polymers

Article
Understanding the Effects of In-Service Temperature
and Functional Fluid on the Ageing of
Silicone Rubber
Sima Kashi 1, * , Mandy De Souza 1 , Salwan Al-Assafi 2 and Russell Varley 1
1 Institute for Frontier Materials, Deakin University, Waurn Ponds, VIC 3216, Australia;
mandy.desouza@deakin.edu.au (M.D.S.); russell.varley@deakin.edu.au (R.V.)
2 Quickstep Technologies Pty Ltd, Waurn Ponds, VIC 3216, Australia; sal-assafi@quickstep.com.au
* Correspondence: sima.kashi@deakin.edu.au




Received: 14 January 2019; Accepted: 16 February 2019; Published: 26 February 2019


Abstract: With an organic/inorganic hybrid nature, silicone elastomers are amongst the most
versatile engineering materials, exploited in a wide range of applications either as end-products
or in manufacturing processes. In many industrial machines, silicone components are exposed to
in-service conditions, such as high or low temperatures, contact with functional fluids, mechanical
loading, and deformations, which can adversely affect these components and reduce their lifespan,
leading to machine failure in turn. The present study investigates the behaviour of a silicone
component of a manufacturing equipment and the variations in the part’s properties due to in-service
conditions (temperature, exposure to heat transfer fluid, and mechanical deformation) to develop a
monitoring tool. An experimental design was employed to study the main and the interaction effects
of temperature (22 ◦ C, 180 ◦ C), medium (air, synthetic heat transfer fluid), and strain (0%, 200%) on the
silicone component’s properties. Results showed that while the chemistry of the component remains
intact, its thermal and in particular mechanical properties are largely influenced by the in-service
conditions. Consequently, leading to a physical rather than a chemical failure of the component and
limiting its service life. Statistical analysis revealed that high temperature and the exposure to the
heat transfer fluid have the most sever effects. Moreover, these two manufacturing parameters were
found to have a significant interaction with one another, whose effect cannot not be neglected.

Keywords: temperature; silicone rubber; thermal properties; mechanical properties; ageing

1. Introduction
Having an inorganic/organic hybrid nature, silicone rubbers fall within a material regime between
silicate minerals and organic polymers with attributes of both sides [1]. Silicone rubbers are known for
their high elasticity, low surface energy, high hydrophobicity, wide working temperature, exceptional
weatherability, significantly high electrical resistivity, and biocompatibility [2–7]. This unique
combination of outstanding properties places silicone rubbers among the most versatile materials with
applications in industries as different as aerospace and automotive, electronics, power transmission
and distribution, household and leisure, food sector, building industry, health and medical,
and pharmaceutical [7,8].
Nevertheless, despite excellent properties and durability, silicone rubbers are still prone to
deterioration depending on their service environment, which can eventually lead to their failure.
Therefore, it is important to understand their behaviour over time under the effect of the in-service
conditions, i.e., high or low temperatures, mechanical load, or chemical attack. Due to the wide
application of silicone rubbers as electrical insulators in electrical apparatus, power transmission,

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Polymers 2019, 11, 388 2 of 14

and distribution systems, etc. [9–13], the studies on the ageing behaviour of silicone rubbers have
mostly focused on weatherability, UV radiation ageing, and dielectric breakdown [10,11,13–15].
In contrast, there have been few studies on the deterioration of silicone rubber properties in other
applications. Recently, Bernardi et al. [16] investigated the cyclic deformation and fracture behaviour of
silicone-rubber elastomers in soft biomedical implants. In another recent study, Wu et al. [17] examined
the thermal oxidation ageing of silicone rubber with a focus on its application as a sealant for equipment.
The ageing behaviour of silicone rubber sealants in fuel cell applications has also been investigated
in another recent study [18]. With the increased usage of silicone rubbers in alternative applications,
such as industrial machinery and processes, it has become crucial to understand their ageing behaviour
and the effects of in-service conditions on properties to prevent failure. Many industrial machines
have silicone rubber components, which are in continuous contact with various lubricants, heat
transfer fluids while at either very high or low temperatures, or also during mechanical loading.
These conditions have the potential to severely affect the rubber’s properties and shorten its useful
service life.
The present article reports on the accelerated ageing study of a silicone rubber in different
environments and ageing conditions selected to replicate the most extreme conditions experienced
by a silicone rubber part in a specific industrial process, where the rubber is exposed to polyalkylene
glycol as a heat transfer fluid at high temperature and large mechanical deformations. The aim of the
study was to investigate the variations in the properties of the silicone rubber due to ageing with a
focus on mechanical and thermal properties. In our previous work [2], we monitored the properties of
silicone rubber over a six-week period for one ageing environment, where the rubber samples were
submerged in polyalkylene glycol and aged in an oven purged with nitrogen. In the current study,
a setup of eight experiments was used to understand the effect of three major processing factors on the
properties of the silicone rubber. Experiments were designed based on a two-level factorial design of
experiment (DOE) with factors of mechanical strain, exposure to heat transfer fluid, and temperature.
Samples were aged for six weeks and then characterised in terms of hardness, tear strength, tensile
properties, thermal properties, and surface chemistry. Furthermore, DOE analysis was performed
to determine the significance of each ageing factor as well as their interaction effects on the silicone
rubber’s properties.

2. Experimental

2.1. Design of Experiment (DOE)

The processing parameters affecting the silicone rubber’s (SR’s) lifetime in the present study are:
Temperature, medium, and strain. To analyse the effect of these factors, DOE was employed as a tool
of a systematic experimental design, enabling an investigation of the effects of each factor and their
interactions on the SR’s properties. Two levels were considered for each factor: At rest condition and
at the most severe condition experienced during processing. Experiments were designed based on a
balanced 23 full factorial model. The factors and their levels are shown in Table 1. The ageing trials
and the allocated sample codes are summarised in Table 2.

Table 1. Processing factors and their levels used in the DOE approach.

Factor Low Level High Level

Temperature 22 ◦C 180 ◦ C
Medium Air PAG
Strain 0% 200%
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Table 2. The 23 full factorial experimental layout and the sample codes.
Table 2. The 23 full factorial experimental layout and the sample codes.
Trial Strain (%) Medium Temperature (°C) Sample Code
Trial Strain (%) Medium Temperature (◦ C) Sample Code
1 0 Air 22 A22-0%
1 0 Air 22 A22-0%
2 200 Air 22 A22-200%
2 200 Air 22 A22-200%
3 3 0 0 PAG
PAG 2222 P22-0%
P22-0%
4 4 200200 PAG
PAG 2222 P22-200%
P22-200%
5 5 0 0 Air
Air 180
180 A180-0%
A180-0%
6 6 200200 Air
Air 180
180 A180-200%
A180-200%
7 7 0 0 PAG
PAG 180
180 P180-0%
P180-0%
8 8 200200 PAG
PAG 180
180 P180-200%
P180-200%

2.2. Materials
A translucent silicone rubber with a Shore-A hardness of 35, tensile strength of 10.67 MPa, tear
44.9 kN/m,
strength of 44.9 kN/m, and and elongation
elongation at
at break
break ofof 1149%
1149% (as
(as per the product’s technical data sheet)
was used
was used in this
this study.
study. Polyalkylene
Polyalkylene glycol (PAG)
(PAG) waswas used
used as
as the
the heat
heat transfer
transfer fluid in the
the present
present
study with the following properties, as per the product’s technical data sheet: Flash point of 246 ◦°C, C,
fire point
fire point of
of 285 ◦
285 °C, and aa pour
C, and pour point of −
point of −34 ◦
34 °C,
C, specific
specific gravity
gravity of
of 1.051,
1.051, and specific heat capacity of
1.95 kJ
1.95 ·kg−
kJ.kg 1K
-1K −1−at
1 at
2020°C.◦ C.

2.3.
2.3. Accelerated
Accelerated Aging
Aging Experiment
Experiment
The ◦
The first four ageing
first four ageing tests
testswere
weresetsetupupininaacontrolled
controlledtemperature
temperatureroom roomatat
2222°C, C, while
while trials
trials 5–
5–8 were set up in a convection oven at 180 ◦ C. To put the SR under strain, a special straining frame
8 were set up in a convection oven at 180 °C. To put the SR under strain, a special straining frame
was
was designed,
designed, as as shown
shown in in Figure
Figure 1a,
1a, and
and four
four frames
frames were
were manufactured
manufactured in-house.
in-house. TwoTwo oil
oil baths
baths
filled ◦
filled with
with PAG,
PAG, at at 22
22 and
and 180
180 °C,C, were
were prepared
prepared for for trials 3–4 and
trials 3–4 and 7–8,
7–8, respectively.
respectively. SR
SR samples
samples were
were
aged
aged for six weeks for all 8 conditions described in Table 2. Once the experiment was finished, the SR
for six weeks for all 8 conditions described in Table 2. Once the experiment was finished, the SR
samples
samples were
were removed
removed from from the
the oil
oil baths
baths and
and unstrained.
unstrained. PAG PAG was
was removed
removed from
from the
the surface
surface ofof the
the
samples ◦ C for one week
samples using
usingpaper
papertowels
towelsand andthen
thenallall
8 samples
8 samples were dried
were in a in
dried vacuum
a vacuumovenoven
at 30 at 30 °C for one
prior to the characterisation.
week prior to the characterisation.

Figure 1.
Figure 1. (a)
(a) Special
Special rig
rig designed
designed for
for straining
straining SR,
SR, (b)
(b) unstrained
unstrained SR
SR framed
framed in
in the
the rig,
rig, (c)
(c) SR
SR under
under
200% strain.
200% strain.

2.4.
2.4. Characterisation
Characterisation
The
The mechanical
mechanical properties
properties of
of the
the SR
SR samples
samples were
were determined
determined via
via tensile,
tensile, tear,
tear, and
and hardness
hardness
measurements.
measurements. Tensile tests were performed using an Instron 4467 Universal testing machine with
Tensile tests were performed using an Instron 4467 Universal testing machine with
self-tightening roller grips (Figure 2c) according to the AS 1683.11-2001 (ISO 37) standard method.
self-tightening roller grips (Figure 2c) according to the AS 1683.11-2001 (ISO 37) standard method.
Self-tightening grips are ideal for testing elastomers, preventing specimen slippage. Six type-2
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Self-tightening grips are ideal for testing elastomers, preventing specimen slippage. Six type-2
dumbbell-shaped specimens
dumbbell-shaped specimens (Figure
(Figure 2a)
2a) were
were cut
cut out
out ofof each
each SRSR sample. Measurements were
sample. Measurements were
performed at
performed at ambient
ambient temperature
temperature withwith aa 100
100 NN load
load cell
cell and
and aa crosshead
crosshead speed
speed of
of 500
500 mm/min.
mm/min.Tear Tear
tests were conducted on the same instrument and according to the AS 1683.12-2001 (ISO
tests were conducted on the same instrument and according to the AS 1683.12-2001 (ISO 34) standard 34) standard
method with
method with trouser
trouser specimens
specimens (Figure
(Figure 2b).
2b). The
The instrument
instrument was was operated
operated without
without interruption
interruptionat at aa
constant rate
constant rate of
of 100
100 mm/min
mm/minuntil untilthe
thesamples
samplesteared.
teared. Six
Sixtrouser
trouserspecimens
specimenswere
were tested
tested for
for each
each
sample. The hardness of the samples was measured by using a Micro-O-Ring hardness
sample. The hardness of the samples was measured by using a Micro-O-Ring hardness tester (Shore tester (Shore
Instruments-Instron)according
accordingto tothe
theASTM
ASTMD2240 D2240standard
standardmethod
methodat atroom
roomtemperature
temperature(22 ◦ C).
(22°C).
Instruments-Instron)
Ten indentation values were recorded for each sample.
Ten

Figure 2. (a) Type-2 dumbbell specimen for tensile testing according to AS 1683.11-2001, (b) trouser
Figure 2. (a) Type-2 dumbbell specimen for tensile testing according to AS 1683.11-2001, (b) trouser
specimen for tear testing according to AS 1683.12-2001, (c) self-tightening grips with the trouser
specimen for tear testing according to AS 1683.12-2001, (c) self-tightening grips with the trouser
specimen in the machine.
specimen in the machine.
The thermal properties of the samples were investigated by differential scanning calorimetry
(DSC)The thermal
[19,20] withproperties
a Netzsch of the
214 samples
Polyma wereunderinvestigated by differential
nitrogen, following scanning calorimetry
a cool-heat-cool-heat cycle
(DSC) [19,20]
according with
to the a Netzsch
following 214 Polyma
procedure: under nitrogen,
(1) Holding for 2 min following
at 20 ◦ C,acooling
cool-heat-cool-heat
down to −160 cycle
◦C
according to the following
◦ procedure: (1) Holding ◦for 2 min at 20 °C, cooling
at a cooling rate of 10 C/min, (2) holding at −160 C for 5 min, heating up to 100 C at a heating rate down
◦ to −160 °C at a
cooling◦ rate of (3)
of 10 C/min, 10 °C/min,
holding (2) holding
at 100 ◦ C forat5−160
min,°C for 5 min,
cooling downheating
to −160 upCtoat100
◦ °C at a rate
a cooling heatingof 10rate
◦ of 10
C/min,
°C/min, (3) holding ◦at 100 °C for 5 min, cooling down
◦ to −160 °C at a cooling
(4) holding at −160 C for 5 min, heating up to 100 C at a heating rate of 10 C/min. Liquid nitrogen◦ rate of 10 °C/min, (4)
holding at −160 °C for 5 min, heating up to 100 °C at a heating rate of 10 °C/min.
was used to achieve the low temperatures for the DSC measurements. To investigate the changes in Liquid nitrogen was
used to achieve
the chemical the low temperatures
composition of the SR with forageing,
the DSC measurements.
a Bruker Vertex 70To investigate
Fourier the changes
transform infrared in the
(FTIR)
chemical composition of the SR with ageing, a Bruker Vertex 70 Fourier transform
(Bruker, Germany) spectrometer was used. The data was obtained in the attenuated total reflectance infrared (FTIR)
(Bruker, Germany)
(ATR) mode, using spectrometer
64 scans at a 4was cm−used. The data
1 resolution was4000
from obtained
to 600incm the
−1attenuated
. total reflectance
(ATR) mode, using 64 scans at a 4 cm resolution from 4000 to 600 cm .
−1 −1

3. Results and Discussion

3. Results and Discussion
3.1. Hardness
3.1. Hardness
Various applications of elastomers, in particular when used in industrial processes, require the
material to perform
Various well of
applications in elastomers,
terms of itsinmechanical properties
particular when used [2,21]. The hardness,
in industrial tear
processes, strength,
require the
tensile strength, elongation at break, and modulus of the silicone rubber are of significant
material to perform well in terms of its mechanical properties [2,21]. The hardness, tear strength, importance
for thestrength,
tensile manufacturing process
elongation of theand
at break, present study.
modulus of The effects of
the silicone different
rubber ageing
are of conditions
significant on the
importance
mechanical
for properties process
the manufacturing of the silicone rubber are
of the present as follows.
study. The effects of different ageing conditions on the
Figure properties
mechanical 3 shows theofvariations
the siliconeofrubber
the SR’s
arehardness
as follows.after a six-week exposure to different ageing
conditions.
Figure 3The changes
shows in the hardness
the variations as a percentage
of the SR’s hardness after of the unaged exposure
a six-week SR hardness are reported
to different on
ageing
conditions. The changes in the hardness as a percentage of the unaged SR hardness are reported on
the left-hand vertical axis. It is observed that the hardness decreases for all ageing conditions except

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the left-hand vertical axis. It is observed that the hardness decreases for all ageing conditions except
for
forsamples
samples aged
agedin inair
airatataatemperature
temperatureof of180
180°C◦ C(samples
(samples55and and6),6),which
whichshow
showaasignificant
significantincrease.
increase.
The highest hardness value belonged to sample 6 (57.35 Shore A), exhibiting a 40%
The highest hardness value belonged to sample 6 (57.35 Shore A), exhibiting a 40% increase compared increase compared
to
to the
the unaged
unaged SR SR (sample
(sample 1) 1) with
with aa hardness
hardness of of4141Shore
ShoreA. A.The
Thehardness
hardnessofofsample
sample7,7,agedagedininPAG
PAG at
at ◦ C,°C,
180180 exhibited
exhibited a decrease
a decrease of 37%,of reaching
37%, reaching
its lowestits value
lowest of value of 26.1
26.1 Shore Shore
A. An A. An observation
interesting interesting
observation
from Figure from Figure
3 is that 3 is that
straining the SRstraining
can boththe SR canand
decrease both decrease
increase the and increase
hardness the hardness
depending on the
depending
temperature. onComparing
the temperature.
sampleComparing
2 with samplesample1, and2 with
samplesample
4 with1, sample
and sample
3, it is4 seen
with that
sample 3, it
strained
is seen that strained samples aged at a low◦ temperature of 22 °C showed a lower
samples aged at a low temperature of 22 C showed a lower hardness compared to their counterparts. hardness compared
to
Ontheir counterparts.
the other On the
hand, strained other athand,
samples a highstrained
temperaturesampleshaveathigher
a high temperature
hardness values have higher
compared to
hardness
not-strainedvalues compared
samples, to not-strained
irrelevant of the aging samples,
medium, irrelevant
as evident of by the aging medium,
comparing sample 6as evident
with sample by5
comparing
and samplesample
8 with 6sample
with sample
7. 5 and sample 8 with sample 7.

60 60

Change in Hardness (%),

(releative to sample 1)
Hardness
Hardness (Shore A)

50 40
40 20
30 0
20 -20
10 -40
0 -60
1 2 3 4 5 6 7 8
Sample number
Figure
Figure3.3.Effect
Effectof
ofdifferent
differentageing
ageingconditions
conditionson
on the
the hardness
hardness of
of the
the SR.
SR.

3.2. Tear
3.2. Tear Testing
Testing
The effect
The effect of ofthe
theageing
ageingconditions
conditions on the SR’sSR’s
on the tear strength is illustrated
tear strength in Figure
is illustrated in 4.Figure
It is observed
4. It is
that tear strength decreases drastically when the SR is exposed to high temperatures.
observed that tear strength decreases drastically when the SR is exposed to high temperatures. The The tear strength
of unaged
tear strength SRof(A22-0%)
unaged SR is 14.2 kN/m,
(A22-0%) which
is 14.2 drops
kN/m, to only
which 3.9 to
drops kN/m
only in
3.9sample
kN/m in 5 (A180-0%)
sample 5 (A180- upon
ageing at 180 ◦ C, exhibiting a 72% reduction. When aged in PAG at 180 ◦ C, the tear strength decreases
0%) upon ageing at 180 °C, exhibiting a 72% reduction. When aged in PAG at 180 °C, the tear strength
to about 95%
decreases of that
to about of unaged
95% of that of SR.unaged
In contrast
SR. Into samples
contrast to aged at highaged
samples temperatures, exposure to
at high temperatures,
PAG at a low temperature of 22 ◦ C slightly enhances the tear strength; sample 3 (P22-0%) has a tear
exposure to PAG at a low temperature of 22 °C slightly enhances the tear strength; sample 3 (P22-
strength
0%) has a of
tear15.7 kN/m,ofwhich
strength is 7.4%
15.7 kN/m, higher
which thanhigher
is 7.4% that ofthan
unaged
that ofSRunaged
(A22-0%). The tear The
SR (A22-0%). strength
tear
strength of sample 4 (P22-200%), with a value of 13.01 kN/m, is also slightly higher than that of sample2
of sample 4 (P22-200%), with a value of 13.01 kN/m, is also slightly higher than that of sample
2(A22-200%).
(A22-200%).This Thismay
maybe bedue
dueto tothe
the PAG
PAGresidue
residuein in samples
samples 33 andand 4. On the
4. On the other
other hand,
hand, samples
samples
aged at
aged at high
high temperature
temperaturePAG PAGhave havea asignificantly
significantly lower
lowertear strength
tear strengthcompared
compared to those agedaged
to those in high
in
temperature air. This could be attributed to the adverse effect of the attack
high temperature air. This could be attributed to the adverse effect of the attack of by-products of by-products of PAG
of
thermal
PAG degradation
thermal on the
degradation onrubber.
the rubber.FTIRFTIR
analysis of PAG
analysis showed
of PAG showedthatthat
it became
it becameacidic during
acidic the
during
ageing
the period.
ageing period.As As
seen in Figure
seen in Figure 7b 7b(in(in
Section
Section 3.4), FTIR
3.4), FTIRspectra
spectrareveals
reveals thethe
appearance
appearance of of
a peak
a peakat
a wavenumber of 1725 cm −1 with an increased height as PAG is aged. This peak is indicative of the
at a wavenumber of 1725 cm with an increased height as PAG is aged. This peak is indicative of the
−1

presence of
presence of aa C=O
C=O [22]
[22] bond
bond and
and itsits increased
increased intensity
intensity with
with thermal
thermal ageing
ageing suggests
suggests the the intensified
intensified
acidity in
acidity in PAG.
PAG.
The SR teared specimens and their tear profiles are depicted in Figure 5. It can clearly be observed
that the tear behaviour of the SR changes with ageing. The first four samples, including unaged SR
(sample 1), exhibit a tear behaviour with several peaks (Figure 5a) while SR samples aged in the oven
show one small peak (Figure 5b) with a smooth constant tearing. The teared specimens (Figure 5c)
also illustrate this difference.

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 Polymers 2019, 11, x FOR PEER REVIEW 6 of 16

18 20

Change in tear strength (%),

Tear strength

Tear strength (kN/m)

15

to sample 1)
Polymers 2019, 11, 388 % Change 0 6 of 14
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12 -20

18 9 -4020

(%),
Tear strength

(relative
Tear strength (kN/m)
15 6 -600

(relative to sample 1)
% Change

Change in tear strength

3 -80
12 -20
0 -100
9 1 2 3 4 5 6 7 8 -40
Sample number
6 -60
Figure 4. Variations of the tear strength of SR with ageing conditions.
3 -80
The SR teared specimens
0 and their tear profiles are depicted in-100
Figure 5. It can clearly be
observed that the tear behaviour 1 of 2 the3SR changes
4 5 with
6 ageing.
7 8The first four samples, including
unaged SR (sample 1), exhibit a tear behaviour with several
Sample number peaks (Figure 5a) while SR samples aged
in the oven show one small peak (Figure 5b) with a smooth constant tearing. The teared specimens
Figure 4.
Figure
(Figure 5c) also illustrate Variations
4. this
Variations of the tear strength of SR with ageing conditions.
difference.

The SR teared specimens and their tear profiles are depicted in Figure 5. It can clearly be
observed that the tear behaviour of the SR changes with ageing. The first four samples, including
unaged SR (sample 1), exhibit a tear behaviour with several peaks (Figure 5a) while SR samples aged
in the oven show one small peak (Figure 5b) with a smooth constant tearing. The teared specimens
(Figure 5c) also illustrate this difference.

5. Tear profiles ofofSRSRspecimens ◦ C and (b) 180 ◦ C. (c) Illustration of teared

Figure
Figure 5. Tear profiles specimens aged
aged atat (a)
(a)22
22°C and (b) 180 °C. (c) Illustration of teared
specimens. It should
specimens. be noted
It should be notedthatthat
in this figure
in this only
figure oneone
only specimen is is
specimen shown
shownfor
foreach
eachsample
samplefor
forclarity
clarity
of the of the graphs.
graphs.

3.3. Tensile Testing

3.3. Tensile Testing

The The tensile

tensile properties
properties ofofSR,
SR,ininparticular,
particular, the
themodulus
modulusand elongation
and at break,
elongation are ofare
at break, significant
of significant
importance
importance for for
thethe industrial
industrial applicationwhich
application which is
is being
beingstudied
studiedinin
thethe
present article.
present Figure
article. 6 depicts
Figure 6 depicts
the effect of ageing conditions on the tensile properties of SR. The modulus at 100% strain
the effect of ageing conditions on the tensile properties of SR. The modulus at 100% strain is reported is reported
for the SR samples instead of the Young’s modulus, a common practice for elastomeric materials. The
for the SR samples instead of the Young’s modulus, a common practice for elastomeric materials.
Figure 2019,
5. Tear x;profiles of SRREVIEW
specimens aged at (a) 22 °C and (b) 180 www.mdpi.com/journal/polymers
°C. (c) Illustration of teared
The Polymers
unaged SR11,has doi: FOR PEER
a modulus of about 0.83 MPa. Samples 2, 3, and 4, which were aged at 22 ◦ C,
specimens. It should be noted that in this figure only one specimen is shown for each sample for
show lower modulus values than that of unaged SR. On the other hand, the moduli of samples aged
clarity of the graphs.
at 180 ◦ C are higher. Samples 5 and 6 with moduli of 1.747 and 2.608 MPa demonstrate very high
increments
3.3. of 111% and 215% compared to unaged SR, respectively. Similar to the hardness behaviour
Tensile Testing
of samples in Figure 3, strained samples at 22 ◦ C have lower moduli compared to their unstrained
The tensile
counterparts, properties
while samples of 6SR,
andin 8particular, the modulus
exhibit significantly and elongation
higher at break, to
moduli compared aresamples
of significant
5 and
importance for
7, respectively. the industrial application which is being studied in the present article. Figure 6 depicts
the effect of ageing conditions on the tensile properties of SR. The modulus at 100% strain is reported
for the SR samples instead of the Young’s modulus, a common practice for elastomeric materials. The
Polymers 2019, 11, x; doi: FOR PEER REVIEW www.mdpi.com/journal/polymers
aged at 22 °C. Furthermore, samples 2 and 4 (strained at 22 °C) show elongations slightly lower than
samples 1 and 3, respectively, resembling their tear behaviour. Figure 6c reveals that exposure to
PAG at low temperatures does not affect the tensile strength of the SR while straining the SR slightly
enhances its tensile strength. On the other hand, when comparing samples 5 and 6 with samples 7
and 8, it is obvious that high temperature PAG decreases the SR tensile strength far more severely
Polymers 2019, 11, 388 7 of 14
than high temperature air.

3 240
(a) Stress

Modulus at 100% strain

Change in Modulus (%)

200
160
2
120

(MPa)
80
1
40
0
0 -40
1 2 3 4 5 6 7 8
Sample number
1,200 20

Change in tensile strain (%)

Tensile strain at break (%)

(b) Strain
1,000 0

800 -20

600 -40

400 -60

200 -80

0 -100
Polymers 2019, 11, x FOR PEER REVIEW
1 2 3 4 5 6 7 8 8 of 16
Sample number
12 20
Tensile stress at break (MPa)

Change in tensile stress (%)

(c)
10 0
Stress
8 -20

6 -40

4 -60

2 -80

0 -100
1 2 3 4 5 6 7 8

Polymers 2019, 11, x; doi: FOR PEER REVIEW

Sample number www.mdpi.com/journal/polymers
Figure 6. Tensile properties
propertiesof
ofSR
SRsamples,
samples,(a)
(a)modulus
modulusatat100%
100%strain,
strain,
(b)(b) tensile
tensile strain
strain at at break,
break, andand
(c)
(c) tensile
tensile stress
stress at break.
at break.

The tensile strain at break or elongation at break of the SR samples in Figure 6b also illustrates
3.4. FTIR
variations comparable to those of the tear strength under the effect of different ageing environments.
To determine whether exposure to PAG and/or high temperatures affect the chemical structure
The elongations at break of the samples aged at 180 ◦ C are markedly lower than those of samples
of SR, attenuated total reflectance-FTIR analysis was conducted on all SR samples. The FTIR spectra
aged at 22 ◦ C. Furthermore, samples 2 and 4 (strained at 22 ◦ C) show elongations slightly lower than
of samples 1, 3, 5, and 7 are shown in Figure 7a. The five characteristic peaks for silicone rubber are
samples 1 and 3, respectively, resembling their tear behaviour. Figure 6c reveals that exposure to
observed at 2964, 1256, 1015–1085, and 795 cm−1, which correspond to the vibrations of methyl (–CH3),
PAG at low temperatures does not affect the tensile strength of the SR while straining the SR slightly
Si–CH3 bond, Si–O–Si, and Si–(CH3)2, respectively [12,23]. As evident from Figure 7a, there is no
enhances its tensile strength. On the other hand, when comparing samples 5 and 6 with samples 7 and
detectable changes in the FTIR spectra of aged samples of 3, 5, and 7 compared with the FTIR spectra
8, it is obvious that high temperature PAG decreases the SR tensile strength far more severely than
of unaged sample 1. This reveals that the surface chemistry of the SR is not impacted by either of the
high temperature air.
ageing environments. It is noteworthy to mention that the FTIR spectra of samples 2, 4, 6, and 8,
which are not shown here for clarity of the graph, were similar to the ones illustrated in Figure 7a.
Considering that straining is a mechanical phenomenon, such an observation is expected. In a
previous study on SR’s ageing behaviour, a similar stability in its chemical structure was observed
[2], which was attributed to the non-existence of oxidative agents due to purging the oven with
nitrogen. However, it appears that even the presence of oxygen in the oven at a high temperature of
Polymers 2019, 11, 388 8 of 14

3.4. FTIR
To determine whether exposure to PAG and/or high temperatures affect the chemical structure
of SR, attenuated total reflectance-FTIR analysis was conducted on all SR samples. The FTIR spectra
of samples 1, 3, 5, and 7 are shown in Figure 7a. The five characteristic peaks for silicone rubber are
observed at 2964, 1256, 1015–1085, and 795 cm−1 , which correspond to the vibrations of methyl (–CH3 ),
Si–CH3 bond, Si–O–Si, and Si–(CH3 )2 , respectively [12,23]. As evident from Figure 7a, there is no
detectable changes in the FTIR spectra of aged samples of 3, 5, and 7 compared with the FTIR spectra
of unaged sample 1. This reveals that the surface chemistry of the SR is not impacted by either of
the ageing environments. It is noteworthy to mention that the FTIR spectra of samples 2, 4, 6, and 8,
which are not shown here for clarity of the graph, were similar to the ones illustrated in Figure 7a.
Considering that straining is a mechanical phenomenon, such an observation is expected. In a previous
study on SR’s ageing behaviour, a similar stability in its chemical structure was observed [2], which was
attributed to the non-existence of oxidative agents due to purging the oven with nitrogen. However,
it appears that even the presence of oxygen in the oven at a high temperature of 180 ◦ C as in the
present study
Polymers does
2019, 11, x not change
FOR PEER the surface chemistry of SR.
REVIEW 9 of 16

1.6 sample 1 (A22-0%) 1015 (a)

Sample 3 (P22-0%) 795
1.4 Sample 5 (A180-0%)
Sample 7 (P180-0%) 1085
1.2
1256
1.0
Absorbance

2964
0.8
0.6
0.4
0.2
0.0
3500 2500 1500 500
0.7 Wavenumber
PAG-Fresh (cm-1) (b)
PAG-aged 2 weeks
0.6
PAG-aged 3 weeks
0.5
Absorbance

0.4
1725
0.3

0.2

0.1

0.0
3500 2500 1500 500
Wavenumber (cm-1)

Figure 7. FTIR spectra of (a) SR samples and (b) PAG samples.

Figure 7. FTIR spectra of (a) SR samples and (b) PAG samples.
3.5. Thermal Properties
3.5. Thermal Properties
While FTIR analyses did not demonstrate any variations among differently aged SR samples, DSC
While FTIR analyses did not demonstrate any variations among differently aged SR samples,
measurements showed that samples that were aged in air in the oven had significantly different DSC
DSC measurements showed that samples that were aged in air in the oven had significantly different
thermograms during both cooling and heating cycles as illustrated in Figure 8. The variations of the
DSC thermograms during both cooling and heating cycles as illustrated in Figure 8. The variations of
crystallisation temperature
the crystallisation (Tc ) and
temperature (Tccrystallisation enthalpy
) and crystallisation (∆H(ΔH
enthalpy c ) obtained from the cooling cycles
c) obtained from the cooling
and the
cycles and the melting temperature (Tm) and melting enthalpy (ΔHm) obtained fromthe
melting temperature (T m ) and melting enthalpy (∆H m ) obtained from the heating cycles are
heating cycles
shown in Figure 9 for all SR samples.
are shown in Figure 9 for all SR samples.
Polymers 2019, 11, 388 9 of 14
Polymers 2019, 11, x FOR PEER REVIEW 10 of 16

(a) 1.0 Exo down

Heat Flow (mW/mg)

0.5

0.0

-0.5 Sample 1 Sample 2

Sample 3 Sample 4
Sample 5 Sample 6
Sample 7 Sample 8
-1.0
-130 -110 -90 -70 -50 -30 -10 10
(b) 1.5 Temperature (°C)
Sample 1 Sample 2 Exo down
1.3 Sample 3 Sample 4
Sample 5 Sample 6
Heat Flow (mW/mg)

1.1 Sample 7 Sample 8

0.9

0.7

0.5

0.3

0.1
-130 -110 -90 -70 -50 -30 -10 10
Temperature (°C)

Figure 8. Comparative DSC thermograms of SR samples in the (a) second cooling cycle and (b) second
Figure
heating
Polymers 8.11,
cycle.
2019, Comparative DSC thermograms of SR samples in the (a) second cooling cycle and (b) second
x FOR PEER REVIEW 11 of 16
heating cycle.
-30 24
Tc Tm
Unaged SR(a) has a Tc and Tm of about −40 and −70.7 (b) ΔHc ΔHm
°C, respectively. All aged samples are
Temperature (°C)

-40 22
Enthalpy (J/g)

observed to have similar values of Tc and Tm except those aged at high temperatures in air. Samples
5 and 6 with
-50 a Tc and Tm of about −44 and −77 °C, respectively, 20 exhibit a decrease of about 10% in
their Tc and Tm values. In a comparable manner, while the ΔHc and ΔHm of samples 2, 3, 4, 7, and 8
have values-60close to those of the ΔHc and ΔHm of unaged 18 SR, samples 5 and 6 show a 12%–14%
reduction.-70
This suggests that samples 5 and 6 have smaller 16 degrees of crystallinity compared to other
samples. It is important to note that the DSC profiles and data reported in Figure 8 and Figure 9 are
-80
from the second cooling and heating cycles and therefore 14 the discrepancies could not be due to the
1 2 3 4 5 6 7 8 1 2 3 4 5 6 7 8
thermal history of the samples since the first heating cycles have erased the thermal history of the
samples [20,24]. It is also Sample
worthnumber
mentioning here that the second cooling Sampleandnumber
heating cycles for all
samples superimposed
Figure 9. Variations the
of first
thermal cooling and
properties ofheating
SR cycles
samples, (a)almost completely.
temperatures
Figure 9. Variations of thermal properties of SR samples, (a) temperatures of of The difference
crystallisation, in the
Tc, and
crystallisation, Tc ,
thermal properties
melting, T m. (b) of samples
Enthalpies of5 and 6 might
crystallisation, be
ΔH due to
c, and different
melting,
and melting, Tm . (b) Enthalpies of crystallisation, ∆Hc , and melting, ∆Hm . ΔHdegrees
m. of crosslinking compared to
other samples. However, further investigation is required to confirm this speculation.
3.6. DOE SR
Unaged Analysis:
has aMain and Interaction
Tc and Tm of about −40 and −70.7 ◦ C, respectively. All aged samples are
Effects
observed to have
Data similaron
obtained values of Tc and Tand
the mechanical m except
thermalthose aged at high
properties of SRtemperatures
samples frominthe air.ageing
Samples 5
with a Tc and
and 6experiment wasTanalysed
m of about in Minitab® −77 ◦for
−44 and 17.1.0 C, respectively, exhibit
the two-level full a decrease
factorial of about in
DOE presented 10%Tablein their
Tc and 2. T
The
m main
values. effects
In a of the ageing
comparable factors
manner,on the SR’s
while the ∆H
different
c and ∆H
properties
m are
of reported
samples in
2, Figure
3, 4, 7, 10.
and The8 have
values close to those of the ∆Hc and ∆Hm of unaged SR, samples 5 and 6 show a 12–14% reduction.
effect for each factor is determined by averaging the response values at the high level (+) and low
level (−) for
This suggests thatthat factor. 5Table
samples and 36 have
presents an example
smaller degrees foroffactor A in a two-level,
crystallinity compared three-factor (23)
to other samples.
factorial design and how the main effect is calculated for this factor. Figure 10 shows that the medium
It is important to note that the DSC profiles and data reported in Figures 8 and 9 are from the second
and temperature are the two most determining factors on SR ageing while strain seems to have the
cooling and heating cycles and therefore the discrepancies could not be due to the thermal history of
least impact and in some cases, even a negligible effect, such as for hardness. It is noteworthy to
the samples
mentionsince
that thethemechanical
first heating cycles
strain have
put on the erased
SR samplethewas
thermal history
a constant of and
strain the samples [20,24].
it is expected that It is
also worth
the SRmentioning
would behave here that theunder
differently second cooling
cyclic and
loading. heating
For cycles
the purpose offor
theall samples
present superimposed
study, constant
the first
strain was chosen rather than cyclic. In Figure 10, the steeper the line for a factor, the stronger its of
cooling
Polymers 2019, and
11, x; heating
doi: FOR PEERcycles
REVIEWalmost completely. The difference in the thermal properties
www.mdpi.com/journal/polymers

samples 5 and
effect 6 might
on the response.be due to different degrees of crosslinking compared to other samples. However,
further investigation is required to confirm this speculation.
Table 3. Example of the calculation of the main effect for one factor in a two-level, three-factor (23)
factorial design.

Run A Response Run A Response

1 - 𝑌 5 - 𝑌
2 + 𝑌 6 + 𝑌
3 - 𝑌 7 - 𝑌
Polymers 2019, 11, 388 10 of 14

3.6. DOE Analysis: Main and Interaction Effects

Data obtained on the mechanical and thermal properties of SR samples from the ageing experiment
was analysed in Minitab®17.1.0 for the two-level full factorial DOE presented in Table 2. The main
effects of the ageing factors on the SR’s different properties are reported in Figure 10. The effect
for each factor is determined by averaging the response values at the high level (+) and low level
(−) for that factor. Table 3 presents an example for factor A in a two-level, three-factor (23 ) factorial
design and how the main effect is calculated for this factor. Figure 10 shows that the medium and
temperature are the two most determining factors on SR ageing while strain seems to have the least
impact and in some cases, even a negligible effect, such as for hardness. It is noteworthy to mention
that the mechanical strain put on the SR sample was a constant strain and it is expected that the SR
would behave differently under cyclic loading. For the purpose of the present study, constant strain
was chosen rather than cyclic. In Figure 10, the steeper the line for a factor, the stronger its effect on
the response.
Polymers 2019, 11, x FOR PEER REVIEW 12 of 16

Figure 10.
Figure 10. Main
Main factors
factorseffects
effectson
onthe
theproperties
propertiesofof
the SRSR
the samples.
samples.
3)
The 3.
Table contrasts
Exampleofofaverages determined
the calculation in theeffect
of the main factorial design
for one factorprovide statistical
in a two-level, power to(2the
three-factor
estimated
factorialeffects
design.compared to the one-factor-at-a-time (OFAT) experiments, which require more runs
to provide the equivalent precision power. In addition to the reduced number of runs, revealing the
Run A Response Run A Response
impacts of the “interactions” of factors on the response is another significant aspect of DOE [7]. It is
important to investigate 1 the interactions
- Ysince
1 Y5 are significant, one
if their5 effects on- the response
cannot interpret the main effects without considering the interaction effectsY[8,25].
2 + Y 2 6 + 6 Figure 11 depicts
3 - Y3 7 - Y7
the two-way interaction plots for the strain, medium, and temperature of the SR samples. In these
4 + Y4 8 + Y8
plots, the parallel and non-parallel lines are indicative of the non-existence and existence of an
Main effect for factor A: Contrast between the high and the low averages obtained from formulas: High average =
interaction
Y2 +Y4 +Y6 +between
Y8 each two factors, respectively. The more non-parallel the lines are, the greater
4 ; Low average = Y1 +Y3 +4 Y5 +Y7 .
the strength of the interaction. Figure 11 shows that there are some interactions between the ageing
factors.
The A strong interaction
contrasts of averages between
determined the medium and temperature
in the factorial is observed
design provide for thepower
statistical hardness,
to the
followed by the temperature/strain interaction and a negligible strain/medium
estimated effects compared to the one-factor-at-a-time (OFAT) experiments, which require more runs interaction (Figure
11a). For the tear strength, the plots reveal negligible to no interactions (Figure 11b). For the tensile
properties, however, interactions are observed between all the ageing factors (Figure 11c,d,e). On the
other hand, the plots for the thermal properties show a very strong interaction between medium and
temperature with negligible to no interactions among other factors.
Polymers 2019, 11, 388 11 of 14

to provide the equivalent precision power. In addition to the reduced number of runs, revealing
the impacts of the “interactions” of factors on the response is another significant aspect of DOE [7].
It is important to investigate the interactions since if their effects on the response are significant,
one cannot interpret the main effects without considering the interaction effects [8,25]. Figure 11
depicts the two-way interaction plots for the strain, medium, and temperature of the SR samples.
In these plots, the parallel and non-parallel lines are indicative of the non-existence and existence of an
interaction between each two factors, respectively. The more non-parallel the lines are, the greater the
strength of the interaction. Figure 11 shows that there are some interactions between the ageing factors.
A strong interaction between the medium and temperature is observed for the hardness, followed by
the temperature/strain interaction and a negligible strain/medium interaction (Figure 11a). For the
tear strength, the plots reveal negligible to no interactions (Figure 11b). For the tensile properties,
however, interactions are observed between all the ageing factors (Figure 11c–e). On the other hand,
the plots for the thermal properties show a very strong interaction between medium and temperature
with negligible to no interactions among other factors.
Polymers 2019, 11, x FOR PEER REVIEW 13 of 16

Figure
Figure 11.11.Interaction
Interaction effects
effects of
of ageing
ageingfactors
factorsonon
thethe
mechanical andand
mechanical thermal properties
thermal of theof
properties SRthe
samples.
SR samples.

Factors’interactions
Factors’ interactionseffects
effects can
can be
be more
more clearly
clearly observed
observed from
from the
thePareto
Paretocharts.
charts.Figure
Figure12 12
illustrates the Pareto charts for the experimental factors of the present study. These charts depict
illustrates the Pareto charts for the experimental factors of the present study. These charts depict the the
relevant
relevant significance
significance ofofthe
theageing
ageingfactors’
factors’main
main and
and interaction
interactioneffects
effectsononthe
themechanical and
mechanical thermal
and thermal
properties of SR. As was seen in Figure 11a, Figure 12a also shows that the medium/temperature
properties of SR. As was seen in Figure 11a, Figure 12a also shows that the medium/temperature
interaction (BC) and strain/temperature interaction (AC) are much more significant than the
interaction (BC) and strain/temperature interaction (AC) are much more significant than the
strain/medium (AB) and the three-way interaction (ABC). It is also interesting to note that the
strain/medium (AB) and the three-way interaction (ABC). It is also interesting to note that
medium/temperature interaction has a larger impact on the hardness than the temperature. In
the medium/temperature interaction has a larger impact on the hardness than the temperature.
accordance with Figure 11b, Figure 12b clearly illustrates the very small effects of the factors’
In accordance with Figure 11b, Figure 12b clearly illustrates the very small effects of the factors’
interactions on the SR’s tear strength. It is observed that the effect of temperature is far more
significant than those of the other ageing factors or the interactions. Temperature is also found to be
the most influential factor on the SR’s tensile properties. However, as seen in Figure 12c,d, the
medium and strain as well as the factors’ interactions affect the tensile strength, elongations, and
modulus of the SR. On the other hand, the thermal properties of SR are mostly influenced by the
temperature, medium, and their two-way interaction (Figure 12f–i).
Polymers 2019, 11, 388 12 of 14

interactions on the SR’s tear strength. It is observed that the effect of temperature is far more significant
than those of the other ageing factors or the interactions. Temperature is also found to be the most
influential factor on the SR’s tensile properties. However, as seen in Figure 12c,d, the medium and
strain as well as the factors’ interactions affect the tensile strength, elongations, and modulus of the SR.
On the other hand, the thermal properties of SR are mostly influenced by the temperature, medium,
and their two-way interaction (Figure 12f–i).
Polymers 2019, 11, x FOR PEER REVIEW 14 of 16

Figure 12.
Figure 12. Pareto charts illustrating
illustrating the effects
effects of ageing factors (A: strain, B: medium, C: temperature)
and their
and their two-
two- and
and three-way
three-wayinteractions
interactions(AB,
(AB,AC,
AC,BC,
BC,ABC)
ABC)ononthe
theSRSRproperties.
properties.

4.
4. Conclusions
Conclusions
The
The design
design of of the
the experiment
experiment was was used
used toto investigate
investigate the
the effects
effects of
of three
three ageing
ageing factors
factors and
and
investigate
investigate their interactions on the physical properties of silicone rubber used in a industrial
their interactions on the physical properties of silicone rubber used in a particular particular
process. Statistical
industrial process.analysis revealed
Statistical that revealed
analysis temperature thatand medium were
temperature andthe most influential
medium were theageing
most
factors.
influential ageing factors. The temperature/medium interaction was also observed to havethea
The temperature/medium interaction was also observed to have a significant effect on
SR’s properties.
significant effectThe
on mechanical propertiesThe
the SR’s properties. of SR were found
mechanical to be more
properties of susceptible
SR were found to deterioration
to be more
than the thermal properties. The hardness decreased for all ageing conditions
susceptible to deterioration than the thermal properties. The hardness decreased for expect for samples aged
all ageing
in high temperature
conditions expect forair and it reached
samples a value
aged in high of 57.35 in air
temperature sample
and itA180-200%, showing
reached a value an increase
of 57.35 of
in sample
40%. The tear strength, however, decreased markedly when exposed to both
A180-200%, showing an increase of 40%. The tear strength, however, decreased markedly when high-temperature air
and PAG,to
exposed with
botha decrease of 96% in sample
high-temperature air and P180–200%.
PAG, with aFor both hardness
decrease of 96% inand tear strength,
sample strained
P180–200%. For
samples showed lower values compared to their unstrained counterparts.
both hardness and tear strength, strained samples showed lower values compared to their unstrained
counterparts.
Ageing at 22 °C did not impact the tensile properties of SR samples significantly. In contrast,
ageing at 180 °C resulted in a 90% reduction in the elongation at break as well as an 86% reduction in
the tensile strength of sample P180-200%. Statistical analysis showed that temperature, medium, and
their interaction affected the tensile properties. Strain also showed an impact on the elongation at
Polymers 2019, 11, 388 13 of 14

Ageing at 22 ◦ C did not impact the tensile properties of SR samples significantly. In contrast,
ageing at 180 ◦ C resulted in a 90% reduction in the elongation at break as well as an 86% reduction in the
tensile strength of sample P180-200%. Statistical analysis showed that temperature, medium, and their
interaction affected the tensile properties. Strain also showed an impact on the elongation at break of
the samples. No appreciable change was detected in the FTIR spectra of the aged samples, suggesting
that the SR ageing mechanism is mainly physical. Thermal properties (Tc , Tm , ∆Hc , and ∆Hm ) of the
SR, determined via DSC measurements, did not demonstrate any significant variation compared to
those of unaged SR except for samples aged in air at 180 ◦ C, which showed reduced values.

Author Contributions: S.K., M.D.S., S.A.-A. and R.V. conceived and designed the experiments; S.K. performed
the experiments; S.K. analyzed the data; S.A.-A. and M.D.S. contributed reagents/materials/analysis tools; S.K.
and R.V. wrote the paper.
Funding: This research was funded by the Australian Research Council (ARC) Research Hub for Future Fibres,
grant number IH140100018.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Goudie, J.; Owen, M.; Orbeck, T. A review of possible degradation mechanisms of silicone elastomers in
high voltage insulation applications. In Proceedings of the 1998 Annual Report Conference on Electrical
Insulation and Dielectric Phenomena, Atlanta, GA, USA, 25–28 October 1998.
2. Kashi, S.; Varley, R.; De Souza, M.; Al-Assafi, S.; Di Pietro, A.; De Lavigne, C.; Fox, B. Mechanical, Thermal,
and Morphological Behavior of Silicone Rubber during Accelerated Aging. Polym.-Plast. Technol. Eng. 2018,
57, 1687–1696. [CrossRef]
3. Characteristic Properties of Silicone Rubber Compounds. 2012. Available online: https://www.shinetsusilicone-
global.com/catalog/pdf/rubber_e.pdf (accessed on 25 February 2018).
4. Mark, J.E. Some Interesting Things about Polysiloxanes. Acc. Chem. Res. 2004, 37, 946–953. [CrossRef]
[PubMed]
5. Mark, J.E.; Lin, G.; Schaefer, D.W. The Polysiloxanes; Oxford University Press: New York, NY, USA, 2015.
6. Andriot, M.; Chao, S.H.; Colas, A.R.; Cray, S.E.; DeBuyl, F.; DeGroot, J.V.; Dupont, A.; Easton, T.; Garaud, J.L.;
Gerlach, E.; et al. Silicones in industrial applications. Inorg. Polym. 2007, 61–161.
7. Jerschow, P. Silicone Elastomers; Rapra Technology Limited: Wolverhampton, UK, 2001.
8. Colas, A. Silicones: Preparation, Properties and Performance; Dow Corning, Life Sciences: Corning, NY, USA,
2005; pp. 1–14.
9. Yuan, X.; Lu, H.; Lan, L.; Wang, H.; Wen, X.; Liao, Y.; Zhang, F. Study on the effect of corona on hydrophobicity
recovery performance of RTV silicone rubber and its failure criterion. In Proceedings of the IEEE Electrical
Insulation Conference (EIC), Montreal, QC, Canada, 19–22 June 2016.
10. Wang, Z.; Zhang, X.; Wang, F.; Lan, X. Chemical characterization and research on the silicone rubber material
used for outdoor current transformer insulation. Phosphorus Sulfur Silicon Relat. Elem. 2016, 192, 109–112.
[CrossRef]
11. Bleszynski, M. Aging Assessment of High Voltage Single Component Room Temperature Vulcanized Silicone
Rubber (RTV-1) Subjected to Aqueous Salt. Ph.D. Thesis, University of Denver, Denver, CO, USA, 2016.
12. Ohki, Y.; Hanada, S.; Miyamoto, M.; Hirai, N.; Yang, L. Aging mechanism of silicone rubber by heat and
gamma-rays. In Proceedings of the 2016 IEEE Conference on Electrical Insulation and Dielectric Phenomena
(CEIDP), Toronto, ON, Canada, 16–19 October 2016.
13. Haddad, G.; Wong, K.; Gupta, R. Dielectric breakdown characteristics of htv silicone rubber under multiple
stress conditions. In Proceedings of the 2014 International Symposium on Electrical Insulating Materials
(ISEIM), Niigata City, Japan, 1–5 June 2014.
14. Yan, Z.; Liang, X.; Gao, Y.; Liu, Y. Aging and self-healing properties of superhydrophobic silicone rubber.
IEEE Trans. Dielectr. Electr. Insul. 2016, 23, 3531–3538. [CrossRef]
15. Verma, A.R.; Reddy, B.S. Aging studies on polymeric insulators under DC stress with controlled climatic
conditions. Polym. Test. 2018, 68, 185–192. [CrossRef]
Polymers 2019, 11, 388 14 of 14

16. Bernardi, L.; Hopf, R.; Sibilio, D.; Ferrari, A.; Ehret, A.E.; Mazza, E. On the cyclic deformation behavior,
fracture properties and cytotoxicity of silicone-based elastomers for biomedical applications. Polym. Test.
2017, 60, 117–123. [CrossRef]
17. Wu, J.; Dong, J.; Wang, Y.; Gond, B.K. Thermal oxidation ageing effects on silicone rubber sealing performance.
Polym. Degrad. Stab. 2017, 135, 43–53. [CrossRef]
18. Chang, H.; Wan, Z.; Chen, X.; Wan, J.; Luo, L.; Zhang, H.; Shu, S.; Tu, Z. Temperature and humidity effect
on aging of silicone rubbers as sealing materials for proton exchange membrane fuel cell applications.
Appl. Therm. Eng. 2016, 104, 472–478. [CrossRef]
19. Kashi, S.; Gupta, R.K.; Kao, N.; Bhattacharya, S.N. Electrical, thermal, and viscoelastic properties of graphene
nanoplatelet/poly (butylene adipate-co-terephthalate) biodegradable nanocomposites. J. Appl. Polym. Sci.
2016, 133. [CrossRef]
20. Kashi, S.; Gupta, R.K.; Baum, T.; Kao, N.; Bhattacharya, S.N. Morphology, electromagnetic properties and
electromagnetic interference shielding performance of poly lactide/graphene nanoplatelet nanocomposites.
Mater. Des. 2016, 95, 119–126. [CrossRef]
21. Brüning, K. In-Situ Structure Characterization of Elastomers during Deformation and Fracture. Ph.D. Thesis,
Technische Universität Dresden, Dresden, Germany, 2014.
22. Characteristic IR Absorption Frequencies of Organic Functional Groups. 2019. Available online: http:
//www2.ups.edu/faculty/hanson/Spectroscopy/IR/IRfrequencies.html (accessed on 5 February 2019).
23. Stathi, K.; Tarantili, P.A.; Polyzois, G. The effect of accelerated ageing on performance properties of addition
type silicone biomaterials. J. Mater. Sci. Mater. Med. 2010, 21, 1403–1411. [CrossRef] [PubMed]
24. Kashi, S.; Gupta, R.K.; Kao, N.; Hadigheh, S.A.; Bhattacharya, S.N. Influence of graphene nanoplatelet
incorporation and dispersion state on thermal, mechanical and electrical properties of biodegradable
matrices. J. Mater. Sci. Technol. 2017, 34, 1026–1034. [CrossRef]
25. Kashi, S.; Satari, B.; Lundin, M.; Horváth, I.S.; Othman, M. Application of a mixture design to identify the
effects of substrates ratios and interactions on anaerobic co-digestion of municipal sludge, grease trap waste,
and meat processing waste. J. Environ. Chem. Eng. 2017, 5, 6156–6164. [CrossRef]

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