at relevant wavenumbers from 0 (virgin) to 9000 h

1
O at ∼870–850 cm−1 and Si-of Si-(CH3 )3 at ∼700 cm−1
2000 h

0.045

showed decrease in absorption peaks and at the end of 9000 h

0.27

0.72
0.15
0.92
0.15
0.4

of aging their peaks recorded were 75, 70, 70 and 56% of vir-
gin, respectively. Variation in absorption peaks can be seen
1000 h

0.05
0.35
0.42

0.17
1.05
through data extracted from FTIR spectrographs of virgin to
0.8

0.2
Absorbance

9000 h aged samples of SiR-0 given in Table 5.

Virgin

FTIR analysis for SiR-1 showed that absorption peak at

0.06
0.37
0.47

0.25

∼2963–2960 cm−1 exhibited gradual increase, which shows

0.8
0.2
1

transfer of hydrophobic methyl group from material bulk

∼2963–2960
∼1280–1255
∼1110–1050
∼1130–1000

to the surface. Similarly, though initial decrease in Si–CH3

Wave-band

∼870–850
∼840–790

symmetric bending was greater, it recovered and showed 5%

∼700

decrease at the end of 9000 h.

Si–O–C stretching showed 23.7% decrease which is lesser
in comparison to SiR-0. At the end of 9000 h, absorp-
Symmetric C–H stretching of CH3

tion peaks at Si–O-Si asymmetric stretching at ∼1130–

Si–O–Si asymmetric stretching

1000 cm−1 , Si–O of O–Si(CH3 )3 at ∼1130–1000 cm−1 ,

Si–CH3 symmetric bending

Si–O of O–Si(CH3 )2 –O at ∼ 870–850 cm−1 and Si- of Si-

Si–O of O–Si(CH3 )2 –O

(CH3 )3 at wavenumber ∼700 were 80, 74, 74.5 and 75%

Si–O of O–Si(CH3 )3
Si–O–C stretching

of virgin, respectively. Variation in the absorption peaks can

Si- of Si-(CH3 )3

be seen through data extracted from FTIR graphs of virgin

to 9000 h aged samples of SiR-1 given in Table 6. SiR-2
Group

showed slightly higher absorption peaks related to impor-

tant groups as compared to SiR-1. Like SiR-1 at the end of

123
 Electr Eng

Table 6 Absorption peaks in SiR-1 at relevant wavenumbers from 0 (virgin) to 9000 h

Group Wave-band Absorbance

Virgin 1000 h 2000 h 3000 h 4000 h 5000 h Percentage of 6000 h 7000 h 8000 h 9000 h Percentage of
virgin after 5000 h virgin after 9000 h

Symmetric C–H stretching of CH3 ∼2963–2960 0.05 0.05 0.11 0.05 0.07 0.055 110 0.05 0.05 0.07 0.07 120
Si–CH3 symmetric bending ∼1280–1255 0.42 0.3 0.35 0.32 0.35 0.4 95.2 0.32 0.32 0.35 0.42 95.2
Si–O–C stretching ∼1110–1050 0.55 0.45 0.47 0.45 0.47 0.45 81.8 0.41 0.45 0.47 0.45 76.4
Si–O–Si asymmetric stretching ∼1130–1000 0.9 0.77 0.75 0.77 0.82 0.605 67.2 0.75 0.85 0.82 0.85 80
Si–O of O–Si(CH3 )3 ∼870–850 0.27 0.19 0.25 0.2 0.19 0.19 70. 0.17 0.18 0.2 0.2 74.07
Si–O of O–Si(CH3 )2 –O ∼840–790 1.1 0.95 0.92 0.97 0.97 0.9 81.8 0.9 1.0 0.95 0.95 74.5
Si- of Si-(CH3 )3 ∼700 0.28 0.2 0.26 0.18 0.21 0.22 78.5 0.18 0.2 0.21 0.21 75

Table 7 Absorption peaks in SiR-2 at relevant wavenumbers from 0 (virgin) to 9000 h

Group Wave-band Absorbance

Virgin 1000 h 2000 h 3000 h 4000 h 5000 h Percentage of 6000 h 7000 h 8000 h 9000 h Percentage of
virgin after 5000 h virgin after 9000 h

Symmetric C–H stretching of CH3 ∼2963–2960 0.05 0.05 0.12 0.05 0.055 0.055 110 0.06 0.05 0.055 0.06 120
Si–CH3 symmetric bending ∼1280–1255 0.32 0.3 0.37 0.32 0.255 0.257 80.3 0.255 0.255 0.302 0.31 96.88
Si–O–C stretching ∼1110–1050 0.45 0.45 0.52 0.45 0.357 0.4 89 0.352 0.355 0.402 0.4 88.9
Si–O–Si asymmetric stretching ∼1130–1000 0.77 0.77 0.85 0.77 0.557 0.65 84 0.605 0.657 0.7 0.6 77.92208
Si–O of O–Si(CH3 )3 ∼870–850 0.19 0.17 0.25 0.18 0.158 0.152 80 0.152 0.155 0.155 0.15 78.94737
Si–O of O–Si(CH3 )2 –O ∼840–790 0.97 0.97 1 0.95 0.7 0.75 77.3 0.705 0.75 0.752 0.7 72.16495
Si- of Si-(CH3 )3 ∼700 0.21 0.17 0.25 0.2 0.205 0.157 74.7 0.155 0.2 0.157 0.16 76.19048

123

Fig. 10 SEM images. a Samples before and after 9000 h aging. b Magnified SiR-0. SiR-1 and SiR-2 after 9000 h
9000 h, aging period hydrophobic methyl group at ∼2963–
2960 cm−1 increased which is also clear from hydrophobic
analysis and Si-CH3 ∼1280–1255 cm−1 remained almost
97% of the virgin. Variation in the absorption peaks can be
seen through data extracted from FTIR spectrographs of vir-
gin to 9000 h aged samples of SiR-0 given in Table 7.
Only 11% loss in the absorption peak occurred at
∼1110–1050 cm−1 which represents Si–O–C stretching.
Other important groups also degraded lesser comparative
to SiR-0 and SiR-1. At the end of 9000 h of aging absorp-
tion peaks of Si–O–Si asymmetric stretching at ∼1130–
1000 cm−1 , Si–O of O–Si(CH3 )3 at ∼1130–1000 cm−1 ,
Si–O of O–Si(CH3 )2 –O at ∼870–850 cm−1 and Si- of Si-
(CH3 )3 at wavenumber ∼700 were 77.9, 78.9, 72.16 and 76%
of virgin, respectively. Variation in the absorption peaks can
be seen through data extracted from FTIR graphs of virgin
to 9000 h aged samples of SiR-2. In composites, least loss
of important hydrocarbons and minimum impact of oxida-
tion are due to the intactness provided by hydrogen bonding
of silanol groups of silica and oxygen atom of backbone
chain in SiR [51–53]. The second reason for good hydropho-
bic behavior of nanocomposite is due to the interaction of
acidic Si–OH group with polymer groups, which reduces the
swelling of polymer and water resistive interface is formed
between nanosilica and the main polymer [54,55].
123
Electr Eng
3.5 Scanning electron microscopy (SEM)
To analyze the surface topography of samples at micro-level
before and after aging, scanning electron microscopy (SEM)
was used. SiR-0 which is neat RTV-SiR showed signifi-
cant material loss and erosion as a response to application
of stresses for 9000 h. SiR-1 which is a microcomposite
showed less surface degradation in comparison to neat sam-
ple. SiR-0 ended with loss of materials along with minor
holes and ruptures. After 9000 h of accelerated aging, sur-
face of SiR-0 showed higher degradation in comparison to
SiR-1 and SiR-2. Although SiR-1 affected less as compared
to SiR-0, SiR-2 had better surface intactness than SiR-1.
In SiR-1 surface erosion was slightly higher than SiR-2.
This is due to the fact that nanosilica has better interac-
tion with polymer matrix in comparison to microsilica. After
aging, fillers in SiR-1 were relatively highly exposed in com-
parison to SiR-2. In Fig. 10a, SEM images of virgin and
9000 h aged samples are given. Figure 10b shows magni-
fied SEM image of the samples after 9000 h aging. Large
specific surface area of nanosilica with abundance of silanol
(Si–OH) groups provides intactness to the functional groups
of SiR, which may cause in lower loss of material from
surface of the SiR-2 [56]. Among all the three samples,
SEM results showed that surface of the sample without silica
Electr Eng
(SiR-0) affected more in comparison to silica-based compos-
ites.
4 Conclusions
To investigate the aging characteristics of silicone rubber
composites, microsilica and nano/microsilica-based com-
posites were prepared and tested for 9000 h in a specially
fabricated aging chamber under multiple stresses along with
neat SiR. Silica was found effective in bringing improve-
ments in aging behavior of silicone rubber. In case of
addition of both nanosilica and microsilica, this improve-
ment was profound. Relatively best hydrophobic behavior
and least leakage currents were recorded for hybrid com-
posite. Similarly, FTIR results also showed least reductions
in intensities of important hydrocarbon groups of hybrid
composite. SEM results also concurred with other investi-
gatory techniques. Neat SiR was found with lower aging
resistance in comparison to both composites. Microcompos-
ite performed moderate. At the end of 9000 h aging hybrid
composite had leakage current of 0.6 µA, hydrophobicity
class HC-1 and comparatively had less loss in methyl groups
and organo-silicon bonding. In SiR-2, Si–CH3 and Si–O–
C reduced only 11 and 4%, respectively. From this work,
it was found that decrease in the surface quality of SiR
and its composites contribute to loss in hydrophobicity, loss
of important hydrocarbons and increase in leakage current.
Promising results were obtained for SiR/silica composites
aimed at their usage in high-voltage insulation. However,
further exploration of influence of environmental stresses on
the mechanical, dielectric and other physical properties of
these composites is necessary.
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