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Micro Characterization and Degradation Mechanism of Liquid Silicone Rubber

Used for External Insulation

Article in IEEE Transactions on Dielectrics and Electrical Insulation · February 2015

DOI: 10.1109/TDEI.2014.004188

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IEEE Transactions on Dielectrics and Electrical Insulation Vol. 22, No. 1; February 2015 313

Micro Characterization and Degradation Mechanism

of Liquid Silicone Rubber Used for External Insulation
Can Chen, Zhidong Jia, Xilin Wang, Hai Lu, Zhicheng Guan
Laboratory of Advanced Technology of Electrical Engineering and Energy
Graduate School at Shenzhen, Tsinghua University
Shenzhen, Guangdong, 518055, P. R. China
and Cuiru Yang
Guangdong Electric Power Research Institute
Guangzhou, Guangdong, 510600 P. R. China

ABSTRACT
In recent years, some hollow core composite insulators, of which housings were made of
liquid silicone rubber (LSR) of current and voltage transformers used in China
Southern Power Grid have showed different levels of degradation and cracking
phenomena. Based on SEM, FTIR, XPS and XRD methods, analyses have been
conducted from several aspects such as organic functional groups concentration,
microscopic appearance, element valence etc. It is found that organic groups (mainly
Si-(CH3)2) on the side-chains of LSR are much more vulnerable than the backbone
during the degradation process, thus Si-O/Si-C absorption peak ratio could be applied
to characterize the degradation level of LSR. For severely aged LSR samples, the ratio
is around 1.787-2.436. The valences of Si element and Si-O, Si-C functional group
relative concentration of the aged LSR surface have changed and crystal structure is
formed. Macro properties tests show that the surface of aged LSR is almost hydrophilic
and tracking and erosion resistance is deteriorated remarkably. It is concluded that the
crystallization caused by thermal/optical oxidation over crosslinking reaction is the
main reason why degradation occurred.
Index Terms - Liquid silicone rubber, cracking, degradation, cross-linking reaction,
crystallization

1 INTRODUCTION core composite insulators of current and voltage transformers

which have already been widely used in substations of voltage
HOLLOW core insulators are used in electrical apparatus level ranging from 110 kV to 500 kV in China Southern Power
in substations like surge arrestor, circuit breaker etc. [1-3]. In Grid, as shown in Figure 1. However, in recent years, some
recent years, hollow core insulators of which the housing hollow core composite insulators showed different levels of
formed from silicone rubber have been more and more widely chalking and cracking phenomena which lead to the loss of
applied due to its excellent performance of anti-pollution hydrophobicity and mechanical strength decrease. Typical
flashover, explosion-proof and mechanical stability [4-6]. For cracking and chalking phenomena are given in Figure 2.
insulators on overhead transmission line, the housing material
is all made of HTV silicone rubber [7-9]. However, as far as
hollow core composite insulator is concerned, the housing
could be formed from HTV silicone rubber as well as liquid
silicone rubber [4,10].
Liquid silicone rubber (LSR) is a type of silicone rubber
which is quite different from the traditionally used HTV silicone
rubber. LSR for application to high voltage insulators is addition
reaction-curable and no inorganic fillers are used such as ATH
or quartz [11,12]. It is “liquid” because of its low viscosity and
good fluidity. LSR is applicable for casting or injection molding
process [13], making it a good choice for the housing of hollow 110 kV transformer 500 kV transformer
(In service) (out of service)
Manuscript received on 7 July 2013, in final form 12 March 2014,
accepted 21 May 2014. Figure 1. LSR hollow core composite insulators.

DOI 10.1109/TDEI.2014.004188
314 C. Chen et al.: Micro Characterization and Degradation Mechanism of Liquid Silicone Rubber Used for External Insulation

The electric field strength distribution was simulated by

using Ansoft software for it is known that the range of electric
field strength variation along the hollow core insulators is
very large. The simulation results are shown in Figure 4.

(a) SVS 123 voltage transformer (b) SAS 550 current transformer
Figure 2. Typical cracking on LSR housing and sheds.

2 SAMPLES
A layered structure is observed by dissecting the shed of
LSR insulator and is shown in Figure 3. An aged shed could
be divided into 3 layers. The surface of the shed is white and
opaque. Non-recoverable cracks are formed when bending the
shed. This part, with a thickness of 0.3-0.5 mm, is called the
chalking layer. Inside the chalking layer, LSR shed is
relatively transparent and the color is much lighter than the
(a) Voltage distribution (b) Electric field distribution
surface. This part is called the transition layer. Inside this Figure 4. Voltage and electric field strength distribution trend along the
layer is the core part of shed and is called the non-chalking insulator.
layer, of which all the properties of LSR are maintained.
The voltage and electric field strength distribution trend are
given in Figure 4 and the authors believed that the electric
field strength should be taken into consideration when
studying the degradation phenomena of LSR hollow core
composite insulators. As a result, samples were collected from
several sheds including the top part, middle part and bottom
part. Samples from SVS123 were numbered as A1, A2, A8,
A9, A16 and A17 and Samples from SAS 550 were numbered
as B1, B2, B35, B36, B69 and B70 respectively according to
Figure 3. Cutaway view of shed with cracking phenomenon.
the sheds they were collected from. Typical cracking
phenomena of the collected samples are shown in Figure 5.
In order to study the properties and the micro structure of
aged LSR hollow core composite insulator, 2 types of samples,
type A and B are used. All samples involved in this paper were
collected from current transformers and voltage transformers
which have been in service for years. Sample A were collected
from a SVS123 SF6 voltage transformer which was
manufactured in Sept. 2004. Sample B were collected from a
Cracking on the upper surface of Cracking on the lower surface of
SAS550 SF6 current transformer which was manufactured in
Sample A1 Sample B1
Feb. 2003. All samples were collected in June, 2011 when these
two insulators had already been out of service. The parameters
of these two types of transformers are shown in Table 1.
Table 1. Parameters of transformers.
Standard
Transformer Max.System Min.Flashover Diameter of Number
creepage Cracking on the lower surface of Cracking on the upper surface of
Type Voltage (kV) distance (mm) Sheds (mm) of Sheds
distance Sample A9 Sample B36
SVS123 123 1216 2880 450 17
SAS550 550 3728 10155 900 70

All sheds were numbered from top to bottom in order to

clarify their positions. For instance, Sample A17 is a sample
collected from the bottom shed of SVS123 voltage
transformer and Sample B1 is a sample collected from the top
Cracking on the upper surface of Cracking on the upper surface of
shed of SAS550 current transformer. All samples are the edge Sample A17 Sample B70
part of sheds. Figure 5. Typical cracking phenomena of the collected samples.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 22, No. 1; February 2015 315

An optical microscope is used to study the differences
between these two types of LSR sample. Figure 6 shows the
typical optically magnified images of Sample A and Sample B.
A thickness gauge is used to measure the thickness of
chalking layer and the measurement results of mean thickness
of all samples are shown in Table 2.
could be acquired with a clean specimen pressed against the
crystal plate of the instrument. As the thicknesses of
specimens (2-3 mm) are much bigger than the penetration
depth of infrared light (<100 m), the height of absorbance
peak of a certain functional group could be used to study the
relative abundance quantitatively and the results are
comparable among several specimens.
FTIR spectra are used to analyze the existing forms of
certain groups [14-16], as is shown in Table 3.

Table 3. Characteristic absorption peak of FTIR spectrum.

Wave number
Functional group Characteristics
（cm-1）
-CH3 ~2960 stretching vibration
1613 C=C stretching vibration
1410-1390 CH=CH2 scissoring vibration
Si-CH=CH2
1020-1000 Trans C-H wagging vibration
980-950 CH2 wagging vibration
CH3 symmetrical deformation
1266,1250 vibration，double peak
Si-(CH3)3
840,765 CH3 rocking vibration, Si-C
stretching vibration,
Sample A Sample B CH3 symmetrical deformation
Figure 6. Chalking layer on the surface of the LSR shed. vibration，sharp single peak
~1260
Si-(CH3)2 CH3 rocking vibration, Si-C
855,800
stretching vibration，strong
Table 2. Thickness of chalking layer of Sample A and B.
absorption
Chalking layer thickness (mm） condensation OH stretching
3390-3200 vibration
Sample Si-OH
Shed edge Shed root 910-830 Si-O stretching vibration，
Identification
wide peak
Upper Lower Upper Lower Si-O stretching vibration，
surface surface surface surface
Si-O-Si (linear) 1080,1025 strong absorption，two similar
A 0.35 0.19 0.28 0.23 peaks
Si-O stretching vibration，
B 0.23 0.14 0.13 0.15 Si-O-Si (ring) ~1020, 1090
strong absorption
Measuring results show that chalking layer at the edge of
sheds is thicker than the root and chalking layer on the upper It is shown in Figure 7 that the heights of absorption peak
surface is thicker than the lower surface. are negatively correlated to the degradation level. The lower
It is concluded from the thickness of chalking layer and the peaks are, the more serious the ageing is.
microscope pictures that the degradation level of Sample A is Considering the spectrum of non-chalking layer in Figure 5,
much more serious than that of Sample B. no absorption peaks are found at 3390-3200 cm-1, which
means there is no Si-OH bond in LSR. High absorbance peaks
at 786 cm-1 and 864 cm-1 demonstrate the existence of Si-CH3.
3 MICROSTRUCTURE ANALYSIS The sharp, single peak at 1008 cm-1 is a symbol of the
In order to study the micro structural changes which led to presence of Si-O cross-linked system. The spectra of chalking
the loss of hydrophobicity and decrease of mechanical layers, however, are quite different. Absorbance of Si-O and
strength, several material analysis methods are utilized, Si-C bond is much lower and Si-O peak is much wider, which
including SEM, FTIR, XPS and XRD analysis. demonstrates that the Si-O chain is longer and cross-linking
system has changed.
3.1 FUNCTIONAL GROUP It is concluded from Figure 7 that the abundance of Si-O
The major component of LSR is polydimethylsiloxane and Si-C bonds in both Sample A and Sample B has declined
(PDMS), which means that Si-O and Si-C bond should be by a large scale. And it is also noticed that the shape of Si-O
given priority to characterize the micro change of LSR absorption peaks in chalking layer differs greatly from that in
samples. ATR-FTIR method is utilized to study the abundance non-chalking layer. Thus, further study has been conducted by
of functional groups in Sample A and B. using inclined plane test based on IEC 60587 to compare the
The advantage of ATR-FTIR is that no particular FTIR spectra of aged sample and arc-ablated sample, as is
preparation is required and the functional group information shown in Figures 7 and 8 respectively.
 316 C. Chen et al.: Micro Characterization and Degradation Mechanism of Liquid Silicone Rubber Used for External Insulation

In Figure 8, all the absorption peaks are much lower than similar. A similarity analysis has been conducted, as is
those of non-chalking layer, demonstrating the reduction of shown in Table 4.
Si-O and Si-C bond. But the shapes of the peaks are very The absorption peaks decline in both aged and arc-
1.2 0.9
ablated samples. However, a major difference between
Si(CH)2
these two kinds of samples is that the Peak 2 to Peak 3 ratio.
The ratio of aged samples is 1.787-2.436; the ratio of arc-
Si-O-Si
0.9
Sample A1 Non-chalking layer 0.6
Sample A1 Chalking layer Sample B1(Non-chalking layer) ablated samples is 1.066-1.073; and the ratio of un-aged
Absorbance

Sample B1(Chalkin layer)

Absorbance
sample is 0.901-0.912.
0.6

Si-CH3
0.3

0.3
C-H in Si-CH3
The result reflects an important characteristic of the
0.0
degradation of LSR: Si-C bond absorption peak declines
0.0

4000 3000 2000 1000

much faster than Si-O bond absorption peak, which
demonstrates the organic groups (mainly Si-(CH3)2) on the
4000 3000 2000 1000
-1
Wave number(cm )
-1 Wavenumber(cm )

(a) Spectra of Sample A1 (b) Spectra of Sample B1 side-chains are much more vulnerable than the backbone.
1.2 1.4
The height of absorption peaks is a very important index
to assess the degradation level of LSR samples for the
1.2

0.9 1.0
Sample B69(Non-chalking layer)
Sample A17 (Non-chalking layer) 0.8
Sample B69(Chalking layer) infrared detecting technology applied in this paper is ATR-
Sample A17 (Chalking layer)
FTIR, as mentioned in the second paragraph of Section 3.1.
Absorbance
Absorbance

0.6
0.6

0.3
0.4
As a result, the percentage decline of Peak 3 could be
0.2

0.0
calculated to quantify the degradation level of LSR. The
0.0
-0.2
non-chalking layer of Sample A and Sample B could be
regarded as un-aged samples and the decline percentage of
4000 3000 2000 1000 4000 3000 2000 1000
-1
Wavenumber(cm )
-1
Wavenumber(cm )

(c) Spectra of Sample A17 (d) Spectra of Sample B69

Peak 3 could be calculated respectively. The decline
Figure 7. FTIR spectra of internal silicone rubber material percentage of Sample A1 and Sample B69 is 88.9% and
transient layer and surface chalking layer. 88.1%, indicating a sharp reduction of organic functional
0.6
groups during the degradation process.

0.5 Sample A interior part 4.5kV

Sample B interior part 3.5kV 3.2 MICROSCOPIC APPEARANCES
LSR powder
0.4 Scanning electron microscope (SEM) is used to study the
microscopic appearances of LSR samples. Figure 7 shows the
Absorbance

0.3 microscopic appearances of 5 samples. The magnification

from top to bottom is 1,000, 5,000 and 10,000 respectively.
0.2
The micro structure of chalking layer of both Sample A and B
0.1
is loose and porous. Cracks are found on the surface. The non-
chalking layer is much more compact and dense. The surface
0.0 is not as smooth as the new LSR sample, raised areas are
observed in the non-chalking layer of Sample A and Sample B
3500 3000 2500 2000 1500 1000 500 0
-1
images but no cracks are found. It could be concluded that the
Wave nunber(cm )
Figure 8. FTIR spectra of liquid silicone rubber samples after the inclined
degradation process is going on the surface as well as the
plane test. interior part.

Table 4. Values of typical absorption peaks of FTIR spectra.

Peak 1 Peak 2 Peak 3

Sample Identification
-1 -1
Wave number (cm ) Absorbance Wave number(cm ) Absorbance Wave number(cm-1) Absorbance

New LSR sample 1257.55 0.339 1008.74 1.025 786.93 1.169

Un-aged Sample A1 (Non-chalking layer) 1257.55 0.310 1008.74 0.951 786.93 1.043

Sample B69 (Non-chalking layer) 1257.54 0.336 1008.73 1.133 786.93 1.258

Sample A 4.5kV 1259.47 0.073 1012.59 0.192 792.72 0.179

Arc-ablated Sample B 3.5kV 1259.47 0.133 1008.74 0.346 788.86 0.324

LSR powder / / 1097.46 0.416 804.29 0.118

Sample A1 (chalking layer) 1259.47 0.030 1068.53 0.207 796.57 0.116

Aged
Sample B69 (chalking layer) 1261.40 0.036 1060.81 0.366 798.50 0.150
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 22, No. 1; February 2015 317

Sample A8 Sample B35 Sample A8 Sample B35

New LSR sample
Non-chalking layer Non-chalking layer Chalking layer Chalking layer

Figure 9. SEM figures of chalking and non-chalking layer of LSR samples.

An overlapping peak resolving analysis is carried out

3.3 ELEMENT VALENCE
[20]. The resolving result and corresponding resolved peak
X-ray photoelectron spectroscopy (XPS) is a commonly area is shown in Figure 10 and Table 7 respectively. The
used analysis method which could be used to measure the resolved peak of Si(-O)1, Si(-O)2, Si(-O)3, and Si(-O)4, are
elemental composition, empirical formula, chemical state and numbered as Peak 1 , Peak 2, Peak 3 and Peak 4
electronic state of the elements that exist within a material respectively.
[17, 18]. In order to study the variation trend of elemental
composition and chemical state of Si, O and C from the
chalking layer to the non-chalking layer, a stratified sampling
method were utilized. Surface layer (chalking layer), Raw Intensity
Raw Intensity
Peak 1

superficial layer (0.4-0.6 mm deep, transition layer) and deep Peak 1

Peak 2
Peak 2
Peak 3
Peak 3
layer (1 mm deep, non-chalking layer) were sampled Peak 4
Peak 4

respectively from Sample A and B. The relative content of Si,

O and C element is shown in Table 5 and a similar
distribution law of element content in both Sample A and
Sample B is conducted.
96 98 100 102 104 106 108 110 112 114 96 98 100 102 104 106 108 110 112 114
B.E.(eV) B.E.(eV)

The content of C element increases as the content of O Sample A16 Surface layer Sample B70 Surface layer
element decreases as the sampling goes on from surface layer
to deep layer. XPS results shows that the chalking layer of
Sample A is thicker than that of Sample B and XPS analysis Raw Intensity
result shows that the relative content of C element in surface Peak 1
Peak 2
Raw Intensity
Peak 1
Peak 2
layer in Sample A is lower than that in Sample B whereas O Peak 3
Peak 4 Peak 3
Peak 4
element in the opposite way. The lower the content of C is,
the lower the content of organic components is.
Table 5. Relative content of Si, C, O in LSR samples (%).
94 96 98 100 102 104 106 108 110 112 96 98 100 102 104 106 108 110 112 114
Sample Identification Si C O B.E.(eV) B.E.(eV)

Surface layer 32.9 19.9 47.2 Sample A16 Superficial layer Sample B70 Superficial layer
Sample A superficial layer 22.1 51.4 26.5
deep layer 21.8 51.9 26.3
Surface layer 24.2 37.4 38.4
Sample B superficial layer 26.1 48.6 25.3 Raw Intensity Raw Intensity
Peak 1 Peak 1
deep layer 22.6 53.3 24.1 Peak 2 Peak 2
Peak 3 Peak 3
Peak 4 Peak 4

Based on the study of Alexander [19], the number of O

atoms bound to the Si atom could determine the binding
energy of Si2p and the corresponding binding energies of
certain Si-O structures are shown in Table 6. 96 98 100 102 104 106
B.E.(eV)
108 110 112 114 94 96 98 100 102 104
B.E.(eV)
106 108 110 112

Sample A16 Deep layer Sample B70 Deep layer

Table 6. Different Si-O units and their corresponding binding energies.
(a) Resolved peaks of Sample A (b) Resolved peaks of Sample B
Structure Si(-O)1 Si(-O)2 Si(-O)3 Si(-O)4
Binding Energy (eV) 101.5 102.1 102.8 103.4 Figure 10. Peak analysis of Si2p peak in A,B samples.
 318 C. Chen et al.: Micro Characterization and Degradation Mechanism of Liquid Silicone Rubber Used for External Insulation
Table 7. Relative content of Si-O structures (%). diffraction peak distribution with the surface layer of Sample A,
Sample Identification Si(-O)1 Si(-O)2 Si(-O)3 Si(-O)4 as shown in Figure 12. Alpha-cristobalite is a crystal form of
Peak Identification Peak 1 Peak 2 Peak 3 Peak 4
mineral cristobalite, which is a high-temperature polymorph of
Surface layer 1.3 0.5 24.8 73.5
Sample
superficial layer 14.6 30.3 14.8 40.4 silica.
A16
deep layer 52.1 15.6 12.4 20.0
Surface layer 23.6 15.1 28.3 33.0 A Chalking layer A Chalking layer
Sample superficial layer 38.1 13.7 14.0 34.2 cristobalite cristobalite
B70
deep layer 25.5 30.2 20.6 23.7

In the surface layer of Sample A, the Si(-O)1 peak and Si(-O)2

peak account for only 1.8% of total area whereas Si(-O)4 peak
accounts for 73.5%；In the deep layer of Sample A, Si(-O)1
peak accounts for 52.1% of total whereas Si(-O)4 peak
accounts for only 20.0%. It is found that from the surface to 10 20 30
Type (2)
40 50 10 20 30
Type (2)
40 50

the interior part, the content of Si(-O)1 increases whereas Si(- Figure 12. Comparison Diagram of XRD spectra between Sample A and cristobalite.
O)4 decreases significantly. Based on Scherrer formula, it is able to calculate the grain
It is also found in Sample B that Si(-O)4 peak accounts for size of samples. The grain size of Sample A is 29.2 nm and
33.0% in surface layer whereas in deep layer accounts for Sample B is 28.3 nm, about the same size of -cristobalite,
23.7%, decreased by about 10%. which belongs to tetragonal system with four SiO2 units in one
It is concluded from the XPS analysis results that as the unit cell.
degradation process goes on, the crosslinking degree of Si-O The existence of crystal structure is a symbol of the
chain raises, which will result in the reduction of organic formation of Si(-O)4 units , which is a crystallization process
groups such as Si-C bond and CH3 and this could lead to the as well as a crosslinking-degree-rising process.
loss of hydrophobicity and mechanical performance reduction.
It also means that the micro structure of LSR has changed. 4 DEGRADATION MECHANISM ANALYSIS
The aim of microstructural analysis is to establish a
3.4 MICRO STRUCTURE
X-ray Diffraction (XRD) analysis is a method in which X- mapping between micro condition parameters and macro
ray is used to study the diffraction spectrum of samples, which performance parameters of insulation materials. Thus, macro
reflects the crystal structure in samples. Based on analysis properties such as hydrophobicity, mirror glossiness, Shore
conducted in 3.4, it is believed that the inorganic component in hardness and tracking and erosion resistance are tested.
aged LSR has increased significantly and crystal structure Comparisons between Sample A and B are conducted and
could be observed. The XRD spectra of Sample A and Sample results show that the degradation level of Sample A is much
B are shown in Figure 11. 4-5 sharp diffraction peaks could be more serious than that of Sample B, which also reconfirmed
observed in the surface layer of samples whereas in internal the results of micro structural analysis.
part, only 1-2 diffraction peaks could be observed. Table 8. Macro properties of LSR samples.
A B New LSR
Hydrophobicity HC7 HC6-HC7 HC1
B Chalking layer
A Chalking layer B Non-chalking layer Shore hardness (HA) 54.40 53.42 37.7
A Non-chalking layer
Mirror glossiness (GS 60
＜10 20-30 60-75
°)
Tracking and erosion Fail Pass TMA2.5, fail Pass
resistance TMA2.5 TMA3.5 TMA4.5

Based on the results, it is able to analyze the differences

10 20 30 40 50 10 20 30 40 50
between the aged and new LSR samples. The change of
Type(2) Type() properties and performances are listed in Table 9.
Sample A17 Sample B70
Figure 11. XRD spectra of A and B samples. Table 9. Property changes of LSR
Properties and
The sharpness of peaks defines the existence of crystal New to Aged
Performances
structure and the distribution of peaks defines the crystal type. Hardness(HA) Increase
Compared with spectra of internal samples, the diffraction Mirror glossiness Decrease
peaks of surface layer samples are sharper and clear, which Hydrophobicity Decrease
indicates that crystal structure is formed in these samples. In SEM Smooth and compact  Loose and porous
order to study the crystal type and element composition, FTIR Si-C peak declines, Si-O/Si-C peak ratio increases
retrieval based on diffraction peak angle and element C content decreases, O content increases, Si(-O)4
XPS
composition was processed in the Cambridge Structural content increases
Database [21]. It is believed that the possible chemical TGA
Thermal stability decreases, weight loss peaks
change
formulas of these crystal structures are SiO2 and Al2O3, and the
XRD Occurrence of crystal structure
searching result shows that alpha-cristobalite has the same
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 22, No. 1; February 2015 319

According to the tests results in session 3.4 and 3.5, it

could be concluded that the main changes occurred in
aged LSR samples are due to the rise of crosslinking
degree and formation of crystal structure, which are the
main internal reasons why organic part in LSR decreased.
Environment factors such as heat, strong sunlight and
oxygen could lead to the formation of oxygen free
radicals and these free radicals are easy to react with Si-
C bond, which causes the dropout of -CH 3 or other
organic functional groups and the formation of new
crosslinking points. As a result, the organic part in LSR
is becoming lower and lower and the crosslinking degree
is rising. The reaction [22] is shown in Figure 13.
It is concluded that the crystallization caused by over
crosslinking reaction is the main internal reason why
LSR hollow core composite insulators aged. As far as the
same kind of polymer is concerned, the larger the
molecular weight is, the slower the crystallization is. The
molecular weight of HTV silicone rubber used to
manufacture composite insulator is ranging from 450,000
to 700,000 [23] whereas that of LSR is less than 200,000
in order to maintain its low viscosity. Besides, the Shore
Hardness of LSR is about 40HA, much lower than that of
HTV silicone rubber, which shows that the crosslinking
degree of LSR is relatively low. According to [24, 25],
low molecular weight and low crosslinking degree are all
advantages in the crystallization process of polymer.
On the other hand, as far as external factors are
concerned, the aged hollow core composite insulators of
CT and VTs are all used in the southern coastal area of
CH3 CH3 CH3 CH3
China with a hot and humid climate, which could
accelerate the thermal oxidation process and lead to the
Si O Si O Si O Si O degradation of LSR.
Thus, it is recommended that silicone rubber featuring
CH3 CH3 OH low molecular weight or low crosslinking degree is better
CH2O
not to be used in areas where the climate is hot and
H C H
humid. If these kinds silicone rubber are not substitutable
CH3 CH3 OH
due to certain reasons, corresponding examining and
monitoring work should be guaranteed in case the
Si O Si O Si O Si O material is aged.

CH3 CH3 CH3 CH3

Figure 13. Chemical reaction of LSR degradation process.
5 CONCLUSIONS
The results of FTIR showed that Si-C bond absorption
peak declined much faster than Si-O bond absorption
peak, which demonstrated that the organic groups
(mainly Si-(CH3) 2) on the side-chains were much more
vulnerable than the backbone during the degradation
process. It also demonstrated that electric arc ablation
was not the cause of LSR degradation.
XPS analysis results showed that the crosslinking
degree of Si-O chain rose as the degradation process
went on, resulting in the reduction of organic groups
such as Si-C bond and CH3. This could lead to the loss of
hydrophobicity and mechanical performance reduction.
The relative content of C and O also changed during the
process.
320 C. Chen et al.: Micro Characterization and Degradation Mechanism of Liquid Silicone Rubber Used for External Insulation
XRD results showed that crystal structure was formed
in the aged LSR samples. The structure was very similar
to that of -cristobalite.
Comparisons between Sample A and Sample B showed
that FTIR, XPS and XRD analysis methods could be used
to characterize the degradation level of LSR.
Low molecular weight and crosslinking degree of LSR
were internal causes of crystallization. In hot and humid
environment, large molecular weight and high crosslinking
degree silicone rubber was recommended, such as HTV
silicone rubber.
ACKNOWLEDGMENT
The authors would like to thank for the financial support
from the National Natural Science Foundation of China
(No. 51477085 and No. 51477086). The authors would
like to thank for the financial support from Specialized
Research Fund for the Doctoral Program of Higher
Education (SRFDP, Research on high fatigue resistance
silicon rubber material for EHV composite insulators, No.
20130002130009). The authors also would like to thank
the Analysis Center of Tsinghua University for doing some
of the measurements.
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Process of LSR Composite Hollow Insulator", Insulators and
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[2] S. M. Gubanski, A. Dernfalk, J. Andersson and H. Hillborg.
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Can Chen was born in Shanxi province, China, on
October 28, 1988. He received the B.S. degree in
electrical engineering from Tsinghua University, P.
R. China, in 2010. He is now a Ph.D. degree
candidate in Tsinghua University, P. R. China. His
major research fields are characterization and
degradation mechanism of silicone rubber and
composite insulators.
Cuiru Yang was born in Hebei province, China in
1980. She received the Ph.D. degree in electrical
engineering from Tsinghua University, Beijing,
China in 2010. She is now working at Guangdong
Electric Power Research Institute, Guangzhou,
China since 2010. Her major research fields are high
voltage insulation and high voltage test techniques.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 22, No. 1; February 2015
Zhidong Jia was born in Shanxi province, China, on
October 4, 1966. He received the B.Sc. degree from
Xi'an Jiaotong University, Xi’an, P. R. China, in
1987, the M.Sc. degree from Tsinghua University,
Beijing, P. R. China in 1992 and the Ph.D. degree
from Xi'an Jiaotong University, Xi’an, P. R. China,
in 2001. From 2001 to 2003 he worked as a
postdoctoral fellow in Tsinghua University. Now he
is a professor and works at Graduate School at
Shenzhen, Tsinghua University. His major research
fields are high voltage insulation, improvement of RTV coating, preventing
ice on outdoor insulators and nano electrical spin.
Xilin Wang was born in Hebei Province, China, on
April 10, 1983. He received B.S. degree in
Materials Science and Technology from
Department of Materials Science and Technology,
Beijing University of Chemical Technology and Ph.
D degree in Materials Science and Technology
from Department of Materials Science and
Technology, Tsinghua University. Now he is a
postdoctor in Electrical Engineering at Graduate
School at Shenzhen, Tsinghua University. His
major research fields are high voltage insulation
and dielectrics, interdisciplinary field between materials science and
electrical engineering.
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Hai Lu was born in Yulin, Guangxi province, China,
on 1989. He received the B.Sc. degree in electrical
engineering from Tsinghua University, Beijing, P.R.
China in 2012, and is now pursuing the M.Sc. degr
ee
in electrical engineering in Tsinghua University. His
major research fields are outdoor insulation,
application of silicone rubber and anti-pollution
flashover RTV coating.
Zhicheng Guan was born in Jilin province, China,
on November 10, 1944 and received the B.Sc., M.Sc.,
and Ph.D. degrees in high voltage engineering, from
the Department of Electrical Engineering, Tsinghua
University, Beijing, P.R. China, in 1970, 1981,
respectively. Now he is Vice President of Tsinghua
University Council and Dean of the Graduate School
at Shenzhen, Tsinghua University. His major research
fields are high voltage insulation and electrical
discharge, composite insulators and flashover of
contaminated insulators, electrical environment technology and application
of plasma and high voltage technology in biological and environment
engineering.