16 A. Shimada et al.

: Degradation Mechanisms of Silicone Rubber (SiR) by Accelerated Ageing for Cables of Nuclear Power Plant

Degradation Mechanisms of Silicone Rubber (SiR)

by Accelerated Ageing for Cables of Nuclear Power Plant
Akihiko Shimada, Masaki Sugimoto
Japan Atomic Energy Agency (JAEA)
Quantum Beam Science Directorate,
Takasaki, Gunma, 370-1292, Japan

Hisaaki Kudoh
The University of Tokyo
Nuclear Professional School
Tokai, Ibaraki, 319-1195, Japan

Kiyotoshi Tamura and Tadao Seguchi

Japan Atomic Energy Agency (JAEA)
Nuclear Safety Research Center
Tokai, Ibaraki, 319-1195, Japan

ABSTRACT
The degradation behavior of SiR for the cable insulation by accelerated thermal and
radiation ageing was studied and the degradation mechanism was proposed. The
degradation was observed by the change of tensile properties, the distribution of
crosslinking, and the change of weight. The chemical reaction under the both ageing in
oxidation conditions was crosslinking and the oxidation mechanism was found to be the
same between thermal and radiation ageing. The yield of crosslinking was proportional
to the ageing time and also the dose. The effect of irradiation temperature on oxidation
was accelerated with an increase of temperature above around 120 0C, which might be
due to the specific radiation chemical reactions. Therefore, the degradation by
simultaneous ageing at higher temperatures above 155 0C was much higher than that
for sequential ageing, such as irradiation followed by thermal ageing or thermal ageing
followed irradiation. At a high temperature, the degradation by thermal ageing under
vacuum (without oxidation) was more progressed than that for the ageing in air (with
oxidation). The reason was assumed to be the thermal decomposition of crosslinks
between SiR molecules formed by the chemical crosslinking agent. The hardness
(Shore hardness) reflected well the degradation of the SiR material for any ageing
conditions.
Index Terms — SiR, cable, ageing, thermal, radiation, degradation, mechanism.

1 INTRODUCTION
IN nuclear power plants, silicone rubber (SiR) is one of
the important insulation materials for cables as well as
crosslinked polyethylene (XLPE) and ethylene propylene
rubber (EPR). The characteristics of SiR are its excellent
heat resistance and high resistance for chemical agents.
However, the radiation resistance has been classified to be
relatively low [1, 2]. Recently, the various cables for nuclear
power plants (NPP) were investigated from the view point of
safety management [3, 4]. In the JNES report of the
comprehensive study of NPP cables by the accelerated
Manuscript received on 1 July 2013, in final form 17 October 2013,
accepted 18 October 2013.
ageing, SiR insulation was much different from XLPE and
EPR in degradation behavior. Namely the activation energy
of the thermal degradation for SiR was 42-55 kJ/mol over
the temperature range of 135 - 175 0C, which was much
lower than those of XLPE (100-110 kJ/mol) or EPR (66-95
kJ/mol) over the range of 100-120 0C. The difference should
be caused by the different degradation mechanisms, due to
the molecular structure of SiR. As SiR contains oxygen
atoms in the main chain, the oxidation would be completely
different from hydrocarbon polymers.
The radiation effects on SiR had been studied since 1955,
and the chemical reaction was determined to be crosslinking
by irradiation without oxidation [1, 5-9]. In radiation oxidation
conditions, the crosslinking was found to the major reaction

DOI 10.1109/TDEI.2013.004177
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 21, No. 1; February 2014
though the yield was lower than that without oxidation
conditions, and the yield increased with irradiation
temperature [7].
The purpose of this study was an analysis of SiR
degradation mechanism by accelerated thermal and radiation
ageing for the evaluation of cable life time for a series of
degradation mechanisms of cable insulation materials for NPP.
In our previous studies, the mechanical properties and
chemical reactions were investigated for EPR and XLPE by
the accelerated ageing using various experimental techniques
[10-14]. The same technique was applied to SiR insulation
material and the degradation mechanism was elucidated.
2 EXPERIMENTAL METHODS
The sheet specimens of SiR were the same insulation
material as the practical SiR cables for NPP. The core
specimen was of a cylindrical shape prepared from SiR cable
by pulling out the metal wire. The thicknesses of sheet
specimens were 0.5, 1.0, and 2.0 mm. The SiR specimens
were supplied from two cable companies (A and B), and
named to SiR-A and SiR-B, respectively. For a specific
sample, SiR-B sheet containing 1.0 phr (parts per hundred
resin by weight) cerium oxide (CeO2) powder was prepared,
because the CeO2 improves the heat resistance of SiR. The
samples of SiR were shown in Table 1.
Table 1. SiR samples.
Name Shape & Size Supplier
SiR-A Sheet (10 cm length and 0.5, 1.0, 2.0 Company A
mm thickness)
SiR-B Sheet (same above) Company B
SiR-B-CeO2 Sheet with CeO2 (1 phr), (10 cm Company B
length and 1.0 mm thickness)
SiR-B-core Cable core (10 cm length, OD 3mm, Company B
ID 1mm)
The SiR molecules of both SiR-A and SiR-B were
comprised of poly-dimethyl-siloxane (-Si (CH3)2-O-)n
containing phenyl-siloxane (-Si (C6H5)2-O-) as shown by the
FTIR analysis in Figure 1. The content of phenyl-siloxane
may be 10 - 20% by mole ratio, though content was not
released by the supplier. The various small peaks in the
absorption would be due to the additives in the SiR.
The accelerated thermal ageing was performed in air by
using a gear type oven at constant temperatures of 175, 205,
and 235 0C. For the ageing in vacuum, the specimens were
put in glass tubes and evacuated, and the glass tubes were
put in the same oven. The radiation ageing was performed by
60
Co gamma rays with a dose rate of 1.0 kGy/h at room
temperature (RT), 100, 155, 175, and 195 0C in air using a
gear type oven.
The combination of radiation and thermal ageing was as
for the following three procedures; (1) simultaneous ageing
(irradiation at elevated temperature), (2) sequential ageing
(thermal then radiation), and (3) reverse sequential ageing
(radiation then thermal). The radiation ageing was conducted
with 1.0 kGy/h at 100 0C for the sequential ageing of (2) and
(3) in order to induce the radiation induced oxidation
throughout the SiR specimens.
17
3
Si-phenyl Si-(CH3)2
-CH3 1429 1259
2960, 2870
2
Absorbance
1
Phenyl Si-O-Si
3600-3800 1065
0
4000 3600 3200 2800 2400 2000 1600 1200 800
Wave number / cm-1
Figure 1. FTIR spectrum of SiR (transmission spectrum of 0.1 mm sliced
specimen).
The mechanical properties were measured by a tensile test
at room temperature using Dumbbell shape specimens for
sheet samples. For core specimens, the tensile test was
conducted in the state of the core. Hardness was measured by
a durometer (HD-1120 TYPE-D, Ueshima Seisakusho Co.,
Ltd.), which was Shore hardness (HDD) for plastics according
to ISO 7619.
For the gel fraction and swelling ratio measurements, SiR
sheets (2 mm thick) were sliced to 0.3 mm thickness along the
sheet by a specific slicer. Each of the sliced specimens was
soaked in the solvent tetrahydrofuran (THF) at boiling
temperature (66 0C) for 1 day and the soluble component was
extracted. The gel fraction was the weight ratio of gel
component to the initial weight, and the swelling ratio was the
weight ratio of the gel component swollen with THF to the dry
gel component at room temperature.
The change of weight on ageing was measured by a
balance. The FTIR spectrum was observed by the transmission
method using a sliced specimen of 0.1 mm thickness.
3 RESULTS AND DISCUSSION
3.1 DISTRIBUTION OF OXIDATION IN SIR SHEET
SPECIMEN
A reliable analysis of the change in the chemical structure
with the progress of oxidation for both the SiR specimens
could not be observed from the FTIR spectrum; that is, the
degradation could not be followed by FTIR analysis as
reported for EPR or XLPE in previous papers [10, 11]. As the
chemical changes on ageing were well reflected in the changes
in the gel fraction and the swelling behavior, the distribution
of degradation in the sheet samples was determined by
measurements of the gel fraction and swelling ratio. Figure 2
shows the gel fraction and swelling ratio along the position
(depth) for a SiR-B sheet specimen of 2 mm thickness for the
thermal aging at 235 0C for 800 h and radiation ageing to 800
kGy (800 h) at RT and for 200 kGy (200 h) at 195 0C in air,
respectively. For both thermal and radiation ageing, the gel
fraction increased and the swelling ratio decreased with the
ageing time or dose. The distribution of both values was
almost homogeneous along the depth of sheet.
The behavior of gel fraction and swelling ratio indicated
that crosslinking occurred homogeneously in the 2 mm
18 A. Shimada et al.: Degradation Mechanisms of Silicone Rubber (SiR) by Accelerated Ageing for Cables of Nuclear Power Plant

sheet specimens by the ageing in oxidation condition. As
the oxygen penetration rate (or diffusion coefficient) into
SiR material is very high even at room temperature, the
oxidation occurred throughout the specimen of 2 mm thick
sheet in the radiation ageing of relatively high dose rate of
1 kGy/h.
100
195℃/200kGy
Gel fraction / %
For the radiation ageing, the decay of the tensile properties
was same or similar between SiR-A and SiR-B, as shown in
Figure 4. The additives mixed in SiR would not be effective in
radiation ageing. The decay of tensile properties with dose
was almost same between RT and 100 0C irradiation, but the
decay at 155 0C irradiation was much increased, whereas the
thermal degradation at 155 0C was small for an ageing time
less than 800 h. The enormous effect of irradiation
temperature above about 120 0C could be caused by the
temperature effect on the radiation chemistry, that is, the

99
RT/800kGy
radical yield on radiation increased for temperatures above
98 120 0C.
235℃/800h
97 120
Original

Elongation at break /rel.
96 100 A: T/175℃

80 B: T/175℃
95
0.0 1.0 2.0 A: T/205℃
60
Position in depth / mm
B: T/205℃
3.0 40
A: T/235℃
Original 20 B: T/235℃
2.5
Swelling ratio 

235℃/800h 0
0 500 1000
2.0 RT/800kGy Ageing time / h
120
1.5 195℃/200kGy
100
Tensile strength / rel.  

A: T/175℃

1.0 B: T/175℃
80
0.0 1.0 2.0 A: T/205℃
Position in depth / mm 60
Figure 2. Distribution of gel fraction and swelling ratio of SiR-B (2 mm) B: T/205℃
sheet after thermal ageing at 235 0C for 800h, and radiation ageing at RT for 40 A: T/235℃
800 h and at 195 0C for 200 h.
20 B: T/235℃
3.2 MECHANICAL PROPERTIES
The changes of mechanical properties by tensile tests for 0
SiR-A (2 mm) and SiR-B (2 mm) for thermal ageing at 175, 0 500 1000
Ageing time / h
205 and 235 0C are shown in Figure 3. The tensile tests for the
6.0
same specimens by radiation ageing at RT, 155, and 175 0C A: T/175℃
are shown in Figure 4. The elongation at break decreased with 5.0
B: T/175℃
the ageing time or dose, but the decay of tensile strength was
100% Modulus / MPa

4.0 A: T/205℃
rather small. The 100% modulus (tensile strength at 100%
elongation) increased with the ageing time or dose for any 3.0 B: T/205℃
ageing conditions. For SiR core specimens, the changes of 2.0 A: T/235℃
tensile properties were the same for the sheet specimens for
B: T/235℃
thermal and radiation ageing. 1.0
These results indicate that the SiR molecules were 0.0
crosslinked by both thermal and radiation ageing in oxidation 0 500 1000
conditions, which is consistent with the changes in the gel Ageing time / h
fraction and swelling ratios in Figure 2. In a case of thermal Figure 3. Change of mechanical properties (Elongation at break, Tensile
ageing, the decay of elongation was small until (1-2) x103 h at strength, and 100% Modulus) of SiR-A and SiR-B by thermal ageing at 175,
155 0C for SiR insulations [4], which is consistent with the 205 and 235 0C. The initial values: SiR-A 351%, 10.6 N/mm2; SiR-B 575%,
observations in this study. Above 175 0C the elongation 10.3 N/mm2.
decreased, and the decay rate increased with the ageing
temperature. The behavior of the elongation, tensile strength, For the radiation chemistry of PE and EPR under vacuum,
and 100% modulus are different between SiR-A and SiR-B. the yield of products increased sharply with irradiation
The reason would be the difference between the additives used temperature above a certain temperature, and the reason was
as stabilizers. attributed to an increase of radical yield [15].
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 21, No. 1; February 2014 19

120 For SiR insulation material no organic antioxidant is

A: rad/RT mixed the SiR (no necessity). Therefore, no effect due to the
Elongation at break /rel.

100 decay of antioxidant during thermal oxidation was observed

B: rad/RT
80 for SiR, unlike that for XLPE or EPR [10-12] at the higher
A: rad/155℃ temperature.
60 B: rad/155℃

40 A: rad/175℃
120
B: rad/175℃ 1: T/175℃
20
100 2: T/205℃

Elongation at break / rel.
0 3: T/235℃
0 500 1000 80
Radiation ageing / kGy & h 4: rad/RT

60 5: rad/175℃
120 1
A: rad/RT 40 2
100
Tensile strength /rel.

B: rad/RT 3
80 20
A: rad/155℃ 4
B: rad/155℃ 5
60 0
A: rad/175℃ 10 100 1000
40 Ageing time / h & kGy
B: rad/175℃
20 Figure 5. Change of elongation at break of SiR-A against logarithm ageing
time or dose for thermal or radiation ageing under various conditions.
0
0 500 1000 The degradation for the combination of thermal ageing
Radiation ageing / kGy & h
and radiation ageing, that is, (1) the simultaneous ageing,
(2) sequential ageing and (3) reverse sequential ageing
10.0 was compared for SiR-B sheet specimens (2 mm). The
A: rad/RT ageing conditions were 205 0C, 75 h for thermal ageing
100% Modulus / MPa

8.0 and 75 kGy (1 kGy/h) for radiation ageing. The tensile

6.0
4.0
2.0
0.0
0 200 400
Radiation ageing / kGy & h
Figure 4. Change of mechanical properties of SiR-A (2 mm) and SiR-B (2
mm) with dose for radiation ageing at RT (room temperature), 155 and 175 0C.
The 100% modulus at 175 0C could not observed at 100 kGy.
As the decay of tensile properties was induced by the
crosslinking of SiR molecules, the elongation at break for
SiR-A is plotted on a log scale for ageing time or dose
under different ageing conditions in Figure 5. The slopes of
the decay lines are same for any ageing conditions and each
line shifts along the ageing time or dose axis for different
ageing conditions. The results support the conclusion that
the degradation of SiR follows same mechanism for
thermal and radiation ageing in oxidation conditions. For
example, the activation energy of degradation by thermal
ageing between 175-235 0C was 58 kJ/mol, and this value
is nearly same as 55 kJ/mol observed at 135-175 0C for
thermal ageing (SiR-A and SiR-B are the same as SiR of C
company and SiR of B company, respectively, in the JNES
report [4]).
B: rad/RT
properties for the three ageing conditions are shown in
A: rad/155℃
Figure 6. The decay for sequential ageing was the same as
B: rad/155℃ for the reverse sequential ageing, but the decay for the
simultaneous ageing was much larger. The thermal
degradation at less than 155 0C was very small, and the
radiation degradation at 100 0C was almost same as that at
RT. Degradation for the thermal ageing and then radiation
ageing should be independent of each other. Therefore,
600
the degradation was the same between the sequential and
reverse sequential ageing. However, the degradation for
the simultaneous ageing was much accelerated, which was
induced by the irradiation temperature effect, as explained
in Figure 4.
The thermal degradation of SiR-B without oxidation
(ageing in vacuum) was compared with the oxidation at a
high temperature of 235 0C. The changes in the tensile
properties by ageing with and without oxidation are
shown in Figure 7. In vacuum, the elongation at break and
100% modulus changed a little with the ageing time, but
the tensile strength decreased significantly. The behaviors
for vacuum ageing suggested that the crosslinking density
tends to decrease with ageing time at the beginning, and
subsequently to increase gradually. The decrease would
be due to the destruction of SiR chemical crosslinks and
the increase might be due to new crosslink formation
resulting from the pyrolysis of SiR molecules in vacuum.
At a lower ageing temperature of less than 200 0C in
vacuum, the destruction of chemical crosslinks might be
20 A. Shimada et al.: Degradation Mechanisms of Silicone Rubber (SiR) by Accelerated Ageing for Cables of Nuclear Power Plant

the major process because the crosslinking by pyrolysis 700

should be negligible, where the mechanical properties

Elongation at break / %
decay significantly for a longer ageing time. In oxidation 600
conditions, the destruction of SiR crosslinking should 500
proceed as for that in vacuum at high temperature, 400
however, the crosslinking by oxidation would lead to
much more destruction. 300 Air/235 ℃
200 Vac/235 ℃
100
SiR‐B / 205 0C & 1 kGy/h 0
120
0 50 100 150 200
Elongation at break / rel.

100 Simul (R&T)
Ageing time / h
80 Seq (T→R)
12
R.Seq (R→T)

Tensile strength / MPa
60
10
40 8
20 6
Air/235 ℃
4
0 Vac/235 ℃
0 20 40 60 80 2
Ageing / time (h) & dose (kGy) 0
0 50 100 150 200
120 Ageing time / h
Simul (R&T)
100
Tensile strength / rel.

Seq (T→R) 2.5
100% Modulus/ MPa

80 R.Seq (R→T) 2.0
60 1.5
40 1.0 Air/235 ℃
Vac/235 ℃
20 0.5

0 0.0
0 20 40 60 80 0 50 100 150 200
Ageing / time (h) & dose (kGy) Ageing time / h

Figure 7. Tensile properties (elongation at break, tensile strength, and 100%

5.0 modulus) of SiR-B by thermal ageing in air and in vacuum at 235 0C.

Simul (R&T)
4.0
100% Modulus / MPa

3.3 THE RELATION OF HARDNESS AND

Seq (T→R) ELONGATION AT BREAK
3.0 The hardness of SiR sheet was measured after ageing
R.Seq (R→T)
for all specimens. The relationships between hardness and
2.0 50% modulus, and hardness and elongation at break are
plotted for SiR-A and SiR-B in Figure 8. For both SiR-A
and SiR-B, the hardness was nearly proportional to the 50%
1.0 modulus, but the linear relationship is composed of two
lines, below and above HDD at around 75. Also the
0.0 hardness related well to the elongation at break for a wide
0 20 40 60 80 range, regardless the oxidative degradation conditions, as
Ageing / time (h) & dose (kGy) shown in Figure 8. As the practical application for
Figure 6. Elongation at break, tensile strength, and 100% modulus for SiR-B
condition monitoring of SiR degradation is the index of
sheet (2 mm) by simultaneous ageing (1 kGy/h at 205 0C), sequential, and elongation at break, the hardness could provide an
reverse sequential ageing at 205 0C and a dose rate of 1 kGy/h at 100 0C. alternative reliable monitoring.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 21, No. 1; February 2014 21

8.0 In the radiation ageing at RT in air, oxygen uptake would

be almost equivalent to the gaseous oxidation products, CO2
and H2O. For oxidation conditions at higher temperature, the
6.0 oxidation products of SiR (low molecular weight products)
and of the additives, including the crosslinking agent, should
50% Modulus / MPa

be gradually evaporated during the ageing process. For ageing

4.0 in vacuum at 2350C, a small amount of gases, such as H2 and
SiR‐A CH4, might be evolved within a short ageing time. For other
SiR‐B types of SiR (phenyl content is higher than methyl), the
2.0 gaseous products observed were CO2 (55%), H2 (30%), CH4
(10%) for irradiation in oxygen at RT, and H2 (12%), CH4
(4%), CO2/CO (80%) for thermal ageing at 2500C in oxygen,
0.0 and H2 (33%), CH4 (12%), others (55%) for thermal ageing at
40 60 80 100 2500C for 72 h in vacuum [16].
Hardness / HDD
600
3.5 EFFECT OF CeO2 AS STABILIZER
SiR‐A Cerium oxide (CeO2) is one of the stabilizers used for
500
SiR‐B improvement of the thermal resistance of SiR material. The
400 effect of CeO2 (1.0 phr content of fine powder) was examined
for the degradation of a SiR-B sheet specimen by thermal and
Elongation at break / %

300 radiation ageing. The thermal ageing was at 205 0C in air, and
the radiation ageing was for a dose rate of 1.0 kGy/h at RT and
200 1000C in air. Figure 10 shows the elongation at break for SiR
with 1.0 phr CeO2 and without CeO2 for thermal ageing at 205
0
100 C and for radiation ageing at 100 0C. The extents of radiation
degradation at RT and 100 0C were the same for elongation at
0 break, tensile strength and 100% modulus, which means no
40 60 80 100 effect by CeO2 addition. For the thermal degradation at a high
Hardness / HDD
temperature, the effect of CeO2 was observed, but it was a little.
Figure 8. Relations between hardness and 50% Modulus, and hardness and
elongation at break for SiR-A and SiR-B after ageing at various conditions.
600
3.4 WEIGHT CHANGE OF SPECIMEN CeO2 
For analysis of the degradation mechanisms, the weight 500 1phr/205℃
Elongation at break / %

change of SiR was monitored by thermal ageing and radiation 400 CeO2 
ageing. Figure 9 shows the weight change for SiR-B sheet 0phr/205℃
specimens by thermal ageing at 235 0C in air and in vacuum, 300 CeO2
and radiation ageing at RT and 195 0C in air. 1phr/Rad
200
CeO2
1 100 0phr/Rad
Rad/RT/Air
0 0
Weight change / %

235℃/Vac 0 100 200 300 400 500

‐1
Ageing time / h or Dose / kGy
‐2 175℃/Air Figure 10. Elongation at break of SiR containing 0 and 1 phr of CeO2 versus
ageing time or dose for thermal ageing at 205 0C and radiation ageing at 100
‐3 0
Rad/195℃ C, 1 kGy/h.
/Air
‐4
235℃/Air 3.6 MECHANISMS OF SIR DEGRADATION
‐5 Both the SiR-A and SiR-B specimens are crosslinked by a
0 200 400 600 800 chemical peroxide compound. The chemical structure of
Ageing time / h or Dose /kGy original specimen would be in Figure 11a. The crosslinking
Figure 9. Weight change of SiR-B sheet by thermal ageing at 175, 235 0C in point (-R-) means -CH2- or -CH2-CH2-, and the number of -R-
air and at 235 0C in vacuum, and radiation ageing at RT, 195 0C in air with a per chain may be 1-2 per 100 Si atoms.
dose rate of 1.0 kGy/h.
For thermal or radiation ageing under oxidation conditions,
The weight of SiR increased slightly with dose by the Si-CH3 in main chain is broken by oxidation and a Si-O-Si
radiation at RT in air. At higher temperatures, the weight crosslinking point is formed, as shown in Figure 11b. The
decreased with ageing time for thermal ageing and radiation CH3- is converted to CO2 and H2O. The free radical Si-CH2•
ageing in air. However, the decrease was little for the thermal introduced by radiation or thermal activation would be the
ageing in vacuum at high temperature, such as 235 0C. initiator of the oxidation, and the resulting oxidation may be
22 A. Shimada et al.: Degradation Mechanisms of Silicone Rubber (SiR) by Accelerated Ageing for Cables of Nuclear Power Plant

same for both thermal and radiation ageing. For radiation with chemical crosslinking and radiation crosslinking in a
oxidation, the same chemical reaction mechanism was vacuum, the changes in the mechanical properties were found
proposed by Menhofer et al [6]. to be similar for both processes.

a SiR chemical structure (original specimen) 4 CONCLUSION

The degradation mechanism of SiR is completely
M: Methyl (CH3)  
different from that of the polyolefins such as XLPE, EPR
         M          M           M          Ph
‐ O ‐ Si – O – Si – O – Si – O – Si ‐ O‐  Ph: Phenyl (C H ) 
used as cable insulation materials. The degradation of SiR
         M           |            M          Ph
6 5 properties was via crosslinking induced by oxidation during
R: CnH2n   thermal and also radiation ageing, whereas the degradation
                       R
         M           |            M          M (Chemical crosslinking) of XLPE and EPR was via scission of the polymer chains
‐ O ‐ Si – O – Si – O – Si – O – Si ‐ O‐  Ph/M = 0.1 – 0.2  following oxidation. As a specific behavior, SiR was found
R/Si = ca. 1/100 
         M          M           M           M                        to be more degradable by thermal ageing at a higher
by number ratio  temperature without oxidation than with oxidation. The
reason was proposed to be the destruction of the crosslinks
b Crosslinking by oxidation produced by the chemical agent.
The SiR insulation material has the high permeability for
oxygen gas, so the oxidation occurs uniformly throughout a
  M   M relatively thick sheet (2 mm) for thermal and radiation
‐ Si ‐ ‐ Si ‐ ageing in air, even with the high dose rate of 1 kGy/h at RT.
  M    | For XLPE, the oxidation was limited to within 0.1 mm from
  M   O       + 2 (CO2 +H2O) the surface under at the same irradiation conditions at RT
‐ Si ‐ Oxidation    | [13].
  M by thermal ‐ Si ‐ The yield of oxidation, which is equivalent to the yield of
or radiation   M
crosslinking, is proportional to the ageing time or dose under
Crosslinking  oxidation conditions, so the behavior of the tensile properties,
via oxygen especially the elongation at break, was similar for any ageing
conditions. Also, the activation energy for thermal oxidation
c Thermal decomposition of chemical crosslinking was almost same for a wide range of ageing temperatures.
  M The radiation induced oxidation showed a rather large
  M ‐ Si ‐ dependency on the irradiation temperature above around 120
‐ Si ‐ 0
   X C. The radical yield, as the initiator of oxidation, would
   |                    X, Y : H or CH3   increase at elevated temperatures, which may be the
   R Thermal     Y fundamental aspect in the radiation chemistry for polymers.
   | ageing at high ‐ Si ‐ In a comparison of the degradation amongst three
‐ Si ‐ temperature   M combinations of thermal and radiation ageing, sequential
  M
ageing (thermal then radiation) was the same as for reverse
Break at 
chemical 
sequential ageing (radiation then thermal), but simultaneous
Chemical 
crosslinking ageing (radiation at elevated temperature) was much greater
crosslinking than for both of the other ageing protocols. The reason could
Figure 11. Mechanisms of chemical change of SiR. a: SiR chemical structure be explained by a dependency on irradiation temperature.
of original specimen, b: Crosslinking by thermal and radiation oxidation, c: For a qualification test for ageing of SiR cables, the
Thermal decomposition of chemical crosslinking at high temperature. temperature used for simultaneous ageing must be
considered well, particularly the use of irradiation
For high temperature ageing above around 150 0C, the temperatures above around 120 0C.
crosslinking molecule (-R-) would be decomposed gradually The hardness reflected well the degradation in the wide
with or without oxidation as seen in Figure 11c. On ageing in range for the any ageing conditions. Therefore, the hardness
vacuum, the probability of crosslinking would be small and could be applied for the condition monitoring.
less than that for breaking a crosslink (-R-) at around 150 –
200 0C. As a result, the mechanical properties, especially the ACKNOWLEDGMENT
tensile strength decreased more for vacuum ageing (no This research was done under contract between NISA
oxidation) than under oxidation conditions. (Former: Nuclear and Industrial Safety Agency, Japan) and
For radiation crosslinking without oxidation, the chemical JAEA. The authors wish to thank Dr. David J. T. Hill,
structure of the crosslink is proposed to be Si-CH2-Si, or Si- University of Queensland, Australia for his suggestion and
CH2-CH2-Si [6, 7], which are the same as that for chemical valuable comments, Hitachi Cable Ltd. (Dr. T. Yamazaki) and
crosslinking using peroxides. The other structure, T type Mitsubishi Cable Ltd. (Mr. S. Araki) for the sample
crosslink (chain branch), was detected by NMR study [9]. In preparation, and Japan Electric Cable Technology Center (Mr.
our preliminary study of a comparison of thermal degradation H. Satoh, Mr. H. Watabe) for the tensile test.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 21, No. 1; February 2014 23

REFERENCES Akihiko Shimada received the B.E. degree in 2000

in sanitary engineering and the M.E. degree in 2002
[1] M. Dole, Ed., The radiation Chemistry of Macromolecules, Vol.1I, in environmental earth engineering from Kyoto
Academic Press, New York, 1973. University. He jointed Japan Atomic Energy
[2] J. Brandrup, E. H. Immergut, E. A. Grulke, Ed., Polymer Handbook, 4th Agency in 2002. He is engaged on research on
Edition”, VI/583-587, 1999. environmental preservation by radiation application
[3] International Atomic Energy Agency (IAEA) Technical report, “Assessing and for radiation resistance of polymer materials as
and Managing Cable Ageing in Nuclear Power Plants”, 2012. IAEA cable ageing.
Nuclear Energy Series, No. NP-T-3.6. Available: http://www-
pub.iaea.org/MTCD/ Publications/ PDF/Pub1554_web.pdf
[4] T. Yamamoto and T. Minakawa, Final report of the project of “Assessment
of Cable Aging for Nuclear Power Plants”, Japan Nuclear Energy Safety Masaki Sugimoto received the B.E. in 1989, the
Organization (JNES) report, Report No. : JNES-SS-0903, 2009, Available: M.E. in 1991, and the Dr. Eng. Degrees in 1994
http://www.jnes.go.jp/english/katsudou/activity_reports.html from the Department of Metallurgy and Materials
[5] A. Charlesby, “Changes in silicone polymeric fluids due to high energy Science, the College of Engineering, University of
radiation”, Proc. Roy. Soc., London, Vol. A230, pp. 120-135, 1955. Osaka Prefecture. He is currently a deputy principal
[6] A. A. Miller, “Radiation Chemistry of Poly-dimethyl-siloxane. I. researcher with Japan Atomic Energy Agency and
Crosslinking and Gas Yields”, J. Am. Chem. Soc., Vol. 82, pp.3519-3523, engaged in the research and development of
1960. functional ceramic materials using radiation
[7] H. Menhofer, J. Zluticky, and H. Heusinger, “The Influence of Irradiation irradiation technique.
Temperature and Oxygen on Crosslink Formation and Segment Mobility
in Gamma-Irradiated Polydimethylsiloxanes”, Radiat. Phys. Chem., Vol.
33, pp. 561-566, 1989. Hisaaki Kudoh received the B.E. in 1988, the M.E.
[8] D. J. T. Hill, C. M. L. Preston, D.J. Salisbury and A. K. Whittaker, in 1990, and the Dr. Eng. in 1996 from the
“Molecular weight changes and scission and crosslinking in poly(dimethyl Department of Nuclear Engineering, The University
siloxane) on gamma radiolysis”, Radiat. Phys. Chem., Vol. 62, pp.11-17, of Tokyo. He is engaged on research of polymer
2001. radiation effects in Japan Atomic Energy Research
[9] D. J. T. Hill, C. M. L. Preston, A. K. Whittaker, “NMR study of the Institute for 1990-2000. At 2001 he is engaged The
gamma radiolysis of poly(dimethyl siloxane) under vacuum at 303K”, University of Tokyo for nuclear power research and
Polymer, Vol., Vol. 43, pp.1051-1059, 2002 the education.
[10] T. Seguchi, K. Tamura, T. Ohshima, A. Shimada, and H. Kudoh,
“Degradation mechanisms of cable insulation materials during radiation-
thermal ageing in radiation environment”, Radiat. Phys. Chem., Vol. 80, Kiyotoshi Tamura received the B.E. in 1975 and
pp. 268-273, 2011. M.S. in 1977 in electrical engineering from Tokyo
[11] T. Seguchi, K. Tamura, A. Shimada, M. Sugimoto, and H. Kudoh, Institute of Technology, and joined Hitachi Cable,
“Mechanism of antioxidant interaction on polymer oxidation by thermal Ltd., in 1977. In 2007-2011 he was engaged in
and radiation ageing”, Radiat. Phys. Chem., Vol. 81, pp. 1747-1751, 2012. coordinating research group of Nuclear Safety
[12] M. Sugimoto, A. Shimada, H. Kudoh, K. Tamura, and T. Seguchi, Research, JAEA.
“Product analysis for polyethylene degradation by radiation and thermal
ageing”, Radiat. Phys. Chem., Vol. 82, pp. 69-73, 2013.
[13] A. Shimada, M. Sugimoto, H. Kudoh, K. Tamura, and T. Seguchi,
“Radiation Ageing Technique for Cable Life Evaluation of Nuclear Power
Plant”, IEEE Trans. Dielect. Elect. Ins., Vol. 19, pp. 1768-1773, 2012.
[14] A. Shimada, M. Sugimoto, H. Kudoh, K. Tamura, and T. Seguchi, Tadao Seguchi received the B.E. in 1964, the M.E. in
“Degradation Distribution in Insulation Materials of Cables by 1966 and the Dr. Eng. in 1977 degrees from Hokkaido
Accelerated Thermal and Radiation Ageing”, IEEE Trans. Dielectr. Electr. University. He jointed Japan Atomic Energy Research
Insul., Vol. 20, No. 6, pp. 2107-2116, 2013. Institute in 1966-2003. His research activity was
[15] T. Seguchi, Y. Haruyama, M. Sugimoto, “Temperature dependence of radiation application for material development and
gas evolution from polyolefins on irradiation under vacuum”, Radiat. evaluation of radiation resistance for polymer materials.
Phys. Chem., Vol. 85, pp. 124-129, 2013. In 2006-2012 engaged in research for cable life
[16] JAERI (Japan Atomic Energy Research Institute) unpublished report, evaluation of nuclear plant at JAEA.
1977.