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energies

Article
Study on the Effects of Thermal Aging on Insulating
Paper for High Voltage Transformer Composite with
Natural Ester from Palm Oil Using Fourier Transform
Infrared Spectroscopy (FTIR) and Energy Dispersive
X-ray Spectroscopy (EDS)
Abi Munajad * ID
, Cahyo Subroto and Suwarno ID

School of Electrical Engineering and Informatics, Institut Teknologi Bandung, 40132 Bandung, Indonesia;
cahyosubroto@rocketmail.com (C.S.); suwarno@stei.itb.ac.id (S.)
* Correspondence: abi.munajad@gmail.com; Tel.: +62-857-465-76059

Received: 16 October 2017; Accepted: 8 November 2017; Published: 13 November 2017

Abstract: Mineral oil is widely used as liquid insulation in high voltage equipment. Due to
environmental considerations, recently natural esters have been considered as naturally friendly
liquid insulation candidates for high voltage transformers. In this experiment, transformer insulation
paper was subjected to get accelerated aging test with copper strip in natural ester in a hermeneutical
heat-resistant glass bottle at temperatures of 120 ◦ C and 150 ◦ C for 336 h, 672 h and 1008 h.
The experimental results of Fourier transform infrared spectroscopy (FTIR) showed that the intensity
of the absorbance peak of the O–H functional group decreased with aging, while the intensity of
the C–H and C=O functional group absorbance peaks have increased with aging and the intensity
of the C–O functional group absorbance peak has a tendency to increase with aging. The energy
dispersive X-ray spectroscopy (EDS) experimental results showed that the weight percent of the
element C increased with aging and the weight percent of the element O has decreased with aging.
The experimental results show a good correlation between the degree of polymerization (DP) and the
weight percent of O element. This indicates that EDS may be used as a new method for estimating
the DP of transformer insulation paper.

Keywords: transformer insulation paper; natural ester; thermal aging; Fourier transform infrared
spectroscopy (FTIR); energy dispersive X-ray spectroscopy (EDS)

1. Introduction
An electric power system consists of generating stations, transmission, and distribution systems.
One of the most important pieces of equipment in electric power systems are power transformers.
The performance of transformers depends substantially on the condition of its liquid and solid
insulation. Insulating liquids provide two purposes in the transformer operation, as an insulation
material and the cooling medium [1]. The lifetime of a transformer is mainly determined from
the degradation of the insulation paper due to thermal-depolymerization and mechanical stress [2].
Heat, moisture and oxygen accelerate the degradation/aging process of transformer insulation paper
which is subjected to irreversible degradation [3]. Liquid insulating and solid insulating materials of
transformers interact during operation so that their performance can affect each other.
For a long time, mineral oil has been extensively used as the transformer oil. Petroleum products
are eventually going to run out, and that could be a serious problem even by the mid-twenty-first
century [4]. In the future, natural esters will take over the role of mineral oils as transformer insulation
liquids due to escalating price of conventional oils and increasing environmental constraints imposed

Energies 2017, 10, 1857; doi:10.3390/en10111857 www.mdpi.com/journal/energies


Energies 2017, 10, 1857 2 of 15

by the authorities [3]. The advantage of using natural esters as transformer insulating liquids is the
non-toxic characteristics of the material which will not produce any toxic products during fires [1] and
higher fire point of about 300 ◦ C [5]. Natural esters are more environmentally compatible because they
are biodegradable [1]. Natural esters have a significantly higher breakdown voltage level than mineral
oil [6]. Some authors have suggested that the good performance of transformer insulation paper as
solid insulation of transformers immersed in natural esters is due to the fact that these oils are more
hydrophilic than mineral oil [7,8]. In natural ester/pressboard insulation, moisture tends to remain in
the natural ester, while in the mineral oil/pressboard insulation system moisture tends to remain in
the pressboard [9]. Thus water is absorbed by the natural esters, making the transformer insulation
paper drier [10,11]. The lifetime of paper aged in natural esters is higher than that of the paper aged
in mineral oil [12]. Many researchers agree that the insulating paper performance in natural esters is
better than in mineral oil [3,7,13,14]. In other hand, the acidity level of natural esters rapidly increases
with aging in a moisture rich environment due to hydrolytic processes [14]. The acidity levels of
natural esters are not detrimental to paper insulation performance, but it is necessary to investigate
the effect of high acidity level on paper and steel materials, especially its corrosion effects [14].
One of the alternative insulating liquids are natural esters from palm oil [1]. Investigation of
electrical, physical and chemical properties of palm oil shows that the liquid possesses good properties
to be used as substitutes for mineral oil in high voltage experiments [1,15,16]. This study focuses
to present the results of a laboratory study of the chemical structure of the transformer insulation
paper under accelerated thermal aging test in natural ester from palm oil. In this paper, accelerated
thermal aging test at 120 ◦ C and 150 ◦ C was conducted for 336 h, 672 h and 1008 h. The degree of
polymerization (DP) and tensile strength (TS) were measured and analyzed. The chemical structure of
transformer insulation paper was identified using Fourier transform infrared spectroscopy (FTIR) and
energy dispersive X-ray spectroscopy (EDS). Spectroscopy is a powerful non-destructive technique
that utilizes electromagnetic radiation interaction effect to determine the energy level and structure
atomic or molecular substance [17]. Spectroscopy has been successfully used to quantify 2-FAL
compound in transformer oil, identify the interfacial tension number of transformer oil, quantify and
identify the dissolved decay product in oil [17–20]. In this research paper, the correlation between DP
and chemical structure will also be presented to estimate the DP value of paper insulation using a
spectroscopy technique.

2. Materials and Methods

2.1. Samples
The insulating liquid used in this experiment was a commercially available natural ester from palm
oil. The type of transformer insulation paper used for these studies was Kraft paper for transformer
windings. The thickness of the paper is 0.01 mm and the basis weight is 0.011 g/cm2 . The initial water
content for new transformer insulation paper is about 5% at the room humidity and temperature levels.
Each aging test bottle contained transformer insulation paper (10 g), natural ester (200 g) and a copper
metal strip (8.75 g) [21]. The transformer insulation paper was wrapped around the copper metal strip.
Firstly, the natural ester samples in the glass bottles were heated without sealing at a temperature of
100 ◦ C for 24 h in order to ensure the same initial conditions [1,15,16]. Then the transformer insulation
paper and copper metal strip were put into heat-resistant and sealed glass bottles. Thermal aging in
sealed systems was chosen based on the recommendation of the IEEE loading guide for modern sealed
transformers [22]. All the sealed glass bottles were put in a different aging oven and heated to 120 ◦ C,
while the other oven was heated to 150 ◦ C for 336, 672 and 1008 h. The 150 ◦ C temperature level
selected from the reference published in IEEE by McShane, et al. [13], while the 120 ◦ C temperature
level is a hot spot temperature according to the IEEE [23]. Samples and their treatments are shown in
Table 1.
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Table 1. Samples and treatment.


Table 1. Samples and treatment.
Sample Aging
T0
Sample NewAging
T1.120
T0 120 °C forNew
336 h
T2.120
T1.120 120 °C
120 C672
for
◦ forh336 h
T3.120
T2.120 120 °C for◦ C
120 1008
for h
672 h
T1.150
T3.120 150 120 ◦ C336
°C for for h
1008 h
T1.150 ◦ C for 336 h
150for
T2.150 150 °C 672 h
T2.150 150 ◦ for 672 h
T3.150 150 °C for C1008 h
T3.150 150 ◦ C for 1008 h
2.2. Tensile Strength (TS) and Degree of Polymerization (DP)
2.2. Tensile Strength (TS) and Degree of Polymerization (DP)
A Mark-10 Force Gauge was used in this experiment to conduct TS test. It has ±0.1% accuracy, a
A Mark-10
sampling rate of Force
14,000Gauge
Hz andwas used in for
is suitable thistension
experiment to conduct TS
and compression test. It has ±
measurement 0.1% accuracy,
applications up
a sampling
to rate of
500 lbF (2500 N).14,000 Hz and is suitable
The transformer insulationfor paper
tensionwasandinserted
compression
to the measurement
Mark-10 Forceapplications
Gauge and
up to 500
pulled lbFit(2500
until tore. N).
TheThe speedtransformer
of the tensileinsulation
test was paper was inserted
10 mm/min. to the Mark-10ofForce
The measurement the DP Gauge
was
and pulled until
conducted it tore.
by using theThe speed ofviscometer
intrinsic the tensile method,
test was 10 mm/min.
including theThe measurement
capillary of theand
viscometer DP
was conducted
cupryetilene by using
solvent the intrinsic
diamine. The DP test viscometer method,
was conducted byincluding
referring tothethe
capillary viscometer
ES ISO 5351 standard.and
cupryetilene solvent diamine. The DP test was conducted by referring to the ES ISO 5351 standard.
2.3. Fourier Transform Infrared Spectroscopy (FTIR) and Energy Dispersive X-ray Spectroscopy (EDS)
2.3. Fourier Transform Infrared Spectroscopy (FTIR) and Energy Dispersive X-ray Spectroscopy (EDS)
An ALPHA FTIR Spectrometer (Bruker Corporation, Billerica, Massachusetts, USA) was used in
An ALPHAto
this experiment FTIRget Spectrometer
infrared spectra (Bruker Corporation,
of functional Billerica,
groups Massachusetts,
of transformer USA)paper.
insulation was used
The
in this experiment
attenuated to get (ATR)
total reflection infrared spectra of
technique was functional
used to getgroups of transformer
the infrared spectra.insulation paper.
The penetration
The attenuated
depth of the lighttotal
beamreflection
into the (ATR)
sampletechnique wasmode
using this used to
is get the0.5–3
about infrared
μm,spectra.
dependingThe on
penetration
the ATR
depth of the light beam into the sample using this mode is about 0.5–3
material used [3]. Small samples of transformer insulation paper were prepared to conduct µm, depending on the ATR
this
material used [3]. Small samples of transformer insulation paper were
measurement. The measurement of each sample was conducted twice to ensure the value of intensity prepared to conduct this
measurement.
of peak absorbance.The measurement
Figure 1a shows of each
the sample
ALPHAwas FTIRconducted twice to ensure the value of intensity
spectrometer.
of peak absorbance. Figure 1a shows the ALPHA FTIR spectrometer.
The analysis of the chemical structure of the paper was conducted by using EDS measurement.
Theresearch,
In this analysis aofHitachi
the chemical
SU 3500 structure
(Hitachiof the paper was conducted
High-Technologies by using Minato-ku,
Corporation, EDS measurement.
Tokyo,
In this research, a Hitachi SU 3500 (Hitachi High-Technologies
Japan) and EDAX (Ametek, Inc., Mahwah, NJ, USA) instrument was used to conduct the Corporation, Minato-ku, Tokyo,
EDS
Japan) and EDAX
measurements. (Ametek,
Before the EDS Inc.,measurements
Mahwah, NJ, were USA) conducted,
instrument small
was used to conduct
samples the EDS
of transformer
measurements.
insulation paperBefore
were theputEDS measurements
on the specimen holderwere conducted,
to performsmall samplesprocess
the coating of transformer
using aninsulation
MC1000
paper were put on the specimen holder to perform the coating
Ion Sputter. EDS measurements have the purpose to identify the chemical elements process using an MC1000 Ion Sputter.
of the
EDS measurements have the purpose to identify the chemical elements
transformer insulation paper. Figure 1b shows the Hitachi SU 3500 and EDAX system used for theof the transformer insulation
paper.
EDS Figure 1b shows the Hitachi SU 3500 and EDAX system used for the EDS measurements.
measurements.

(a) (b)
Figure
Figure 1.
1. (a)
(a) ALPHA
ALPHA FTIR
FTIR Spectrometer;
Spectrometer; (b)
(b) Hitachi
Hitachi SU
SU 3500
3500 and
and EDAX.
EDAX.
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3.
3. Results
Results and
and Discussion
Discussion
3.1.
3.1. Degree of Polymerization (DP) and Tensile Strength (TS)
3.1. Degree
Degree ofof Polymerization
Polymerization (DP)(DP) andand Tensile
Tensile Strength
Strength (TS)
(TS)
Figure
Figure 2 shows the reduction of of the DP of transformer insulation paper with aging at the
Figure 22 shows
shows ◦the
the reduction
reduction ◦ C.of
the
the DP
DP of of transformer
transformer insulation
insulation paperpaper with
with aging
aging atat the
the
temperatures
temperatures of
of 120
120 C
°C and
and 150
150 °C. The
The DP
DP indicates
indicates the
the number
number ofofCC
6 H O glucose rings
6H10O5 glucose rings that
10 5 that
temperatures of 120 °C and 150 °C. The DP indicates the number of C6H10O5 glucose rings that
compose
compose the cellulosic macromolecule and it is the valuable indicator that provides information
compose the the cellulosic
cellulosic macromolecule
macromolecule and and it
it is
is the
the valuable
valuable indicator
indicator thatthat provides
provides information
information
about
about the
the degradation
degradation state
state of
of cellulose
cellulose and
and mechanical
mechanical strength
strength [24].
[24]. It is
It is seen
seen that
that the
the DP has
about the degradation◦ state of cellulose and mechanical strength [24]. It is seen
◦ C. At about 140 ◦ C, the rate of the degradation process that the DP
DP has
has
decreased
decreased faster
faster at
at 150
150 C
°C than
than at
at 120
120 °C. At about 140 °C, the rate of the degradation process increases
increases
decreased faster at 150 °C than at 120 °C. At about 140 °C, the rate of the degradation process increases
significantly,
significantly, implying either a change in the activation energy or in in the pre-exponential
pre-exponential factor [25]. [25].
significantly, implying
implying either
either aa change
change◦in in the
the activation
activation energy
energy oror in thethe pre-exponential factorfactor [25].
The
The DP of paper samples aged at 150 C was significantly decreased due to thermal stress at high
The DP
DP ofof paper
paper samples
samples aged aged atat 150
150 °C
°C was
was significantly
significantly decreased
decreased due due toto thermal
thermal stress
stress at
at high
high
temperature,
temperature, in
in which
which the
the weak
weak links
links existing
existing in
in polymer
polymer chains
chains are
are easily
easily chopped
chopped [3,9,26,27].
[3,9,26,27].
temperature, in which the weak links existing in polymer chains are easily chopped [3,9,26,27].

2500
2500

2000
2000

1500
1500
DP
DP

1000
1000

500
500

0
0
0
0 336
336 672
672 1008
1008
Aging
Aging Time
Time (h)
(h)

120
120 C
C 150
150 C
C

Figure 2.
Figure2.
Figure Measured
2. Measured DP
Measured DP of
DPof paper
ofpaper samples.
papersamples.
samples.

Figure
Figure 333 shows
Figure shows
showsthethe time
thetime dependence
dependenceofof
timedependence TS
ofTS under
TSunder accelerated
underaccelerated
accelerated thermal
thermal
thermal aging
aging at at
aging thethe
at temperatures
temperatures
the of
temperatures
120 ◦ C °C
of 120 andand ◦ C.°C.
150150 TheThe figure
figure indicates
indicates thatthat
the the
TS TS
has has reduced
reduced faster
faster underunder
higherhigher temperature
temperature [28].
of 120 °C and 150 °C. The figure indicates that the TS has reduced faster under higher temperature
[28].
[28]. From
From thesethese
From figures
these figures it
it seems
it seems
figures that
that the
seems the
the reduction
thatreduction behavior
behavior
reduction of theof
behavior DP
of the
is DP
the is
is similar
similar
DP to theto
similar TS.
to the
the TS.
TS.

100
100
90
90
80
80
70
70
60
(%)

60
TS (%)

50
50
TS

40
40
30
30
20
20
10
10
0
0
0
0 336
336 672
672 1008
1008
Aging
Aging Time
Time (h)
(h)

120
120 C
C 150
150 C
C

Figure 3.
Figure3. Measured
3. Measured TS
Measured TS of
TSof paper
ofpaper samples.
papersamples.
samples.
Figure
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Energies 2017, 10, 1857 5 of 15
Figure
Figure333333shows
Figure
Figure
Figure
Figure shows
shows
showsTS
shows
shows TSTS
TS
TS values
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values
valuesof
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values of
of
of
of insulation
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ester
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at
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and 150
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within
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within
within 0–1008
0–1008
0–1008
0–1008
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h.
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The
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transformer
transformer
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ester h.reached
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The degradation
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to
to thermal
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under at 336accelerated
under
50%accelerated accelerated
h, andthermalTS 25% thermal
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aging672
aging.
aging.
at ah.temperature
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degradation
of 150DP °C andinTS process
process
haveester
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of transformer
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explained
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byby
by
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the
the
the
the
the structural
structural
structural
structural
structural
structural changes
changes
changes
changes
changes
changes of
ofof
of
ofof the
the
the
the
the
the natural
natural
natural
natural
natural
natural ester
ester
ester
ester
ester
ester and
and
andthe
and
and
and the
the
the
the
the
stressend-of-life
under accelerated criteria of TS thermal
50% at aging.
336 h, and TheTSdegradation
25% 672 h. The process
value of DP transformer
and TS have insulation
decreasedpaper due due
transformer
transformer
transformer
transformer
transformer insulation
insulation
insulation
insulation
insulation paper
paper
paper
paper using
using
using
using FTIR
FTIR
FTIR
FTIR and
andand
and EDS.
EDS.
EDS.
EDS. The
The
The
The interactions
interactions
interactions
interactions between
between
between
between the
the
the
the natural
natural
natural
natural ester
ester
ester
ester and
and
and
and
transformer
to to thermal
thermal insulation
aging stresscanunderbepaper
paper using
using
accelerated
explained byFTIR
FTIR
thermal andand
the structural EDS.
aging.EDS. The The
The interactions
degradation
changes interactions
of the process between
naturalbetween the
the
of transformer
ester and natural
natural
the ester
insulation esterand
transformer and
transformer
transformer
transformer
transformer
transformer
transformer
paper due
insulation
insulation
insulation
insulation
insulation
insulation
to thermal
paper
paper
paper
paper
paper
paper
aging
during
during
during
during
during
canduring
be explained
thermal
thermal
thermal
thermal
thermal
thermal aging
aging
aging
aging
by aging
aging
the structural
involve
involve
involve
involve
involve
involve changes
hydrolysis
hydrolysis
hydrolysis
hydrolysis
hydrolysis
hydrolysis and
and
and
and
and
and transesterification
transesterification
transesterification
transesterification
transesterification
transesterification
insulation paper using FTIR and EDS. The interactions between the of the natural
natural ester ester
and and the
transformer
processes.
processes.
processes.
processes.
processes.
processes.
transformer insulation paper using FTIR and EDS. The interactions between the natural ester and
insulation paper during thermal aging involve hydrolysis and transesterification processes.
Figure
Figure4a,b
transformer
Figure
Figure
Figure 4a,b
4a,bshow
4a,b
4a,b show
showthe
insulation
show
show the
the
the correlation
thecorrelation
correlation
paper during
correlation
correlation between
between
between
between
betweenthermal DP
DP
DPDP and
DPagingandTS
and
and
and TSTSTS
TS of
of
ofof paper
ofpaper
involve paper
paper
paper samples
samplesand
hydrolysis
samples
samples
samples at
at
at
at the
atthethe
the
the aging
aging
aging
aging temperatures
agingtemperatures
transesterification temperatures
temperatures
temperatures
Figure 4a,b show the correlation between DP and TS of paper samples at the aging temperatures
of
ofof
of
of 120
120
120
120
of120 °C
°C °C
processes.
120°C °C and
and
and
and 150
150
150
150 °C.
°C.
°C.
°C. In
In
In
In these
these
these
these studies,
studies,
studies,
studies, linear
linear
linear
linear regression
regression
regression
regression is
isis
is used
used
used
used to
to
to
to get
get
get
get the
the
the
the correlation
correlation
correlation
correlation between
between
between
between DP
DPDPand
DP and
and
and
and
of 120 ◦°CCandand150
and 150°C.
150 C.In
◦°C. Inthese
In thesestudies,
these studies,linear
studies, linearregression
linear regressionis
regression isused
is usedto
used toget
to getthe
get thecorrelation
the correlationbetween
correlation betweenDP
between DP
DP and
and
TS.
TS.
TS.
TS.
TS.
TS.R R
R
R
R
R2 is
22 2 is
22222 isis
is the
Figure
the
the
the
the
isthe correlation
4a,b
correlation
correlation
correlation
correlation
thecorrelation show
correlationcoefficient coefficient
the correlation
coefficient
coefficient
coefficient
coefficient
coefficient which
which
which
which between
which
which has
has
has
has
has
has DPthe
the
the
the
the
the andvalue
valueTS
value
value
value
value ofrange
paper
range
range
range
range
range of
of
of of
of
of0–10–1
samples
0–1
0–1
0–1 or
oror
or
or at 0–100%.
the
0–100%.
0–100%.
0–100%.
or0–100%.
0–10–100%. 0–100%.aging RR
RRR measures
temperatures
22222 measures
R measures
22 2 measures
measures
measures how
how
how
how
how
how
TS. R is which has the value range ofto0–1 or R2between
measures how
and close
closeof
close
close
close
close
close thethe
thethe
the
the
120 °C and
data
data
data
data
data
data is
isisto
is
is
is to150
to
to
to
to the
the
the
the
the
the
°C.regression
In these studies,
regression
regression
regression
regression
regression line.
line.
line.The
line.
line.
line.
linear
The
The
Thecloser
The
The
regression
closer
closer
closer
closer
closer the
the
thevalue
the
the
the
is used
value
value
value
value
value of
of
of
of
of
of R
RR
RR
R
get is
2222isis
is
2222is
is
the
at
atat
at
at
at
correlation
1
1
11
1
1 or
or
oror
or
or 100%,
100%,
100%,
100%,
100%,
100%, the
the
the
the
the
the more
more
moremore
more
more
DPpositive
positive
positive
positive
positive
positive aaaaaa
the data
TS. Ris2 is
to thethecorrelation
regressioncoefficient line. The which closerhas thethe value value of R2 is at
range 10–1
ofwas or or 100%,0–100%. the moreR2 measures positive howa linear
linear
linear
linear
linear
linear relationship
relationship
relationship
relationship
linearrelationship
relationship the
the
the
the
the correlation
correlation
correlation
correlation
thecorrelation
correlation has.
has.
has.
has.
has.
has. The
The
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value
value
value
value
value ofof
ofof
of
of RR
RRR 22222= =
=
R ===97.5%
2 2 2 97.5%
97.5%
97.5%
97.5%
97.5% was
was
was
was
wasfor for
for
for
for
forthe the
the
the
the correlation
correlation
correlation
correlation
thecorrelation
correlationbetween between
between
between
between
between DP
DP
DPDP
DP
DP
relationship
close the the datacorrelation
is to the regression has. The value
line. The closer R2 =the 97.5%
valuewas of Rfor
2 is the
at 1 correlation
or 100%, the between more DP and a TS
and
and
and TS
and
and
and TS
TS
TS of
TS
TS of
of
of
of paper
of paper
paper
paper samples
paper
paper samples
samples
samples at
samples
samples at
at
at
at the
at the
the
the
the aging
the aging
aging
aging
aging temperature
aging temperature
temperature
temperature
temperature
temperature of
of
of
of
of
of 120
120
120
120
120
120 °C
°C
°C
°C
°C
°C and
and
and
and
and
and the
the
the
the
the
the value
value
value
value
value
value of
of
of
of
of
of R
RR
R
R
R
2222 =
2222 = ====positive
96.9%
96.9%
96.9%
96.9%
96.9%
96.9% for
for
for
for
for the
the
the
the
the
of paper
linearsamples relationship at the theaging temperature
correlation has. The of value ◦
120 ofCRand 2 = 97.5% the value
was for ofthe 2
R correlation
= 96.9% for between DP the
the correlation for
correlation
correlation
correlationbetween
correlation between
between
betweenDP DP
DP
DPand and
and
andTS TS
TSTSofof
of paper
ofpaper
paper
papersamplessamples
samples
samplesat at
at
atthethe
the
theaging aging
aging temperature
agingtemperature
temperature
temperature of
ofof150150
150
150°C, °C,
°C, °C,so so
so there
sothere
there
thereis is
isisaaaaaa
correlation
correlation
betweenand TS DPbetween
between
ofandpaper DP
DP
TS samples
of and
and
paper atTS
TStheof
of
samples paper
paper
aging samples
samples
attemperature
the agingat atofthe
the 120aging
temperature aging
°C and temperature
temperature
the150
of value ◦ C,of of
of
soof 2150
150
Rthere= 96.9% °C,
°C,is asoso
for there
the is
there
correlation is
correlation
correlation
correlation
correlation
correlation
correlation
correlation
between
between
between
between
between
between between
physical
physical
physical
physical
physical
DP andand
physical and
and
and
and
and chemical
chemical
chemical
chemical
chemical
chemical
TScharacteristics
of paper samples
characteristics
characteristics
characteristics
characteristics
characteristics
characteristics
at the aging
of
of
of
of
of paper
paper
paper
paper
ofpaper
paper
temperature
samples
samples
samples
samples
samples
samples which
which
which
which
which
which is
isis
isis
istheshown
shown
shown
shown
shown
shown is by
by
byby
by
abythe
the
the
the
the
the
between physical and chemical of paper samples which isofshown
150 °C,by so therecorrelation
correlation
correlation
correlation
correlation between
between
between
between DP
DPDP
DP and
and
and
and TS.
TS.
TS. Table
Table
Table 222 shows
shows
shows the
the
the visual
visual
visual appearances
appearances
appearances of
of
of transformer
transformer
transformer insulation
insulation
insulation paper
paper
paper
correlation
correlation
betweencorrelation DP between
between
and between
TS. DPDP and
andTS.
physical
Table 2TS.
TS. Table
Table
Table
and
shows 222shows
the shows
shows
chemical visual the
the
the visual
visual
visualappearances
characteristics
appearances appearances
appearances
of paper of
samples
of transformer of transformer
oftransformer
transformer
which is shown
insulation insulation
insulation
insulation by thepaper
paper paper
paper
under
under
under
under
under
under accelerated
accelerated
accelerated
correlation
accelerated
underaccelerated between thermal
thermal
thermal
thermal DP andaging
aging
aging
agingTS. at
atat
Table
at different
different
different
2 shows
different aging
aging
aging
the
aging time
time
time
visual
time and
and
and
appearances
and temperature.
temperature.
temperature.
temperature.of transformer The
The
The
The color
color
color
insulation
color of
of
of
of transformer
transformer
transformer
paper
transformer
accelerated thermalthermal
accelerated aging ataging
thermal aging at
different atdifferent
different
aging time aging
agingandtimetime
temperature.and
andtemperature. The colorThe
temperature. The color
colorof
of transformer oftransformer
transformer
insulation
insulation
insulation
insulation
underpaper
insulation
insulation
insulation paper
paper
paperbecome
accelerated
paper
paper become
become
become
become
become thermal darker
darker
darker
darker
darker
darker agingwith
with
with
with
with
with aging
aging
aging[29].
at aging
different
aging
aging [29].
[29].
[29].
aging time and temperature. The color of transformer
[29].
[29].
paper become darker with aging [29].
insulation paper become darker with aging [29].

(a) (b)
(a)
(a)
(a)
(a)
(a)
(a) (b)
(b)
(b)
(b)
(b)
(b)
Figure 4. Correlation between DP and TS of paper samples at aging temperature (a) 120 °C and (b) ◦ C and
Figure
Figure
Figure
Figure 4.
4.
4.
4. Correlationbetween
Correlation
Correlation
Correlation betweenDP
between
between DP
DPDP and
and
and
and TS
TSTS
TS ofof
of
of paper
paper
paper
paper samples
samples
samples
samples at
at at aging
aging
ataging
aging
aging temperature
temperature
temperature
temperature (a)
(a) (a)
120120
120
(a)120
120 °C
°C and
°Cand
and (b)
and(b)
(b)
(b)
Figure
Figure
Figure
Figure 4.
1504.
4.
◦4. Correlation
Correlation
Correlation
°C.Correlation between
between
between
between DP
DP
DP
DP and
and
and
and TS
TS
TS
TS of
of
of
of paper
paper
paper
paper samples
samples
samples
samples at
at
at
at aging
aging
aging temperature
temperature
temperature
temperature (a)
(a)
(a)
(a) 120
120
120 °C
°C
°C
°C and
and
and (b)
(b)
(b)
(b)
150150
150
150 °C. C.
°C.
°C.
150
150
150
150 °C.
°C.
°C.
°C.
Table2.2.Visual
Table Visual appearances
appearances ofofpaper
papersurface.
surface.
Table
Table
Table
Table
Table
Table 2.
Table2.
2.
2.
2.
2. Visual
2.Visual
Visual
Visual
Visual
Visual appearances
Visualappearances
appearances
appearancesof
appearances
appearances
appearances of
ofof
of
of paper
ofpaper
paper
paper
paper
paper surface.
papersurface.
surface.
surface.
surface.
surface.
surface.
Aging Time (h)
Temperature Aging Time
Time (h)
Temperature 0 336Aging Aging
Aging
Aging
Aging(h)
AgingTime
Time
Time(h)
672
Time
Time (h)
(h)
(h)
(h) 1008
Temperature
Temperature
Temperature
Temperature
Temperature
Temperature 0 336 672 1008
000000 336
336
336
336
336
336 672
672
672
672
672
672 1008
1008
1008
1008
1008
1008
120 °C

120 ◦C
°C
120
120
120
120
120°C
°C
120°C
°C
°C

150 °C

150
150
150
150
150 °C
°C
°C
◦C
°C
150°C
150 °C
Energies 2017, 10, 1857 6 of 15
Energies 2017, 10, 1857 6 of 15

3.2.
3.2. The
The Structural
Structural Changes
Changes of of Transformer
Transformer Insulation
Insulation Paper
Paper
FTIR
FTIR spectroscopy
spectroscopywas wasusedusedtotoanalyze
analyzethe
thestructural
structuralchanges
changeswhich
which areare
shown
shown byby
thethe
intensity of
intensity
peak absorbance of functional group of material. Figure 5 shows the spectra of
of peak absorbance of functional group of material. Figure 5 shows the spectra of transformer transformer insulation
paper in natural
insulation paper inester under
natural accelerated
ester thermal aging
under accelerated thermalforaging
1008 h
forat1008
aging temperatures
h at of 120 ◦of
aging temperatures C
and 150 ◦ C. The intensity of the peak absorbances of paper samples has a tendency to decrease with
120 °C and 150 °C. The intensity of the peak absorbances of paper samples has a tendency to decrease
aging temperature
with aging due to the
temperature duerateto of
thedegradation process which
rate of degradation increases
process which with aging temperature.
increases with aging
Tables 3 and 4 show the intensity of peak absorbance of the functional groups
temperature. Tables 3 and 4 show the intensity of peak absorbance of the functional groups of the paper samples at
of the
the temperatures of 120 ◦ C and 150 ◦ C which will be analyzed in this research paper.
paper samples at the temperatures of 120 °C and 150 °C which will be analyzed in this research paper.

0.3

0.25
C-O
0.2
Absorbance

C-H
C=O
0.15
O-H
0.1

0.05

0
3997
3862
3726
3590
3454
3318
3182
3046
2910
2774
2639
2503
2367
2231
2095
1959
1823
1687
1551
1416
1280
1144
1008
872
736
600
Wavenumber (cm¯¹)

T3.120 T3.150

Figure 5. FTIR Spectra of transformer insulation paper for at aging temperature 120 °C and 150 °C for
Figure 5. FTIR Spectra of transformer insulation paper for at aging temperature 120 ◦ C and 150 ◦ C for 1008 h.
1008 h.
Table 3. Intensity of peak absorbance of functional groups of paper samples at temperature 120 ◦ C.
Table 3. Intensity of peak absorbance of functional groups of paper samples at temperature 120 °C.
Wavenumber (cm−1 ) Functional Group New T1.120 T2.120 T3.120
1159(cm−1)
Wavenumber FunctionalC–O
Group 0.08585
New 0.11775
T1.120 0.09983
T2.120 0.10341
T3.120
1743 C=O 0.01372 0.06336 0.07268 0.10618
1159
2854 C–OC–H 0.08585
0.02616 0.11775
0.05563 0.09983
0.0662 0.10341
0.09905
1743
2922 C=OC–H 0.01372
0.02516 0.06336
0.06646 0.07268
0.08567 0.10618
0.1248
2854
3273 C–HO–H 0.02616
0.08377 0.05563
0.07906 0.0662
0.07358 0.09905
0.06933
2922
3325 C–HO–H 0.02516
0.08305 0.06646
0.08125 0.08567
0.07617 0.1248
0.07111
3273 O–H 0.08377 0.07906 0.07358 0.06933
3325 O–H 0.08305 0.08125 0.07617 0.07111
Table 4. Intensity of peak absorbance of functional groups of paper samples at temperature 150 ◦ C.
Table 4. Intensity of peak absorbance of functional groups of paper samples at temperature 150 °C.
Wavenumber (cm−1 ) Functional Group New T1.150 T2.150 T3.150
1159 C–O 0.08585 0.12555 0.11669 0.10868
Wavenumber (cm−1) Functional Group New T1.150 T2.150 T3.150
1743 C=O 0.01372 0.04943 0.06493 0.08902
2854 C–H 0.02616 0.05131 0.05869 0.08909
1159 C–O 0.08585 0.12555 0.11669 0.10868
2922
1743
C–H
C=O
0.02516
0.01372
0.06143
0.04943
0.07405
0.06493
0.11136
0.08902
3273
2854
O–H
C–H
0.08377
0.02616
0.07764
0.05131
0.07407
0.05869
0.06387
0.08909
3325
2922 O–H
C–H 0.08305
0.02516 0.07947
0.06143 0.07603
0.07405 0.06532
0.11136
3273 O–H 0.08377 0.07764 0.07407 0.06387
3325 O–H 0.08305 0.07947 0.07603 0.06532
Energies 2017, 10, 1857 7 of 15

The
Energiespredominant
2017, 10, 1857 chemical reaction in natural esters subjected to high temperature 7 of 15 is
hydrolysis [30]. Hydrolysis
Energies 2017, 10, 1857 and transesterification process can change the chemical structure
7 of 15 of
transformer The insulation
predominant chemical
paper reaction
which can in benatural
shownesters subjected
by FTIR to high Natural
analysis. temperature esteris hydrolysis
molecules are
[30]. The
Hydrolysis
triglycerides, predominant and transesterification
which consist chemical
of threereaction process
in
fatty acids natural
andcan change
esters
one the chemical
subjected
glycerol structure
to high temperature
molecule ofistransformer
[9]. Triglyceridehydrolysis
and three
insulation
[30]. paper and
Hydrolysis which can be shown by
transesterification FTIR analysis.
process can change Natural
the ester molecules
chemical structure areoftriglycerides,
transformer
water molecules are involved in hydrolysis reaction [10,31]. Figure 6 shows the hydrolysis reaction
which consist
insulation paper of which
three canfattybeacids
shownandbyone FTIR glycerol
analysis. molecule
Natural[9]. Triglyceride
ester molecules are andtriglycerides,
three water
of natural ester [10]. This process generates glycerol and long chain of fatty acids and then the long
molecules are involved in hydrolysis reaction [10,31]. Figure
which consist of three fatty acids and one glycerol molecule [9]. Triglyceride and three 6 shows the hydrolysis reaction
water of
chainnatural
fatty acids
ester
which
[10].
have
This
long-alkyl-chains
process generates
(-R) consisting
glycerol and long
of a lot
chain of
of C–H
fatty
functional
acids and then
groups
the long
bind to
molecules are involved in hydrolysis reaction [10,31]. Figure 6 shows the hydrolysis reaction of
the cellulose
chain fatty
natural through
acids
ester transesterification
[10].which
This have
process generates generating
long-alkyl-chains glycerol transesterified
(-R) consisting
and long chainof a lot cellulose
ofof C–Hacids
fatty and
andthree
functional molecules
groups
then bind of
the long
waterchain
as shown
to the fatty
cellulosein Figure
acidsthrough
which have 7. The transesterification
transesterification
long-alkyl-chains generating process involves
transesterified
(-R) consisting cellulose
of a lotcellulose and the long
and three molecules
of C–H functional groups bind chain
of of
fatty to
acids,
water which
the cellulose bind
as shownthrough to
in Figure cellulose.
7. The transesterification
transesterification generatingprocess involvescellulose
transesterified celluloseand andthree
the long chain of
molecules
fatty acids,
Figure
water as8a,b which
shown inbind
illustrate Figureto cellulose.
the variations
7. of FTIR spectra
The transesterification around
process 2900 cm
involves −1 of the
cellulose andtransformer
the long chain insulation
of
at Figure
paperfatty acids,
the 8a,btemperatures
which
aging illustrate
bind to cellulose. of 120 ◦ C ofand
the variations FTIR ◦ C. Asaround
150spectra shown2900 cm−1 of
in these the transformer
figures, there are two
insulation
absorbance Figure paper
8a,b at
spectra the aging
illustrate
peaks at thetemperatures
2854 cm−1 and
variations of 120
FTIR
2922°C cmand−150
spectra °C. As represent
around
1 which shown
2900 in cmthese
−1 of figures,
C–Hthe there are
transformer
functional groups.
two absorbance
insulation paper spectra
at the peaks
aging at 2854 cm ofand
temperatures −1
120 2922
°C cm150
and −1 which
°C. As represent
shown inC–H
thesefunctional
figures, groups.
there are
Figure 8a,b show that the intensity of the peak absorbances of the C–H functional groups of transformer
Figure
two 8a,b show
absorbance that peaks
spectra the intensity
at 2854 of
cmthe−1 andpeak
2922absorbances
cm−1 which of the C–H
represent C–H functional
functional groups
groups. of
insulation paper have increased with aging due to hydrolysis of the natural ester and transesterification
transformer
Figure 8a,b insulation
show that paper have increased
the intensity of the with
peak aging due to hydrolysis
absorbances of the C–Hof functional
the naturalgroups
ester and of
of thetransesterification
transformer insulation of the
paper. as shown
transformer
in Figure
insulation paper.
8 [10]. So, in
theFigure
long alkyl chainthewhich is initially
transformer insulation paper have increased with agingasdue shownto hydrolysis 8of[10].
the So,
naturallong
esteralkyl
and
part of fatty acids in
transesterification natural
chain which is initially of the ester
part binds to
of fatty acids
transformer cellulose.
in natural
insulation Further,
ester as
paper. binds transesterification
shownto cellulose.
in Figure Further, process in the insulating
8 [10]. transesterification
So, the long alkyl
paperchain
can which
process beinconfirmed
the initiallyby
is insulating C=O
partpaper functional
canacids
of fatty in group
be confirmed
naturalby at 1743
C=O
ester cm− 1 [3].
functional
binds groupFurther,
to cellulose. at 1743 transesterification
cm−1 [3].
process in the insulating paper can be confirmed by C=O functional group at 1743 cm−1 [3].

Figure
Figure 6. 6.Hydrolysis
Hydrolysis reaction
reaction of
ofnatural
naturalester.
ester.
Figure 6. Hydrolysis reaction of natural ester.

Figure 7. Transesterification process of transformer insulation paper.


Figure 7. Transesterification process of transformer insulation paper.
Figure 7. Transesterification process of transformer insulation paper.
Energies 2017, 10, 1857 8 of 15
Energies 2017, 10, 1857 8 of 15

0.14 0.12
Energies 2017, 10, 1857 8 of 15
0.12 0.1
Absorbance

Absorbance
0.1 0.08
0.14
0.08 0.12
0.12 0.06
0.06 0.1
0.04
Absorbance

Absorbance
0.1
0.04 0.08
0.08
0.02 0.02
0.06
0.060 0
0.04
2998
2974
2950
2926
2902
2878
2854
2830
2806
2782
2757
2733
2709

2998
2974
2950
2926
2902
2878
2854
2830
2806
2782
2757
2733
2709
0.04
0.02 0.02
0 Wavenumber (cm¯¹) 0 Wavenumber (cm¯¹)
2998
2974
2950
2926
2902
2878
2854
2830
2806
2782
2757
2733
2709

2998
2974
2950
2926
2902
2878
2854
2830
2806
2782
2757
2733
2709
New T1.120 T2.120 T3.120 New T1.150 T2.150 T3.150
Wavenumber (cm¯¹) Wavenumber (cm¯¹)
(a) (b)
New T1.120 T2.120 T3.120 New T1.150 T2.150 T3.150
Figure 8. FTIR spectra at wavenumber 3000–2700 cm of transformer insulation paper at aging
−1
Figure 8. FTIR spectra at wavenumber 3000–2700 cm−1 of transformer insulation paper at aging
temperature (a) 120
◦ °C(a)and (b) 150
◦ °C. (b)
temperature (a) 120 C and (b) 150 C.
Figure
Figure 8.9 shows
FTIR spectra at wavenumber
the correlation 3000–2700
between cmof
intensity
−1 of transformer insulation paper at aging
peak absorbance of C–H functional group
Figure 9 shows
temperature
absorbance
the
(a) 120correlation
(at wavenumber°C and 2922
(b) 150between
cm°C.
intensity
−1 and 2854 of peak absorbance of C–H functional group
cm−1) and the average number of chain scissions of
absorbance (at wavenumber 2922 − 1
cm studies,
and 2854 − 1
cmregression
) and the average
transformer insulation paper. In these linear is used to get number of chain
the correlation scissions
between
Figure insulation
of transformer 9 shows the paper.
correlation
In between
these intensity
studies, of peak
linear absorbance
regression is of C–Htofunctional
used get the group
correlation
the chemical structure and the aging performance characteristic of transformer insulation paper.
absorbance (at wavenumber 2922 cm−1 and 2854 cm−1) and the average number of chain scissions of
between the chemical
Average number ofstructure and the
chain scissions aging
is used to performance characteristic
describe the degradation of transformer
of cellulose insulation
due to thermal
transformer insulation paper. In these studies, linear regression is used to get the correlation between
aging,
paper. whichnumber
Average is given in ofEquation (1) [32]: is used to describe the degradation of cellulose due to
chain scissions
the chemical structure and the aging performance characteristic of transformer insulation paper.
thermal aging, which is given in Equation (1) [32]:
Average number of chain scissions is used to describe the 1 degradation
1 of cellulose due to thermal
Avg. Chain Scission = − (1)
aging, which is given in Equation (1) [32]: DPt DP0
1 1
Avg. Chain Scission = 1 −1 (1)
Avg. Chain Scission = DP t− DP 0 (1)
6.00 DP0.1
t DP0
(a.u)

(a.u)

5.00 R² = 0.9763 0.08


R² = 0.8104
4.00
Absorbance

Absorbance

6.00 0.06
0.1
3.00
(a.u)

(a.u)

5.00 R² = 0.9763 0.04


0.08
2.00 R² = 0.8104
4.00
Absorbance

Absorbance

1.00 0.02
0.06
3.00
0.00 0.040
2.00
0.00 0.20 0.40 0.60 0.80 1.00 0.00 1.00 2.00 3.00 4.00 5.00
1.00 0.02
Avg. Chain Scission (x1000) Avg. Chain Scission (x1000)
0.00 0
0.00 0.20 0.40 0.60 0.80 1.00 0.00 1.00 2.00 3.00 4.00 5.00
(a) (b)
Avg. Chain Scission (x1000) Avg. Chain Scission (x1000)
0.14 0.12
0.12
(a.u)

(a.u)

R² = 0.9839 0.1
(a) (b) R² = 0.8534
0.1 0.08
Absorbance

Absorbance

0.14
0.08 0.12
0.12 0.06
(a.u)

(a.u)

0.06 R² = 0.9839 0.1


0.04 R² = 0.8534
0.1
0.04 0.08
Absorbance

Absorbance

0.08
0.02 0.02
0.06
0.060 0
0.04 0.00 0.20 0.40 0.60 0.80 1.00 0.04
0.00 1.00 2.00 3.00 4.00 5.00
0.02 0.02
Avg. Chain Scission (x1000) Avg. Chain Scission (x1000)
0 0
0.00 0.20 0.40 0.60 0.80 1.00 0.00 1.00 2.00 3.00 4.00 5.00
(c) (d)
Avg. Chain Scission (x1000) Avg. Chain Scission (x1000)
Figure 9. Correlation between average number of chain scission of transformer insulation paper and
intensity of peaks absorbance
(c) of C–H functional group at aging temperature (d)(a) 120 °C (2922 cm );
−1

Figure 9. Correlation between average number of chain scission of transformer insulation paper and
Figure 9. Correlation between average number of chain scission of transformer insulation paper and
intensity of peaks absorbance of C–H functional group at aging temperature (a) 120 °C (2922 cm−1);
intensity of peaks absorbance of C–H functional group at aging temperature (a) 120 ◦ C (2922 cm−1 );
(b) 150 ◦ C (2922 cm−1 ); (c) 120 ◦ C (2854 cm−1 ); (d) 150 ◦ C (2854 cm−1 ).
Energies 2017, 10, 1857 9 of 15

Energies 2017, 10, 1857 9 of 15


Energies 2017, 10, 1857
Figure 10a,b illustrate−1 the variations of FTIR spectra around 1700 cm−1 . 9 of 15
The C=O functional group
(b) 150 °C (2922 cm ); (c) 120 °C (2854 cm−1); (d) 150 °C (2854 cm−1).
didn’t appear in new transformer insulation paper,
(b) 150 °C (2922 cm−1); (c) 120 °C (2854 cm−1); (d) 150 °C (2854 cm−1).
but there is a peak absorbance in its spectrum
after thermalFigure aging. This carbonyl
10a,b illustrate band indicates
the variations of FTIR spectra the presence
around 1700 of cm
an−1ester bonded
. The C=O to thegroup
functional cellulose,
providing
didn’t evidence
appear
Figure inthat
10a,b new the transesterification
transformer
illustrate insulation
the variations of FTIRhas
paper,taken
spectra place
there [30].
butaround is1700 Figure
a peak 10a,b
cm−1absorbance
. The C=Oshow in itsthe
functional intensity
group of
spectrum
after thermal
didn’t
the absorbance appearpeakaging.
in of
new This
the C=O carbonyl
transformer band indicates
insulation
functional group paper,
has the presence
but ofa an
there iswith
increased peak ester bonded
absorbance
aging, showing to
in the cellulose,
its spectrum
that the chemical
providing
after thermal evidence
aging. that
This the transesterification
carbonyl band indicates has taken
the place
presence [30].
of
structure of transformer insulation paper has changed after thermal aging. The C=O functional group anFigure
ester 10a,b
bonded show
to the
the intensity
cellulose,
ofisthe
whichproviding absorbance
initially part ofpeak
evidence that ofacids
fattythe the C=O functional
transesterification
in natural ester group
has taken
binds has increased
toplace with
[30]. Figure
cellulose. aging, showing
10a,b show
The produced that the
the intensity
ester group firmly
chemical
of structurepeak
the absorbance of transformer
of the C=O insulation
functional paper group has has changed
increasedafterwiththermal aging. The
aging, showing thatC=O
the
bonded water molecules to the ester group and the long chain fatty acids esterified on cellulose were
functionalstructure
chemical group which is initially part
of transformer of fatty acids
insulation paperin hasnatural ester binds
changed after to cellulose.
thermal The produced
aging. The C=O
arranged in parallel with the cellulose chain to form a “water barrier” that can reduce the potential
ester groupgroup
functional firmlywhich
bonded water molecules
is initially part of fattyto the ester
acids in group
naturaland thebinds
ester long tochain fatty acids
cellulose. esterified
The produced
damageesterofgroup
waterfirmly
on cellulose on the
were transformer
arranged
bonded water insulation
in parallel
molecules withtothe paper
the ester[8].
cellulose
groupchain
andto theform
longachain
“water barrier”
fatty that can
acids esterified
Transesterification
reduce
on the potential
cellulose of the long
damage
were arranged chain
of parallel
in water fatty
onwith acids
the transformer
the mayinsulation
cellulose protect
chain toofformcellulose
paper a[8].
“waterinsulation
barrier” in two
that canways:
by strengthening
reduce C–O and
Transesterification
the potential ofC–C
damage bonds
theoflong
water in the
chain
on cellulose
fatty acids and
transformer may forming
protect
insulationofacellulose
barrier
paper preventing
[8].insulation water
in two ingress
ways:
to thebycellulose
strengthening [8]. The
C–O intensity
and C–C of peak
bonds in absorbance
cellulose and of the
forming C–O
a functional
barrier preventing
Transesterification of the long chain fatty acids may protect of cellulose insulation in two ways: groupwater at wavenumber
ingress to
by
1159 cm − 1
thestrengthening
cellulose [8]. The
of the aged C–O intensity
and C–Cofbonds
transformer peak absorbance
paper of
in cellulose
insulation and the C–Othan
forming
is greater functional
a barrier
in new group
preventingat wavenumber
transformer water ingress
insulation1159
topaper
cm−1cellulose
the
as shown ofinthe aged
Figure transformer
[8]. 11.
TheThis
intensity
peakinsulation
ofconfirms paper
thatistransesterification
peak absorbance greater
of thethan
C–Oin new transformer
functional groupmay
process atinsulation
wavenumber
allow the paper as
1159
estimated
shown
cm
lifetime in Figure
−1 of the
of transformers 11. that
Thisuse
aged transformer peak confirms
insulation
natural that
paper
ester asistransesterification
greater thanliquid
insulating in new process may allow
transformer
longer than the
insulation
when usingestimated
paper as oil.
mineral
lifetimein
shown of Figure
transformers
11. This that useconfirms
peak natural ester
that as insulating liquidprocess
transesterification longer maythan when
allow using mineral
the estimated
Figure 12 shows the correlation between the intensity of peak absorbance of C=O functional group at
oil. Figure
lifetime of 12 shows the correlation
transformers between
that use natural theas
ester intensity of peak
insulating absorbance
liquid longer than of C=O
when functional group
using mineral
wavenumber 1743 cm−1 and the average number of chain scission of transformer insulation paper.
at wavenumber
oil. 1743the
Figure 12 shows cmcorrelation
and the average
−1betweennumber of chain
the intensity scission
of peak of transformer
absorbance of C=O insulation
functional paper.
group
at wavenumber 1743 cm−1 and the average number of chain scission of transformer insulation paper.
0.12 0.1
0.12
0.1 0.1
0.08
Absorbance

Absorbance

0.1
0.08 0.08
0.06
Absorbance

Absorbance

0.08
0.06
0.06
0.04
0.06
0.04
0.04
0.02
0.04
0.02
0.020 0.020
18011801
17921792
17841784
17751775
17671767
17581758
17501750
17411741
17331733
17241724
17161716
17071707

18011801
17921792
17841784
17751775
17671767
17581758
17501750
17411741
17331733
17241724
17161716
17071707
0 0

Wavenumber (cm¯¹) Wavenumber (cm¯¹)


Wavenumber (cm¯¹) Wavenumber (cm¯¹)
New T1.120 T2.120 T3.120 New T1.150 T2.150 T3.150
New T1.120 T2.120 T3.120 New T1.150 T2.150 T3.150
(a) (b)
(a) (b)
Figure 10. FTIR spectra at wavenumber 1800–1700 cm−1 of transformer insulation paper at aging
Figure 10. FTIR spectra at wavenumber 1800–1700 cm−1−1 of transformer insulation paper at aging
temperature
Figure (a) 120
10. FTIR °C and
spectra at (b) 150 °C.
wavenumber 1800–1700 cm of transformer insulation paper at aging
temperature (a) 120 ◦ C and (b) 150 ◦ C.
temperature (a) 120 °C and (b) 150 °C.
0.3 0.3
0.3
0.25 0.3
0.25
Absorbance

Absorbance

0.25
0.2 0.25
0.2
Absorbance

Absorbance

0.2
0.15 0.2
0.15
0.15
0.1 0.15
0.1
0.1
0.05 0.1
0.05
0.050 0.050
15001500
14541454
14071407
13601360
13141314
12671267
12201220
11731173
11271127
10801080
10331033
987987
940940

15001500
14541454
14071407
13601360
13141314
12671267
12201220
11731173
11271127
10801080
10331033
987987
940940

0 0

Wavenumber (cm¯¹) Wavenumber (cm¯¹)


Wavenumber (cm¯¹) Wavenumber (cm¯¹)
New T1.120 T2.120 T3.120 New T1.150 T2.150 T3.150
New T1.120 T2.120 T3.120 New T1.150 T2.150 T3.150
(a) (b)
(a) (b)

Figure 11. FTIR spectra at wavenumber 1500–900 cm−1 of transformer insulation paper at aging
temperature (a) 120 ◦ C and (b) 150 ◦ C.
Energies 2017, 10, 1857 10 of 15

Energies 2017, 10, 1857


Figure 11.1857
FTIR spectra at wavenumber 1500–900 cm−1 of transformer insulation paper at aging 10 of 15
Energies 2017, 10, 10 of 15
temperature (a) 120 °C and (b) 150 °C.
Figure 11. FTIR spectra at wavenumber 1500–900 cm−1 of transformer insulation paper at aging
temperature
0.12 (a) 120 °C and (b) 150 °C. 0.1

(a.u) (a.u)

(a.u) (a.u)
0.10 R² = 0.932 0.08 R² = 0.9317
0.12
0.08
Absorbance 0.1

Absorbance
0.06
0.10
0.06 R² = 0.932 0.08 R² = 0.9317
0.08 0.04
0.04
Absorbance

Absorbance
0.06
0.06
0.02 0.02
0.04
0.04
0.00 0
0.02 0.00 0.20 0.40 0.60 0.80 1.00 0.02 0.00 1.00 2.00 3.00 4.00 5.00
0.00 Avg. Chain Scission (x1000) 0 Avg. Chain Scission (x1000)
0.00 0.20 0.40 0.60 0.80 1.00 0.00 1.00 2.00 3.00 4.00 5.00
(a)
Avg. Chain Scission (x1000) (b)
Avg. Chain Scission (x1000)
Figure 12. Correlation between average number of chain scission of transformer insulation paper and
Figure 12. Correlation between
(a) average number of chain scission of transformer(b) insulation paper and
intensity of peaks absorbance of C=O functional group (1743 cm−1) at aging temperature (a) 120 °C;
intensity of peaks absorbance of C=O functional group (1743 cm−1 ) at aging temperature (a) 120 ◦ C;
(b) 150 12.
Figure °C.Correlation between average number of chain scission of transformer insulation paper and
(b) 150 ◦ C.
intensity of peaks absorbance of C=O functional group (1743 cm ) at aging temperature (a) 120 °C;
−1

Figure
(b) 13a,b illustrate the FTIR spectra variations around 3200 cm−1.−There
150 °C. 1
are two absorbance
Figure
peaks at13a,b
3273 illustrate
cm−1 and 3325 the FTIR spectra
cm−1 which variations
represent the around 3200 cmgroups.
O–H functional . ThereThe are two absorbance
intensity of the
peaksabsorbance
at 3273 cm −1 and 3325 cm−1 which represent the O–H functional groups. The intensity of
located
Figure 13a,b close tothe
illustrate 3340
FTIRcmspectra
−1 can be attributed
variations of hydroxyl
around 3200 cm−1groups
. There which
are twoare a typical
absorbance
the absorbance located close to cm
3340 cm −1 can be attributed of hydroxyl groups which are a typical
characteristic
peaks at 3273 of
cmcellulose
−1 and [33].
3325 Figure 13a,b
−1 which show that
represent thethe intensity
O–H of thegroups.
functional absorbance The peaks of the
intensity O–
of the
characteristic
absorbance of cellulose
H functional located [33].toFigure
group decreased
close during
3340 13a,b
cm aging.show
−1 can Thisthat
O–Hthe intensity
functional
be attributed of the
group
of hydroxyl absorbance
decrease
groups can bepeaks
which of the
attributed
are to O–H
a typical
the reduction
characteristic ofof molecular
cellulose [33].weight
Figure [3].
13a,b The
showreduction
that the of O–H
intensity functional
of the groups
absorbance
functional group decreased during aging. This O–H functional group decrease can be attributed to the is
peaks due
of to
the the
O–
hydrolysis
H functional
reduction reaction
group of
of molecular cellulose,
decreased
weight [3].which
during generates
Theaging. Thisglucose
reduction O–H and oxidation
functional
of O–H reactions
decreaseisduring
groupgroups
functional can
due beto aging which
attributed to
the hydrolysis
generate
the CO
reduction 2 and
of H 2O [34]. Figure
molecular weight 14 shows
[3]. The the correlation
reduction of between
O–H DP
functionaland
reaction of cellulose, which generates glucose and oxidation reactions during aging which generate the
groups intensity
is due of
topeak
the
absorbancereaction
hydrolysis of the O–H functional
of cellulose, group
which at wavenumber
generates glucose 3325 cm−1 and 3273
and oxidation cm−1 during
reactions of insulating
aging paper.
which
CO2 and H2 O [34]. Figure 14 shows the correlation between DP and the intensity of peak absorbance
generate CO2 and H2O [34]. Figure 14 shows the correlation between DP and the intensity of peak
of the O–H functional group at wavenumber 3325 cm−1 and 3273 cm−1 of insulating paper.
absorbance
0.1 of the O–H functional group at wavenumber 3325
0.1 cm and 3273 cm of insulating paper.
−1 −1

0.08 0.08
Absorbance

Absorbance

0.1 0.1
0.06 0.06
0.08 0.08
Absorbance

Absorbance

0.04 0.04
0.06 0.06
0.02 0.02
0.04 0.04
0 0
3700
3645
3590
3535
3479
3424
3369
3314
3259
3203
3148
3093
3038

3700
3645
3590
3535
3479
3424
3369
3314
3259
3203
3148
3093
3038

0.02 0.02
0 0
Wavenumber (cm¯¹) Wavenumber (cm¯¹)
3700
3645
3590
3535
3479
3424
3369
3314
3259
3203
3148
3093
3038

3700
3645
3590
3535
3479
3424
3369
3314
3259
3203
3148
3093
3038

New T1.120
Wavenumber (cm¯¹) T3.120
T2.120 New T1.150 (cm¯¹) T3.150
T2.150
Wavenumber

(a) (b)
New T1.120 T2.120 T3.120 New T1.150 T2.150 T3.150
Figure 13. FTIR spectra at wavenumber 3700–3000 cm −1 of transformer insulation paper at aging
(a) (b)
temperature (a) 120 °C and (b) 150 °C.
Figure 13. FTIR spectra at wavenumber 3700–3000 cm−1 of transformer insulation paper at aging
Figure 13. FTIR spectra at wavenumber 3700–3000 cm−1 of transformer insulation paper at aging
The EDS results
temperature (a) 120show that
°C and (b)the
150◦main
°C. elements of transformer insulation paper are the elements
temperature
C and O. The(a) 120 ◦isCinand
result (b) 150
accord withC.the fact that paper is composed of cellulose which has chemical
formula
The CEDS
6H10results
O5 [35].show
Hydrogen was
that the not elements
main detected of
because the H insulation
transformer 1s electrons are valence
paper are the electrons
elements
The EDS results show that the main elements of transformer insulation paper are the elements C
and
C don’t
and participate
O. The result is in
in chemical bonding
accord with [35].
the fact thatHydrogen are not useful
paper is composed in elemental
of cellulose whichidentification
has chemical
and O. Thethe
using
formula result
CEDS is5 in
method
6H10O
accord
[35]. with
[36]. The
Hydrogen the not
result
was factdetected
showsthat
thatpaper
the is composed
weight
because percent
the H 1s ofofthecellulose
C element
electrons which has chemical
in transformer
are valence electrons
formula
and C 6 H10participate
insulation
don’t O5 [35].
paper hasHydrogen
increased
in chemical was
with not detected
aging
bonding as shown
[35]. because arethe
in Figure
Hydrogen notH
15. 1s electrons
Figure
useful 16a,b showarethe
in elemental valence electrons
correlation
identification
and don’t
using participate
the EDS method in chemical bonding
[36]. The result [35].
shows thatHydrogen
the weightare not useful
percent of the Cin elemental
element identification
in transformer
usinginsulation
the EDS paper
method has[36]. The result
increased shows
with aging asthat theinweight
shown Figure percent of16a,b
15. Figure the Cshow
element in transformer
the correlation
insulation paper has increased with aging as shown in Figure 15. Figure 16a,b show the correlation
between the weight percent of C element and the average number of chain scissions of transformer
insulation paper.
Energies 2017, 10, 1857 11 of 15
Energies 2017, 10, 1857 11 of 15
Energies 2017, 10,the
between 1857
weight percent of C element and the average number of chain scissions of transformer11 of 15
insulationthe
between paper.
weight percent of C element and the average number of chain scissions of transformer
insulation paper.
2500 2500
2500
2000 2500
2000
R² = 0.8083
2000
1500 2000
1500
DP DP

DP DP
R² = 0.8083 R² = 0.425
1500
1000 1500
1000
R² = 0.425
1000
500 1000
500
5000 5000
0 0.07 0.075 0.08 0.085 0 0.06 0.065 0.07 0.075 0.08 0.085
0.07 Absorbance
0.075 (a.u)
0.08 0.085 0.06 0.065Absorbance (a.u)0.08 0.085
0.07 0.075
Absorbance (a.u) Absorbance (a.u)
(a) (b)
2500 (a) 2500 (b)
2500
2000 2500
2000
R² = 0.9362
2000
1500 2000
1500
R² = 0.9362 R² = 0.5561
DP DP

DP DP
1500
1000 1500
1000 R² = 0.5561
1000
500 1000
500
5000 5000
0 0.06 0.065 0.07 0.075 0.08 0.085 0 0.06 0.065 0.07 0.075 0.08 0.085
Absorbance
0.06 0.065 (a.u)0.08 0.085
0.07 0.075 0.06 0.065Absorbance (a.u)0.08 0.085
0.07 0.075
Absorbance (a.u) Absorbance (a.u)
(c) (d)

Figure 14. Correlation(c)between average number of chain scission of transformer


(d) insulation paper and
Figure 14. Correlation between average number of chain scission of transformer insulation paper and
intensity
Figure ofCorrelation
peaks absorbance
betweenof O–H functional
number ofgroup
chain at aging of
temperature
transformer(a) 120 °C ◦(3325 cm −1);
intensity of14.
peaks absorbance of average
O–H functional group scission
at aging temperature insulation
(a) 120 Cpaper and
(3325 cm −1 );
(b) 150 °Cof(3325
intensity cmabsorbance
peaks
−1); (c) 120 °C (3273 cm−1); (d) 150 °C (3273 cm−1).
of O–H functional group◦ at aging temperature (a) 120 °C (3325 cm−1);
◦ − 1 ◦ − 1
(b) 150 C (3325 cm );−1 (c) 120 C (3273 cm−1 ); (d) 150 C (3273−1cm ). − 1
(b) 150 °C (3325 cm ); (c) 120 °C (3273 cm ); (d) 150 °C (3273 cm ).

(a) (b)
(a) of C and O elements of transformer insulation paper
Figure 15. Weight percent (b) at aging temperature
(a) 120 15.
Figure °C and (b) 150
Weight °C. of C and O elements of transformer insulation paper at aging temperature
percent
Figure 15. Weight percent of C and O elements of transformer insulation paper at aging temperature
(a)◦120 °C and (b) 150
◦ °C.
(a) 120
TheCresult
and (b)
of 150
EDS C.
shows that the weight percent of O element has decreased with aging due to
oxidation reaction
The result of transformer
of EDS shows that insulation
the weightpaper during
percent aging which
of O element CO2 and Hwith
has decreased 2O are generated
aging due to
The
fromresult
oxidation
of Figure
glucose. EDSofshows
reaction
that the
16c,d show
transformer the weight percent
correlation
insulation
of Oaging
between
paper during DP
elementthehas
andwhich decreased
weight
CO2 and percent with aging due to
of Ogenerated
H2O are element.
oxidation
from reaction
From glucose. of transformer
the TableFigure
5, the value
16c,d of insulation
R =the
show 2 9134 paper
and R = 9971
2
correlation during
indicate
between aging
DP the which CO
andcorrelations and
the weightbetween H O are
average
2percent of generated
chain
2 O element.
fromFrom
glucose.
scission
theandFigure
Table 16c,d
the5,weight
the show
percent
value of R of
2 thethecorrelation
= 9134 Cand
element between
which
R = 9971
2 DPtheand
are greater
indicate thethe
than weight
other
correlations percent of Ochain
correlation.
between average element.
Fromscission
the Table
and5,the
theweight of R2 =of9134
valuepercent the C and R2 = 9971
element whichindicate thethan
are greater correlations
the otherbetween average chain
correlation.
scission and the weight percent of the C element which are greater than the other correlation.
Energies 2017, 10, 1857 12 of 15
Energies 2017, 10, 1857 12 of 15

56 54

Weight Percent (%)

Weight Percent (%)


54 R² = 0.9134 R² = 0.9971
52
52
50
50
48 48

46 46
0.00 0.20 0.40 0.60 0.80 1.00 0.00 1.00 2.00 3.00 4.00 5.00
Avg. Chain Scission (x1000) Avg. Chain Scission (x1000)

(a) (b)
2500 2500
2000 R² = 0.9964 2000 R² = 0.9814
1500 1500
DP

DP
1000 1000
500 500
0 0
44 46 48 50 52 54 46 48 50 52 54
Weight Percent (%) Weight Percent (%)

(c) (d)

Figure 16. Correlation between average number of chain scission of transformer insulation paper and
Correlation
Figure 16.weight between
percent of C elementaverage number
(a) 120 °C; (b) 150 of
°C chain scission between
and Correlation of transformer insulation paper
DP of transformer
and weight percent
insulation of Cand
paper element (a) 120of ◦OC;element;
weight percent (b) 150 ◦ C and Correlation between DP of transformer
(c) 120 °C; (d) 150 °C.
insulation paper and weight percent of O element; (c) 120 ◦ C; (d) 150 ◦ C .
Table 5. Correlation between average number of chain scission and functional group/chemical
element of transformer insulation paper.
Table 5. Correlation between average number of chain scission and functional group/chemical element
of transformerSample Functional Group/Chemical Element
insulation paper. Testing Method R2
120 0.9763
C–H (2922 cm−1) FTIR
150 0.8104 2
Sample120
Functional Group/Chemical Element Testing Method R
0.9839
C–H (2854 cm−1) FTIR
120 150 0.8534
0.9763
C–H (2922 cm−1 ) FTIR
150 120 0.932
0.8104
C=O (1743 cm−1) FTIR
150 0.9317
120 0.9839
120 C–H (2854 cm−1 ) FTIR 0.9134
150 Weight Percent C EDS 0.8534
150 0.9971
120 0.932
C=O (1743 cm−1 ) FTIR
150 Table 6, the values of R2 = 0.9964 and R2 = 0.9814 are the correlations between0.9317
From DP and the
weight 120
percent of the O element which are greater than the other correlation. The value0.9134
of R2 of the
Weight Percent C EDS
correlation
150 between DP and intensity of peak absorbance of the O–H functional group is very small
0.9971
because the degradation of transformer insulation paper increases significantly during thermal aging.
This research shows that EDS can be used as a testing method to predict DP through the percentage
FromofTable 6, theofvalues
decreasing of R2 = 0.9964 and R2 = 0.9814 are the correlations between DP
O element. and the
weight percent of the O element which are greater than the other correlation. The value of R2 of the
Table 6. Correlation between DP and functional group/chemical element of transformer insulation
correlation between
paper.
DP and intensity of peak absorbance of the O–H functional group is very small
because the degradation of transformer insulation paper increases significantly during thermal aging.
Sample Functional Group/Chemical Element Testing Method R2
This research shows120 that EDS can be used as a testing method to predict DP through 0.9362 the percentage of
O–H (3325 cm−1) FTIR
decreasing of O element.
150 0.5561
120 O–H (3273 cm−1) FTIR 0.8083

Table 6. Correlation between DP and functional group/chemical element of transformer insulation paper.

Sample Functional Group/Chemical Element Testing Method R2


120 0.9362
O–H (3325 cm−1 ) FTIR
150 0.5561
120 0.8083
O–H (3273 cm−1 ) FTIR
150 0.425
120 0.9964
Weight Percent O EDS
150 0.9814
Energies 2017, 10, 1857 13 of 15

4. Conclusions
This study confirmed that the DP and TS decreased with aging. There is a correlation between
physical and chemical characteristics of paper samples which is shown by the correlation between DP
and TS. The interactions between natural esters and transformer insulation paper can be explained by
the hydrolysis reaction of natural esters and a transesterification process of transformer insulation paper.
FTIR results showed that the intensity of the absorbances representing C–H and C=O functional groups
have increased with aging due to hydrolysis of the natural ester and the transesterification process
which involved the long alkyl chains of fatty acids. The peak absorbance at 1743 cm−1 in the FTIR
spectra of transformer insulation paper aged in natural ester confirms the transesterification process
of cellulose in the natural ester. The good performance of transformer insulation paper in natural
ester can be explained by the chemical structure analysis using FTIR and EDS. The strengthening of
the intensity of peak absorbance of the C–O functional group at wavenumber 1159 cm−1 of the aged
transformer insulation paper give evidence that the moisture within the transformer insulation paper
tends to remain in the natural ester and this causes the paper to become drier. This peak confirms that
transesterification process of transformer insulation paper in natural ester as insulating liquid may
make the estimated lifetime of transformers longer than using mineral oil as insulating liquid. There is
a correlation between the intensity of the absorbance of the peaks of C–H and C=O functional group
and the weight percent of the C element with the average number of chain scission of transformer
insulation paper. There is also a correlation between DP with the intensity of the absorbance of O–H
functional group peaks at wavenumbers of 3325 cm−1 and 3273 cm−1 and the weight percent of the O
element of transformer insulation paper. The experimental results using FTIR and EDS show a good
correlation between the chemical structure and DP. These results give initial information about the
feasibility of using spectroscopy techniques to identify and quantify the DP value. Further, EDS can be
more suitable to be used as a testing method to predict DP through the weight percent of the element O.

Acknowledgments: This research was carried out with financial support of the Ministry of Research,
Technology and Higher Education of Indonesia (KEMENRISTEKDIKTI).
Author Contributions: The authors contributed collectively to the experimental setup, testing and measurement,
data analysis and manuscript preparation.
Conflicts of Interest: The authors declare no conflict of interest.

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