energies

Article
Fourier Transform Infrared (FTIR) Spectroscopy
Analysis of Transformer Paper in Mineral Oil-Paper
Composite Insulation under Accelerated
Thermal Aging
Abi Munajad * ID
, Cahyo Subroto ID
and Suwarno ID

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

Received: 26 December 2017; Accepted: 29 January 2018; Published: 4 February 2018

Abstract: Mineral oil is the most popular insulating liquid for high voltage transformers due to
its function as a cooling liquid and an electrical insulator. Kraft paper has been widely used as
transformer solid insulation for a long time already. The degradation process of transformer paper
due to thermal aging in mineral oil can change the physical and chemical structure of the cellulose
paper. Fourier transform infrared (FTIR) spectroscopy analysis was used to identify changes in the
chemical structure of transformer paper aged in mineral oil. FTIR results show that the intensity
of the peak absorbance of the O–H functional group decreased with aging but the intensity of the
peak absorbance of the C–H and C=O functional groups increased with aging. Changes in the
chemical structure of the cellulose paper during thermal aging in mineral oil can be analyzed by
an oxidation process of the cellulose paper and the reaction process between the carboxylic acids
in the mineral oil and the hydroxyl groups on the cellulose. The correlation between the functional
groups and the average number of chain scissions of transformer paper gives initial information
that the transformer paper performance can be identified by using a spectroscopic technique as
a non-destructive diagnostic technique.

Keywords: transformer paper; mineral oil; thermal aging; Fourier transform infrared (FTIR)
spectroscopy

1. Introduction
Operational conditions of the transformer such as increased loading and short-circuit power
might affect the ability of the transformer to endure the mechanical, electrical, and thermal stresses
that occur. Those situations may accelerate the thermal aging of the transformer because electrical and
mechanical properties of the transformer become worse due to those stresses. Cellulose paper has
been used in power transformers as solid insulation for 100 years [1]. Cellulose is a homopolymer of
D -anhydroglucose units bonded together with C1–C4 glycosidic oxygen linkages [2]. Cellulose paper
plays an important role in considering the lifetime of power transformers [3–5]. Cellulose has been
characterized by the degree of polymerization (DP), which is the average number of glucose rings
of its polymeric chain [6,7]. The DP that is related to the tensile strength of the paper decreases with
aging. At low DP levels, the ability to withstand high mechanical stresses is significantly reduced,
increasing the risk of electrical failures such as generating the inrush current through windings [6,7].
By considering the effects of the damage of solid insulation of transformers, it can be concluded
that the life of a transformer is directly related to its solid insulation condition. During operation,
the degradation process of the cellulose paper takes place due to thermal aging, which is the dominant

Energies 2018, 11, 364; doi:10.3390/en11020364 www.mdpi.com/journal/energies

Energies 2018, 11, 364 2 of 12

aging in power transformers. The lifetime of the solid insulation is affected by temperature, water, and
oxygen [8]. The aging mechanism of solid insulation can be explained by the degradation process of
cellulose, which is the combined effect of pyrolysis, hydrolysis, and oxidation [7]. Cellulose paper and
insulating liquid are the main parts of power transformers’ insulation.
Nowadays, mineral oil is the most popular insulating liquid for high voltage transformers. Mineral
oil has been used not only for liquid insulation but also as a cooling medium of power transformers.
Mineral oil is well known as an insulating liquid for power transformers due to several advantages: good
compatibility with cellulose paper as solid insulation, good physical and electrical properties, suitable
properties such as good electrical arc quenching, availability, low cost, and long history [9–11]. Mineral
oil is a complex mixture of several hydrocarbon molecules and its chemical formula consists of alkenes
(paraffin), cyclic alkenes (naphthene), and aromatics [9,11]. Oxidation is the major degradation mechanism
of hydrocarbon oil and the rate of oxidation depends on temperature [12]. The degradation process due
to thermal aging can change the physical and chemical structure of transformer paper in mineral oil.
Fourier transform infrared (FTIR) spectroscopy analysis can identify chemical bonds by using an infrared
spectrum that is absorbed by the material. Spectroscopy is a powerful non-destructive technique that uses
an electromagnetic radiation interaction effect to determine the atomic or molecular structure and the
energy level of the substance [13]. So far, many researchers have developed the non-destructive technique
to measure the condition of both the oil and the paper in a power transformer using spectroscopy
techniques. For insulating liquid performance measurements, the combination of spectroscopy techniques
and an artificial neural network is used to obtain the correlation between the spectral response and the
chemical and physical properties of the oil. This combined method has been used to investigate a 2-FAL
compound in transformer oil, the interfacial tension number of transformer oil, and various dissolved
gases within transformer oil [13–15]. For insulating paper performance measurements, the spectroscopy
technique and statistical analyses have been developed to obtain a correlation between the spectral
response and the chemical properties of the paper. Several works have reported that this combined
method has shown the possibility of using the spectroscopy technique for determining the degree of
polymerization (DP) and water content of the transformer paper [6,16–18]. Currently, destructive methods
such as viscometry have been widely used for the direct measurement of DP [6,19].
This paper reports the chemical structures of transformer paper aged in mineral oil using Fourier
transform infrared (FTIR) spectroscopy. Fourier transform infrared (FTIR) spectroscopy shows the
intensity of the peak absorbance of the functional groups of transformer paper, which can identify
the chemical bond in a molecule of cellulose paper. This study was conducted to provide a better
understanding of transformer paper characteristics in mineral oil during thermal aging using Fourier
transform infrared (FTIR) spectroscopy. This study also gives initial information that the condition of
the cellulose paper as transformer solid insulation, which has a direct correlation with the life of the
transformer, can be identified by using a spectroscopy technique.

2. Experimental Specimens and FTIR Measurement

2.1. Preparation of Experimental Specimens

The sample needed for this experiment was a copper conductor, kraft paper, and mineral oil.
Mineral oil used in this experiment is an uninhibited transformer oil that is typically used for high
voltage transformers and conforms to IEC 60296. The transformer paper (thickness of 0.061 mm and
a base weight of 0.0064 g/cm2 ) used for these studies was kraft paper, which is available commercially
for power transformer windings. The initial water content of all kraft paper samples was about
5%. The copper conductor was needed in this experiment in order to obtain the real conditions of
a transformer where the transformer coils are insulated by kraft paper and immersed in insulating
liquid. IEEE Standard C57.100–2011 also recommends using a copper conductor in experiments relating
to transformer solid insulation [20]. A total amount of 10 g kraft paper, 8.75 g copper conductor, and
200 g mineral oil were placed in a hermetical glass bottle [17,21]. A pre-treatment process was carried
Energies 2018, 11, 364 3 of 12

out on the mineral oil samples by putting the mineral oil in the oven for 24 h at 100 ◦ C [9,11,17].
Energies 2018,
The purpose of 11, x FOR
this PEER
step wasREVIEW
to reduce the amount of water content inside the mineral oil. 3 of 12
Kraft paper was cut into strips and wrapped around the copper conductor before the paper samples
on the mineral oil samples by putting the mineral oil in the oven for 24 h at 100 °C [9,11,17]. The purpose
were ofinserted
this stepinto
was heat-resistant glass of
to reduce the amount bottles. After that,
water content insideeach aging oil.
the mineral test bottle was sealed. In this
experiment, Kraft paper was cut into strips and wrapped around the copper conductorrecommendation
thermal aging using a sealed system was chosen based on the of the IEEE
before the paper samples
Standard
were C57.91–1995
inserted into [22]. An accelerated
heat-resistant thermal
glass bottles. aging
After that, test
eachwas conducted
aging test bottletowas
obtain the aged
sealed. In thispaper
samples in a short
experiment, time.aging
thermal All ofusing
the sealed
a sealedglass
systembottles were placed
was chosen based on inthe
two different ovens
recommendation offor
the aging
IEEE and
Standard ◦
C57.91–1995 ◦
[22]. An accelerated thermal aging test was conducted to
heated to 120 C and 150 C, respectively, for a certain period of time. Samples were taken out of the obtain the aged paper
ovenssamples in a intervals:
at regular short time.336,
All of theand
672, sealed glass
1008 bottles were
h. Aging placed in twoof
at a temperature 150 ◦ Covens
different for agingaccording
was selected and
heated to 120 °C and 150 °C, respectively, for a certain period of time. Samples were taken
to a reference published in IEEE by Mc Shane et al. [23], while aging at a temperature of 120 C is a hot out of the ovens
◦
at regular intervals: 336, 672, and 1008 h. Aging at a temperature of 150 °C was selected according to a
spot temperature according to the IEEE [24]. A list of samples is shown in Table 1.
reference published in IEEE by Mc Shane et al. [23], while aging at a temperature of 120 °C is a hot spot
temperature according to the IEEE [24].
TableA list of samples
1. Sample andistreatment.
shown in Table 1.

Table 1. Sample and treatment.

Sample Aging
MO.T0 Initial state
Sample Aging
MO.T1.120 120 ◦ C for 336 h
MO.T0
MO.T2.120 Initial
120 ◦ C state
for 672 h
MO.T1.120
MO.T3.120 120
120°C◦ Cfor
for336 hh
1008
MO.T1.150 ◦ C for 336 h
MO.T2.120 120150
°C for 672 h
MO.T2.150 ◦ C for 672 h
MO.T3.120 120150
°C for 1008 h
MO.T3.150 150 ◦ C for 1008 h
MO.T1.150 150 °C for 336 h
MO.T2.150 150 °C for 672 h
2.2. Fourier Transform Infrared (FTIR) Spectroscopy
MO.T3.150 150 °C for 1008 h

Electromagnetic radiation
2.2. Fourier Transform Infraredthat interacts
(FTIR) with a substance can be absorbed, transmitted, reflected,
Spectroscopy
scattered, or have photoluminescence (PL), which provides significant information on the molecular
Electromagnetic radiation that interacts with a substance can be absorbed, transmitted, reflected,
structure and the energy level transition of that substance [13,25]. Paper samples placed in the path of
scattered, or have photoluminescence (PL), which provides significant information on the molecular
an infrared beam will absorb and transmit light and then the light signal will penetrate the sample
structure and the energy level transition of that substance [13,25]. Paper samples placed in the path
to theofdetector.
an infrared The detector
beam measures
will absorb the intensity
and transmit light andof thethe
then radiation moving
light signal into a sample
will penetrate and the
the sample
intensity
to theofdetector.
the radiation transmitting
The detector measures through a sample.
the intensity of theFigure 1a moving
radiation shows the intoschematic
a sample anddiagram
the of
an FTIR spectrometer.
intensity Its output
of the radiation as a function
transmitting throughof time is Figure
a sample. converted into the
1a shows a plot of absorption
schematic diagram against
of
an FTIR spectrometer.
wavenumber by a computer Its using
outputaas a function
Fourier of timemethod
transform is converted
[25].into a plot
In this of absorption
experiment, theagainst
application
wavenumber by a computer using a Fourier transform method [25].
of an ALPHA FTIR spectrometer was used to measure infrared spectra of the functional groups In this experiment, the of
application of an ALPHA FTIR spectrometer was used to measure infrared
transformer paper. An ALPHA FTIR spectrometer is shown in Figure 1b. FTIR using an attenuated spectra of the functional
total groups of transformer paper. An ALPHA FTIR spectrometer is shown in Figure 1b. FTIR using an
reflection (ATR) technique was used in this experiment to investigate the structural changes
attenuated total reflection (ATR) technique was used in this experiment to investigate the structural
of cellulose paper by obtaining its infrared spectra. The penetration depth of a light beam using
changes of cellulose paper by obtaining its infrared spectra. The penetration depth of a light beam
an ATR technique into a sample is about 0.5–3 µm [7]. This measurement only needed small samples
using an ATR technique into a sample is about 0.5–3 μm [7]. This measurement only needed small
of transformer paper andpaper
samples of transformer each and
sample was conducted
each sample was conducted twicetwice
to ensure
to ensure the
theinfrared
infrared spectra
spectra ofof the
investigated paper samples.
the investigated The observed
paper samples. spectra
The observed are the
spectra areabsorbance of theofdifferent
the absorbance paper
the different samples
paper
versus the wavenumber range 4000–400 −1 .
samples versus the wavenumber range cm4000–400 cm−1.

(a) (b)

Figure 1. (a) Schematic diagram of Fourier transform infrared (FTIR) spectrometer. (b) ALPHA FTIR
Figure 1. (a) Schematic diagram of Fourier transform infrared (FTIR) spectrometer. (b) ALPHA
spectrometer.
FTIR spectrometer.
Energies 2018, 11, 364 4 of 12

3. Results
Energies 2018, and
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11,
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Discussion
x2018,
FOR x2018,x11,
PEER
11,
FOR x FOR
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3.3.1.
3.Fourier
Results 3. Transform
and
Results Results Infrared
and
Discussion
3. Results
and and Discussion
Discussion (FTIR) Spectroscopy Analysis of Transformer Paper
Discussion
During operation, the oil–paper composite insulation within a transformer experiences an aging
3.1. 3.1.
Fourier
3.1. 3.1. Fourier
Transform
Fourier
Fourier Transform
Infrared
Transform
Transform Infrared
(FTIR)
Infrared
Infrared (FTIR)
Spectroscopy
(FTIR)
(FTIR) Spectroscopy
Analysis
Spectroscopy
Spectroscopy Analysis
Analysis
Analysis of Transformer
of Transformer Paper
of Transformer
of Transformer Paper
Paper
Paper
process that is caused by a combination of thermal, electrical, and mechanical stresses. Thermal stress
During
During
in oil–paper DuringDuring
operation,
operation,
composite operation,
the
operation, the the
oil–paper
the oil–paper
insulation isoil–paper
composite
oil–paper the composite
insulation
composite
composite
most insulation
within
insulation
insulation
significant within
factor inawithin
awithin
transformer a transformer
experiences
a transformer
transformer
insulation experiences
an Due
experiences
experiences
aging [26]. aging an an aging
to aging
an aging thermal
stress, the degradation process of insulation materials within transformers leads to changes instress
process that process
process
process is
thatcaused
that
is that
is
caused by isa
caused caused
combination
by a by a by a combination
of
combination
combination thermal,
of of of thermal,
electrical,
thermal,
thermal, andelectrical,
electrical,
electrical, mechanical
and and and mechanical
stresses.
mechanical
mechanical stresses.
Thermal
stresses.
stresses. Thermal
stress
Thermal
Thermal stressstress the
in oil–paper incomposite
oil–paper
in oil–paper
in oil–paper composite
insulation
composite
composite isinsulation
the
insulation is most is most
the most
significant
is most
the significant
factor
significant infactor
infactor
insulation inaging
insulation
in insulation [26].
aging aging
Due to[26].
[26]. thermal
Due Due to thermal
to thermal
chemical structure of theinsulation
insulation the
material. significant
A chemical factor
reaction insulation
takesagingplace[26].during Due to thermal
the degradation
stress, the stress,
degradation
stress,
stress, the the the degradation
process
degradation
degradation process
of insulation
process
process of materials
insulation
of insulation
of insulation materials
within
materials
materials within withinwithin
transformers transformers
leads
transformers
transformers leads toleads
toleads
changes to
in changes
to changes
changes the
in thein thein the
process. Table 2 shows the visual appearances of paper surfaces aged in mineral oil. The color of
chemical chemical
structure
chemical
chemical ofstructure
the
structure
structure of insulationof the
of insulation
the the insulation
material.
insulation A material.
chemical
material.
material. A chemical
reaction
A chemical
A chemical takesreaction
reaction
reaction place
takes takestakes
during
place place place
the
during duringthe the
degradation
during
the degradation
degradation
degradation
the paper surface
process. becomes darker with aging. Solid dielectrics become darker ascolor
the aging timeof and
process. Table
process. Table
process. 2 Table
2 Table
shows 2the
shows 2visual
shows shows
the visualthe
theappearancesvisual
appearances
visual appearances
of paper
appearances of paper of
ofsurfacespaper
surfaces
paper agedsurfaces
surfaces aged in aged
in aged
mineral
mineral in mineral
oil.
in mineral The oil. oil.
oil. The ofThe
color
The ofcolor
the
color of the the
the
temperature
paper
paperpaperpaper
surface
surface increase.
surface
becomes
surfacebecomes It
darker
becomes can
becomes
darker be
with
darker stated
darker
withaging.
with
aging.that
with
Solid
aging. an
aging.old
dielectrics
Solid Solid transformer
Solid
dielectrics dielectrics
become
dielectrics become might
become
darker
become as
darker have
the
darkeras darker
darker
aging
as the
the astime
aging solid
the
aging aging
and
time dielectrics
time
and time
andand
temperature
compared temperature
temperaturetoincrease.
temperaturea new
increase. It increase.
one. can
increase. be
ItWhen
can It
It stated
can
be can
bethat
higher
stated betemperatures
statedstated
an that
that an that
old an old
old anwere
transformerold transformer
might
transformer
transformer applied, might have
mightmight
darker
thehave have
insulationhave
solid
darker darker
darker
paper
solid solid solid
dielectrics dielectrics
dielectrics
became
dielectrics darker
compared
compared
faster. Thetocompared
compareda to
new
visual a to
new a to
one. new a new
When
one.
appearance one.
Whenone.
higher
When When
ofhigher
the higher
temperatures
higher
paper temperatures
were
temperatures
temperatures
sample applied,
were were
changed were theapplied,
applied,
applied,
with insulation
the the insulation
paper
the insulation
insulation
aging, which became
paper paper paper
became
indicates darker
becamebecame
darker
changes darkerdarker
in the
faster. The
faster. faster.
visual
faster.
The
microstructure The The
visual
and visual
appearance
visual
chemical appearance
ofstructure
appearance
appearance the
of thepaper of
of paper
the the
ofsample
paper paper
thesample sample
cellulosesample
changed with
changed
changed
paper. changed
aging,
with
The with with
which
aging, aging,
aging,
chemicalwhich whichwhich
indicates indicates
changes
indicates
indicates
structure in changes
thechanges
ofchanges in in in
transformer
the the
paper the the inmicrostructure
microstructure
microstructure
aged andand
microstructure
mineral chemical
oiland and
chemical
can be chemical
structure
chemical structure
identified ofstructure
structurethe
of the
by of Fourier
cellulose
of the
using the cellulose
paper.
cellulose
cellulose paper. The paper.
paper.
transform chemical
The The The chemical
structure
chemical
chemical
infrared ofstructure
the
structure
structure
(FTIR) of the of the
of the
spectroscopy.
transformer transformer
transformer
FTIR was paper
transformer
usedpaper aged
to paper paper
in
agedaged
identify aged
mineral
inthe in
oil
infunctional
mineral
mineral mineral
can be oil
oilgroups
oil can can can
identified be identified
by
be identified
be identified
of theby using by
Fourier
by using
using
investigated using Fourier
transform
Fourier
Fourier transform
infrared
transform
transform
material, which infrared
(FTIR)
infrared
infrared (FTIR)
is shown (FTIR)(FTIR)
by the
spectroscopy. spectroscopy.
FTIR
spectroscopy.
spectroscopy. was
FTIR
intensity of peak absorbance. FTIR
was FTIR
used wasto
used was
used
to used
identify to to
the identify
identify
identify functional
the the the functional
groups
functional
functional groups of
groupsgroups
the
of of
the of
investigated
the the investigated
material,
investigated
investigated material,
which
material,
material, whichis
which which
is is is
shown by shown
the
shown
shown by by the
intensity ofintensity
by intensity
the the peak
intensity of
of peak of
peakpeak
absorbance. absorbance.
absorbance.
absorbance.
Table 2. Visual appearances of the paper sample.
Table
Table 2. Table
2. Table
Visual 2.appearances
Visual
2.appearances
Visual
Visual appearances
of the
of paper
appearances the of the
sample.
ofpaper
the paper
paper sample.
sample.
sample.
Aging Time
Aging Time
Aging (h)
Aging
Time (h)(h)
Aging
TimeTime
(h) (h)
Temperature
Temperature
Temperature
Temperature
Temperature
0 0 0 00 336 336 336 336
336 672 672 672
672 672 1008100810081008
1008

120 °C 120
120 °C
120 °C 120°C◦ C

150 °C 150
150 °C
150 °C °C◦ C
150

FigureFigure
Figure 2 Figure
2Figure
shows
2shows2 the
shows 2the
shows shows
FTIR
the the
FTIR
FTIR the
spectra
FTIR FTIR spectra
of transformer
spectra
spectra
spectra of of transformer
paper
of transformer
oftransformer
transformer aged
paper paper
paper
paper aged inaged
inaged
mineral
aged in mineral
oil
in mineralfor
mineral
mineral
in oil 1008
oil
for oil
for
oil1008
for for
h. 1008
h. 1008
Tables
1008 h.h.h.Tables
Tables 3Tables
3Tables 3 33
andand
4 show
and and
the
4 4
show show
peak the the
absorbance
peak peak absorbance
values
absorbance of values
the
values paper
of of
the the paper
samples.
paper samples.
There
samples. is a There
significant
There is a
4 show the peak absorbance values of the paper samples. There is a significant difference between is a significant
difference
significant difference
between
difference between
between
and 4 show the peak absorbance values of the paper samples. There is a significant difference between
FTIRFTIR
spectra,
FTIR FTIR spectra,
especially
spectra,
spectra, especially
the
especially
especially peakthe
the peakthe
peakpeak
absorbance absorbance
value
absorbance
absorbance value ofvalue
ofvalue
the of the
infrared
of the
the infrared
spectra
infrared
infrared spectra
of the
spectra
spectra paper
of the
of the of sample
paperthe
paperpaper
at sample
at at at
sample
sample
FTIR spectra, especially the peak absorbance value of the infrared spectra of the paper sample at
aging
aging aging aging
temperatures temperatures
of 120
temperatures
temperatures °C
of and
of 120 of and
120
◦°C
120
150 °C
°C and
°C and
150 of
150
°C 150
the °Csame
°Csame
of
◦ Cofofthe
ofaging
the the
same same
times.
aging agingaging
This times.
confirms
times.
times. This This This confirms
that
confirms
confirms thermal
that that that thermal
stress
thermal
thermal stress
stress
stress
aging
influencestemperatures
influences influences
the
influences the the
chemical of 120
chemical
structure
chemical
the chemical
C and
of 150ofsamples.
structure
paper
structure
structure of paper paper
the
ofsamples.
paper same
samples.
samples.
aging times. This confirms that thermal stress
influences the chemical structure of paper samples.
0.2 0.2 0.2 0.2
O-HO-HO-HO-H
C-HC-HC-HC-H C=OC=OC=OC=OC-OC-OC-OC-O
0.15 0.15 0.150.15
Absorbance
Absorbance

Absorbance
Absorbance
Absorbance

0.1 0.1 0.1 0.1

0.05 0.05 0.050.05

0 0 0 0
3267

2415

1563

711
3998
3876
3754
3632
3511
3998
3389
3876
3267
3754
3145
3632
3024
3511
2902
3389
2780
2658
3145
2537
3024
2415
2902
2293
2780
2171
2658
2050
2537
1928
1806
2293
1685
2171
1563
2050
1441
1928
1319
1806
1198
1685
1076
954
1441
832
1319
711
1198
589
1076
954
832

589
3998
3876
3754
3632
3511
3389
3267
3145
3024
2902
2780
2658
2537
2415
2293
2171
2050
1928
1806
1685
1563
1441
1319
1198
1076
954
832
711
589
3998
3876
3754
3632
3511
3389
3267
3145
3024
2902
2780
2658
2537
2415
2293
2171
2050
1928
1806
1685
1563
1441
1319
1198
1076
954
832
711
589
3998
3876
3754
3632
3511
3389
3267
3145
3024
2902
2780
2658
2537
2415
2293
2171
2050
1928
1806
1685
1563
1441
1319
1198
1076
954
832
711
589

Wavenumber
Wavenumber (cm¯¹)
Wavenumber
Wavenumber (cm¯¹)
(cm¯¹)
(cm¯¹)

MO.T0 MO.T0
MO.T0
MO.T0 MO.T3.120 MO.T3.120
MO.T3.120
MO.T3.120 MO.T3.150 MO.T3.150
MO.T3.150
MO.T3.150

Figure 2.Figure
FTIR Figure 2. FTIR
spectra of
2. spectra
FTIR spectra
transformer
spectra of paper
transformer
of transformeraged paper
in
paper aged
mineral
aged in inatoil
oil mineral
mineralaging
atoil oilaging
at aging
temperatures temperatures
of 120
of °C andofand
120 °C and
Figure
Figure 2. 2. FTIR
FTIR spectra of
of transformer
transformer paper
paperaged inin
aged mineral
mineral oil atat
aging temperatures
temperatures
aging temperatures ofof
120 120
°C120°C and
◦C and
150 °C
◦ for
150 °C 1008
150 150
for
°C h.°C1008
1008
for for
h. 1008
h. h.
150 C for 1008 h.
Energies 2018, 11, 364 5 of 12
Energies 2018, 11, x FOR PEER REVIEW 5 of 12

Table 3. 3.Peak
Table Peakabsorbance
absorbance values ofIR
values of IRspectra
spectraofof paper
paper samples
samples aged
aged in mineral
in mineral oil at oil 120 ◦ C.
120at°C.

Wavenumber (cm−1)(cm−1 )
Wavenumber MO.T0MO.T0 MO.T1.120
MO.T1.120 MO.T2.120
MO.T2.120 MO.T3.120
MO.T3.120
2922 0.03842 0.0672 0.08303 0.10985
2922 0.03842 0.0672 0.08303 0.10985
2854 0.03715 0.0557 0.06799 0.08303
2854 0.03715 0.0557 0.06799 0.08303
1745 1745 0.01880.0188 0.0283
0.0283 0.03432
0.03432 0.05827
0.05827
1454 1454 0.03391
0.03391 0.04389
0.04389 0.03745
0.03745 0.05759
0.05759
1369 1369 0.04387
0.04387 0.04976
0.04976 0.04438
0.04438 0.05549
0.05549
1314 1314 0.05322
0.05322 0.05592
0.05592 0.05142
0.05142 0.05979
0.05979
1159 1159 0.06123
0.06123 0.06773
0.06773 0.06436
0.06436 0.0834
0.0834
1104 1104 0.09064
0.09064 0.09366
0.09366 0.08533
0.08533 0.10457
0.10457
1050 1050 0.14004
0.14004 0.14092
0.14092 0.1278
0.1278 0.14907
0.14907
1026 1026 0.15272
0.15272 0.15453
0.15453 0.14076
0.14076 0.16223
0.16223
815 0.05484 0.06236 0.05699 0.0658
815 0.05484 0.06236 0.05699 0.0658

Table 4. 4.Peak
Table Peakabsorbance
absorbance values ofIR
values of IRspectra
spectraofof paper
paper samples
samples aged
aged in mineral
in mineral oil at oil 150 ◦ C.
150at°C.

Wavenumber (cm−1) MO.T0 MO.T1.150 MO.T2.150 MO.T3.150

Wavenumber (cm−1 ) MO.T0 MO.T1.150 MO.T2.150 MO.T3.150
2922 0.03842 0.06619 0.07869 0.10029
2922 2854 0.03842
0.03715 0.06619
0.05521 0.064160.078690.07608 0.10029
2854 1745 0.03715
0.0188 0.05521
0.03462 0.049430.064160.0555 0.07608
1745 0.0188 0.03462 0.04943 0.0555
1454 0.03391 0.04588 0.05008 0.05566
1454 0.03391 0.04588 0.05008 0.05566
1369 0.04387 0.05201 0.05488 0.05503
1369 0.04387 0.05201 0.05488 0.05503
1314 1314 0.05322
0.05322 0.06098
0.06098 0.062710.062710.06098 0.06098
1159 1159 0.06123
0.06123 0.07295
0.07295 0.078740.078740.07974 0.07974
1104 1104 0.09064
0.09064 0.09967
0.09967 0.101230.101230.10112 0.10112
1050 1050 0.14004
0.14004 0.14617
0.14617 0.144380.144380.14046 0.14046
1026 1026 0.15272
0.15272 0.15797
0.15797 0.157120.157120.15071 0.15071
815 815 0.05484
0.05484 0.06179
0.06179 0.067550.067550.06297 0.06297

From Figure 2, the FTIR spectrum of new cellulose paper shows absorbance peaks at
From Figure 2, the FTIR spectrum of new cellulose paper shows absorbance peaks at wavenumbers
wavenumbers 3700–3000 cm−1 (which is an O–H functional group), at wavenumbers 3000–2700 cm−1
3700–3000 cm−1 (which is an O–H functional group), at wavenumbers−13000–2700 cm−1 (which is a C–H
(which is a C–H functional group), and at wavenumbers−1500–900 cm (which is a C–O functional
functional group), and at wavenumbers 1500–900 cm 1 (which is a C–O functional group). These
group). These functional groups identified are consistent with the basic structure of cellulose as
functional
shown ingroups identified are consistent with the basic structure of cellulose as shown in Figure 3.
Figure 3.

Figure
Figure3.3.Molecular
Molecularstructure of cellulose.
structure of cellulose.

Figure 4a,b presents the FTIR spectra of transformer paper aged in mineral oil at aging
Figure 4a,bof presents
temperatures 120 °C andthe 150FTIR spectra
°C. These of relate
figures transformer paper aged
to the hydroxyl groupsinof mineral oil The
the spectra. at aging
temperatures of 120 ◦ C and 150 ◦ C. These figures relate to the hydroxyl groups of the spectra. The peak
peak absorbance at 3329 cm represents the O–H functional group. The peak absorbance located close
−1

absorbance
to 3340 cmat −1 3329 cm−1 characteristic
is a typical represents the of O–H functional
cellulose [27]. As group.
shown in The peak
these absorbance
figures, located
it is clear close to
that the
peak
3340 − 1
cmabsorbance value
is a typical of the O–H functional
characteristic group
of cellulose [27].located closein
As shown tothese
3329 cm −1 decreases with aging
figures, it is clear that the peak
due to thevalue
absorbance oxidation
of theprocess. The products
O–H functional of degradation
group located closeof cellulose
to 3329 cm −1 decreases
paper are CO, CO 2, H2aging
with O, H2,due to
CH 4, and furans, which are dissolved in the mineral oil [28]. During thermal aging, the cleavage of
the oxidation process. The products of degradation of cellulose paper are CO, CO2 , H2 O, H2 , CH4 ,
andcellulose
furans, chains
which involves an O–H functional group. An O–H group reacts with a hydrogen atom
are dissolved in the mineral oil [28]. During thermal aging, the cleavage of cellulose
generating a water molecule. An alcohol is transformed into ketone by an oxidation process. In this
chains involves an O–H functional group. An O–H group reacts with a hydrogen atom generating
a water molecule. An alcohol is transformed into ketone by an oxidation process. In this process,
the hydrogen of the O–H group is displaced toward the carbon group and the CH2 OH groups react
 Energies 2018, 11, x FOR PEER REVIEW 6 of 12
Energies
Energies 2018,2018, 11, x FOR PEER REVIEW
11, 364 6 of 126 of 12
process, the hydrogen of the O–H group is displaced toward the carbon group and the CH2OH
process,
groups reactthewith
hydrogen
oxygen of linking
the O–Hthegroup is displaced
glucose molecules,toward the carbon
thereby group
cleaving the and
chaintheasCH 2OH in
shown
with groups
oxygen
Figure react
5 [29,30]. with
linking oxygen
Thisthe glucose
intensity linking the glucose
ofmolecules, molecules,
thereby
peak absorbance thereby
cleaving
located closethe cleaving
tochain
3329 cm the
as shown
−1 chain
can bein as shown in a
Figure 5 [29,30].
associated with
Figure
reduction
This 5 [29,30]. This
in molecular
intensity intensity of
weight or the
of peak absorbance peak absorbance
DP value
located close[7].located close
− 1 to 3329 cm−1 can be associated with a
to 3329 cm can be associated with a reduction in
reduction in molecular weight or the DP value [7].
molecular weight or the DP value [7].

0.07 0.07
0.07 0.07
0.060.06 0.06
0.06
Absorbance

Absorbance
0.050.05 0.05
Absorbance

Absorbance
0.05
0.040.04 0.04
0.04
0.030.03 0.03
0.03
0.020.02 0.02
0.02
0.010.01 0.01
0.01
0 0 00
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
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
Wavenumber(cm¯¹
Wavenumber (cm¯¹)
) Wavenumber
Wavenumber(cm¯¹)
(cm¯¹)

MO.T0 MO.T1.120 MO.T0 MO.T1.150

MO.T0 MO.T1.120 MO.T0 MO.T1.150
MO.T2.120 MO.T3.120 MO.T2.150 MO.T3.150
MO.T2.120 MO.T3.120 MO.T2.150 MO.T3.150
(a) (b)
(a) (b)
Figure 4. FTIR spectra at 3700–3000 cm−1 of transformer paper aged in mineral oil at aging
−1 of transformer paper aged in mineral oil at aging
Figure
Figure4.4. FTIR spectra
FTIR ofspectra at 3700–3000
at and
3700–3000 cm
cm−1 of transformer paper aged in mineral oil at aging
temperatures (a) 120
◦ °C (b) 150◦ °C.
temperatures
temperaturesofof(a)
(a)120
120 °CC and
and(b)
(b)150 C.
150 °C.

Figure 5. Cleavage of cellulose chains.

Figure 6a,b illustrates the variations of the FTIR

Figure5.5. Cleavage
Cleavage spectra chains.
of cellulose
cellulose around 2900 cm−1, which represent a
Figure of chains.
C–H functional group. The intensity of these absorbance peaks at 2922 cm−1 and 2854 cm−1 increase
with aging
Figure dueillustrates
6a,b to the adsorption process of
the variations ofthethemineral oil to thearound
FTIR spectra paper surface
2900 cm during agingrepresent
−1, which [7]. The a
Figure 6a,b illustrates the variations of the FTIR spectra around 2900 cm −1 , which represent a C–H
C–H major degradation
functional group.of The
the aging mechanism
intensity of these inabsorbance
mineral oil ispeaks
oxidation [7,29].
at 2922 cmOxidation
−1 and 2854 decomposes
cm−1 increase
−1 and 2854 cm−1 increase with
withthe
functionalhydrocarbon
aginggroup. The
due to the molecules
intensity
adsorption intoprocess
of other substances:
these absorbance
of the mineral hydroperoxide,
peaks at 2922 alcohol,
cm
oil to the paper aldehyde,
surface during ketones, and The
aging [7].
agingesters.
due The
to theoxidation
adsorptionreaction of
process mineral
of the oil also
mineral generates
oil to the carboxylic
paper acids
surface
major degradation of the aging mechanism in mineral oil is oxidation [7,29]. Oxidation decomposes (R–COOH),
during aging which
[7]. Thebindmajor
to alcoholofthereby
degradation the generating
aging esters. The
mechanism in degradation
mineral oil isprocess
oxidation of transformer
[7,29]. paper aged
Oxidation in mineral the
decomposes
the hydrocarbon molecules into other substances: hydroperoxide, alcohol, aldehyde, ketones, and
oil is due molecules
hydrocarbon to the combined effectssubstances:
into other of pyrolysis,hydroperoxide,
hydrolysis, and oxidation [7]. Temperature,
alcohol, acids
aldehyde, ketones, moisture,
and esters.
esters. The oxidation reaction of mineral oil also generates carboxylic (R–COOH), which bind
The and oxygen
oxidation are the
reaction key
of factors
mineral that
oil determine
also the
generates aging rate
carboxylic of cellulose
acids paper
(R–COOH), [7]. CO 2, water, furanic
which bind to alcohol
to alcohol thereby generating esters. The degradation process of transformer paper aged in mineral
compounds,
thereby generating andesters.
carboxylThe acids (R–COOH)
degradation form of
process through the oxidative
transformer paper ageddegradation
in mineralof cellulose
oilmoisture,
is due to
oil is due to the combined effects of pyrolysis, hydrolysis, and oxidation [7]. Temperature,
paper [7]. During thermal aging, the carboxylic acids generated from the oxidation process of mineral
the combined
andoiloxygen effects
are the of pyrolysis,
keyhydroxyl
factors that hydrolysis,
determine and oxidation [7]. Temperature, moisture, and oxygen
can react with groups on thethe aging rate
cellulose of cellulose
forming papergraft
a cellulose [7]. CO 2, water, furanic
polymer via a
are the key factors
compounds, that
andreaction determine
carboxyl the aging rate of cellulose paper [7]. CO2 , water, furanic ofcompounds,
condensation [31]:acids (R–COOH) form through the oxidative degradation cellulose
and carboxyl
paper acidsthermal
[7]. During (R–COOH) form
aging, thethrough theacids
carboxylic oxidative degradation
generated from theofoxidation
celluloseprocess
paper [7]. During
of mineral
thermal
oil canaging,
react the
with RCOOH
carboxylic + HO-[Cellulose]
hydroxylacids generated
groups ↔ RCOO-[Cellulose]
on thefrom the oxidation
cellulose + H 2O
formingprocess of mineral
a cellulose graftoilpolymer
can reactvia
with
a
hydroxyl groups
condensation on the[31]:
reaction cellulose forming a cellulose graft polymer via a condensation reaction [31]:

RCOOH + HO-[Cellulose]
RCOOH ↔ RCOO-[Cellulose]
+ HO-[Cellulose] + H+
↔ RCOO-[Cellulose] 2OH O
2
Energies 2018, 11, 364 7 of 12

Energies 2018, 11, x FOR PEER REVIEW 7 of 12

Carboxylic acids are an organic compound that contain a carbon–oxygen double bond and
an oxygen–hydrogen
Carboxylic acids single
are an bond.
organicR iscompound
a hydrocarbon group that
that contain has a lot of C–H
a carbon–oxygen doublefunctional
bond and groups.
an
Energies
Theoxygen–hydrogen 2018, 11,
reaction betweensingle x FOR PEER REVIEW
the carboxylic acids in the mineral oil and the hydroxyl groups on the7 of 12
cellulose
bond. R is a hydrocarbon group that has a lot of C–H functional groups. The
reaction
paper is thebetween
cause ofthe thecarboxylic
increasing
Carboxylic acids are an organic acids
C–H incompound
the mineral
functional oil and on
group
that contain theathe
hydroxyl
cellulosegroups
carbon–oxygen
paper on the
double
after cellulose
bond and paper
a hydrocarbon
an
is the
group
oxygen–hydrogen single bond. R is a hydrocarbon group that has a lot of C–H functional groups. The (-
cause
(-R) in of
the the increasing
mineral oil isC–H
movedfunctional
to the group
cellulose on the cellulose
paper. The paper
radicals after a hydrocarbon
generated on thegroup
cellulose
R) in
surface the mineral
facilitate
reaction the
between oilthe
is carboxylic
movedattachment
physical toacids
the cellulose
in theof paper.
low
mineral oil The
molecular
and theradicals
weightgenerated
hydroxyl on
oil molecules
groups thecellulose
on the cellulose
and lead surface
paper to the
facilitate
formationis the cause of the increasing C–H functional group on the cellulose paper after a hydrocarbon group (-of a
of thea physical
layer of attachment
hydrocarbon of low
laminationmolecular on weight
the oil
cellulose molecules
surface and
and lead
an to the
increase formation
in the intensity
layerR) of hydrocarbon
in the
of the corresponding mineralto lamination
oilC–H
is moved to on
vibrations the the[7]. cellulose
cellulose paper.surface
Carboxyl inand
The radicals
acids the an increase
generated
mineral in
onand
oil thethe intensity
cellulose
the hydroxyl ofgroups
surface the
corresponding
facilitate
of cellulose the to
paper C–H
physical
are notvibrations
attachment
only the main [7].
of low Carboxyl
molecular
factors acids in the
weight
increasing oilthe mineral
molecules oil
andand
C–H functional leadthe hydroxyl
togroup
the but groups
formation a ofthe
areofalso
main layer paper
cellulose
factors ofinhydrocarbon
theare not only
emergence lamination
the the on
ofmain thefunctional
factors
C=O cellulose
increasing surface
the C–H
group and an cellulose
increase
on functional
the inpaper
group thebutintensity
are alsoof
surface. thethe
main
corresponding
factors in 7a,b
the emergenceto C–Hof vibrations
the [7].
C=Ospectra Carboxyl
functional acidson
group in the
the cellulose
mineral oil and surface.
paper the hydroxyl groups of
Figure presents the FTIR around 1700 cm− 1 , which represents the C=O functional
cellulose
Figure paper
7a,b are not only
presents the the main
FTIR factorsaround
spectra increasing the
1700 C–H
cm −1,functional group butthe are also the main
group. The intensity of this absorbance peak at 1745 cm increases with aging. ThisC=O − 1 which represents peakfunctional
emerges on
factors
group. The inintensity
the emergenceof thisofabsorbance
the C=O functional peak at group
1745 on −1
cm the cellulose with
increases paperaging.
surface. This peak emerges on
the cellulose paper
Figure 7a,bafter thermal
presents aging
the FTIR in mineral
spectra aroundoil. There
1700 cm−1,iswhich
no absorbance
represents the peak C=O at functional
this functional
the cellulose paper after thermal aging in mineral oil. There is no absorbance peak at this functional
group regionThe
group. forintensity
new transformer
of this absorbance paper. peak The emergence
at 1745 cm−1 increasesof the C=O
with functional
aging. This peak group emergesison due to
group region for new transformer paper. The emergence of the C=O functional group is due to
the cellulose
interactions between paper theafter
lowthermal
molecular aging in mineral
weight acidsoil. There is no
dissolved in absorbance
the mineralpeak at this
oil and the functional
cellulose [31].
interactions between the low molecular weight acids dissolved in the mineral oil and the cellulose
groupacids
Carboxylic region for new transformer
containing a carbon–oxygen paper. The doubleemergence
functional of the C=O react
group functional
with thegroup is due to
hydroxyl groups
[31].interactions
Carboxylicbetween acids containing
the low
a carbon–oxygen
molecular weight
double
acids
functional
dissolved in the
group
mineral
react
oil
with
and the
the hydroxyl
cellulose acid
on the cellulose, forming a cellulose graft polymer and H2 O. A carboxylate of the carboxylic
groups on
[31].in the cellulose,
Carboxylic acids forming a acellulose
containing carbon–oxygen graft polymer
doublethe and H2O. group
functional A carboxylate
react withofthe thehydroxyl
carboxylic
(RCOO-)
acidgroups
(RCOO-)
mineral oil
in mineral
binds to the cellulose; this creates emergence of the C=O functional group
on the cellulose,oil binds atocellulose
forming the cellulose; this creates
graft polymer and H the emergence of the C=O functional
2O. A carboxylate of the carboxylic
on group
the cellulose paper surface, as shown in Figure in 8.
acidon the cellulose
(RCOO-) paper
in mineral oilsurface,
binds toas the shown
cellulose; Figure 8.
this creates the emergence of the C=O functional
group on the cellulose paper surface, as shown in Figure 8.
0.15 0.15
Absorbance
Absorbance

0.15 0.15
0.1 0.1
Absorbance
Absorbance

0.1 0.1
0.05 0.05
0.05 0.05
0 0
0 0
3000
2966
2932
2898
2864
2830
2796
2762
2728
3000
2968
2937
2906
2875
2844
2813
2782
2750
2719

3000
2966
2932
2898
2864
2830
2796
2762
2728
3000
2968
2937
2906
2875
2844
2813
2782
2750
2719

Wavenumber (cm¯¹) Wavenumber (cm¯¹)

Wavenumber (cm¯¹) Wavenumber (cm¯¹)

MO.T0 MO.T1.120 MO.T0 MO.T1.150

MO.T0 MO.T1.120 MO.T0 MO.T1.150
MO.T2.120
MO.T2.120 MO.T3.120
MO.T3.120 MO.T2.150
MO.T2.150 MO.T3.150
MO.T3.150

(a)(a) (b)
(b)

Figure 6. 6.
FTIR spectra
spectraatat3000–2700
3000–2700 cmcm−−1−11 of
of transformer paperaged
agedininmineral
mineral
oil oil
at at aging
FigureFigure
6. FTIRFTIR
spectra at 3000–2700 cm of transformer
transformerpaper
paper aged in mineral oilaging
at aging
temperatures of of
temperatures (a)(a)
120 °C°Cand
120
◦ and(b)
(b)150
150
◦°C.
°C.
temperatures of (a) 120 C and (b) 150 C.

0.06
0.080.08 0.06
0.05
0.05
Absorbance
Absorbance

0.060.06
Absorbance
Absorbance

0.04
0.04
0.04 0.03
0.04 0.03
0.02
0.02 0.02
0.02 0.01
0 0.01
0
0 0
1801
1791
1781
1771
1761
1751
1741
1731
1721
1711
1702

1801
1791
1781
1771
1761
1751
1741
1731
1721
1711
1702
1801
1791
1781
1771
1761
1751
1741
1731
1721
1711
1702

1801
1791
1781
1771
1761
1751
1741
1731
1721
1711
1702

Wavenumber (cm¯¹) Wavenumber (cm¯¹)

Wavenumber (cm¯¹) Wavenumber (cm¯¹)
MO.T0 MO.T1.120 MO.T0 MO.T1.150
MO.T0
MO.T2.120 MO.T1.120
MO.T3.120 MO.T0
MO.T2.150 MO.T1.150
MO.T3.150
MO.T2.120 MO.T3.120 MO.T2.150 MO.T3.150
(a) (b)
(a) at 1800–1700 cm−1 of transformer paper aged in
Figure 7. FTIR spectra (b) mineral oil at aging
Figure 7. FTIR spectra at 1800–1700 cm−1 of transformer paper aged in mineral oil at aging
temperatures
Figure 7. FTIR ofspectra
(a) 120 °C
at and (b) 150 °C.
1800–1700 cm−1 of transformer paper aged in mineral oil at aging
temperatures of (a) 120 ◦ C and (b) 150 ◦ C.
temperatures of (a) 120 °C and (b) 150 °C.
Energies 2018, 11, 364 8 of 12
Energies 2018, 11, x FOR PEER REVIEW 8 of 12

Figure8.8.AAcarboxylate
Figure carboxylate of
of aacarboxlic
carboxlicacid.
acid.

3.2. Correlation between Average Number of Chain Scissions and the Structural Changes of Transformer
3.2. Correlation between
Paper Aged in Average
Mineral Oil Number of Chain Scissions and the Structural Changes of Transformer Paper
Aged in Mineral Oil
The intensity of the peak absorbance of the functional groups within transformer paper changes
The intensity
during thermalofaging
the peak
due toabsorbance of process.
the chemical the functional groups
The higher the within transformer
temperature and the paper
longerchanges
the
during
duration of thermal aging of transformer paper in mineral oil, the higher is the thermal energylonger
thermal aging due to the chemical process. The higher the temperature and the value. the
duration of thermal
The chemical agingisof
reaction transformer
faster in systemspaper in mineral
with higher oil,energy.
thermal the higher is the
Svante thermal
Arrhenius energythe
showed value.
The chemical reaction
relationship between is temperature
faster in systems with
and the ratehigher thermal
constant energy.inSvante
by the reaction Arrhenius
Equation (1): showed the
relationship between temperature and the rate constant
𝐸 by the reaction in Equation (1):
− 𝑎
𝑘 =𝐴∙𝑒 𝑅∙𝑇 (1)
Ea
where k is the rate constant at temperaturek T= (K),
A·e A−isRa·T constant
called ‘frequency factor’, Ea is the (1)
activation energy for the reaction (J/mol), and R is the universal gas constant (8.314 J/mole/K). The
whereactivation
k is theenergy representsatthe
rate constant energy that the
temperature molecule
T (K), A is in the initial state
a constant calledof ‘frequency
the process must haveEa is
factor’,
before it can take part in the reaction. The reaction rate at any time is assumed to be
the activation energy for the reaction (J/mol), and R is the universal gas constant (8.314 J/mole/K).proportional to
the number of unbroken polymer chain bonds in the aging of paper [8,32]. The Arrhenius
The activation energy represents the energy that the molecule in the initial state of the process must equation
about the thermal aging of transformer paper in mineral oil is shown in Equation (2) [33]:
have before it can take part in the reaction. The reaction rate at any time is assumed to be proportional
𝐸𝑎
𝐴𝑣𝑒𝑟𝑎𝑔𝑒 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑐ℎ𝑎𝑖𝑛 𝑠𝑐𝑖𝑠𝑠𝑖𝑜𝑛 = 𝐴 ∙ 𝑒 − 𝑅∙𝑇 ∙ 𝑡The Arrhenius equation
to the number of unbroken polymer chain bonds in the aging of paper [8,32]. (2)
about the thermal aging of transformer paper in mineral oil is shown in Equation (2) [33]:
In this calculation of the average number of chain scissions, the value of A depends on the initial
moisture content within the paper sample and the type of insulating−paper. Ea The value of A used for
Average number o f chain scission = A·e R·T ·t (2)
this calculation was 21 × 10 for non-upgraded kraft paper with a high moisture content [6,34]. For
8

the expected lifetime of the transformer, the energy activation of 111 kJ/mol was used in this
In this calculation of the average number of chain scissions, the value of A depends on the initial
calculation [6,34,35].
moisture content within the paper sample and the type of insulating paper. The value of A used
Table 5 shows the average8 number of chain scissions of each paper sample. The average number
for this calculation
of chain scissionswas 21 ×
of the 10 sample
paper for non-upgraded
increases withkraft paper with
an increasing a high
aging moistureatcontent
temperature the same[6,34].
For the
aging time. The probability of molecules colliding with each other increases with aging temperature. this
expected lifetime of the transformer, the energy activation of 111 kJ/mol was used in
calculation [6,34,35].
As a result, the kinetic energy of the molecules increases, making the effect to the activation energy
Table
of 5 shows
a reaction. thethermal
The average number
energy of chain
increased duescissions of each
to the kinetic paper
energy ofsample. The average
the molecules making number
the
of chain scissions
degradation of theatpaper
process sample of
a temperature increases with than
150 °C higher an increasing agingoftemperature
at a temperature 120 °C. at the same
aging time. The probability of molecules colliding with each other increases with aging temperature.
Table 5. Average number of chain scissions of the paper samples.
As a result, the kinetic energy of the molecules increases, making the effect to the activation energy
of a reaction. The thermal energy increased dueAvg.
Sample to the kinetic
Chain energy
Scission (×1000)of the molecules making the
degradation process at a temperature of 150 C higher than at a temperature of 120 ◦ C.
MO ◦ 0
MO.T1.120 1244
MO.T2.120 2487
Table 5. Average number of chain scissions of the paper samples.
MO.T3.120 3731
MO.T1.150 13,839
Sample
MO.T2.150 27,678 (×1000)
Avg. Chain Scission
MO
MO.T3.150 041,517
MO.T1.120 1244
MO.T2.120 2487
Figure 9 shows the correlation between the intensity of the absorbance peaks of the functional
MO.T3.120 3731
groups at 3329 cm , 2922 cm MO.T1.150
−1 −1 , 2854 cm , and 1745 cm 13,839
−1 −1 and the average chain scissions of the paper
samples. The intensity of the peak absorbance of the functional
MO.T2.150 27,678 group within the transformer paper
MO.T3.150
that changes with aging correlates 41,517 during thermal aging. The intensity
with the aging mechanisms
of the O–H functional group correlates with the average chain scissions due to the breakage of the
Figure 9 shows the correlation between the intensity of the absorbance peaks of the functional
groups at 3329 cm−1 , 2922 cm−1 , 2854 cm−1 , and 1745 cm−1 and the average chain scissions of the paper
samples. The intensity of the peak absorbance of the functional group within the transformer paper
 Energies 2018, 11, 364 9 of 12

that changes with aging correlates with the aging mechanisms during thermal aging. The intensity
Energies 2018, 11, x FOR PEER REVIEW 9 of 12
of the O–H functional group correlates with the average chain scissions due to the breakage of the
hydrogen bonds of cellulose. The reduced intensity of the O–H functional group can be attributed to
hydrogen bonds of cellulose. The reduced intensity of the O–H functional group can be attributed to
the reduction of the molecular weight/degree of polymerization [7]. The average number of chain
the reduction of the molecular weight/degree of polymerization [7]. The average number of chain
scissions correlates with the molecular weight as shown in Equation (3) [7]:
scissions correlates with the molecular weight as shown in Equation (3) [7]:
11 11
Averagenumber
Average numberofofchain scission == DP −
chainscission − DP (3)
(3)
𝐷𝑃t𝑡 𝐷𝑃00
DP
DP representsthe
0 0represents theDP DPvalue
value ofof new
new transformer paper and and DP DPtt represents
representsthetheDPDPvalue
valueofof
transformerpaper
transformer paperafter
after thermal
thermal aging.
aging. From
From these
these figures,
figures, it it can be seen seen that
that there
there isisaalinear
linear
correlation between the intensity of the peak absorbance of the O–H functional group
correlation between the intensity of the peak absorbance of the O–H functional group and the average and the average
numberofofchain
number chainscissions.
scissions.Those
Thosefigures
figuresalso
alsoshow
showthat
thatthere
thereisisa acorrelation
correlationbetween
betweenthetheintensity
intensityof
the peak absorbance of the C–H and the C=O functional groups and the average numberofofchain
of the peak absorbance of the C–H and the C=O functional groups and the average number chain
scissions.ItItindicates
scissions. indicatesthat
thatthe
thereaction
reactionof of the
the carboxylic
carboxylic acids
acids inin the
the mineral
mineral oiloilwith
withthethehydroxyl
hydroxyl
groupson
groups onthe
thecellulose
celluloseoccurred
occurred atat the
the same
same time
time as
as the
the process
processof ofchain
chainscission
scissionon
onthe
thecellulose.
cellulose.

(a)

(b)

Figure
Figure9.9.Intensity
Intensityofofthe
theabsorbance
absorbancepeaks
peaks of
of the
the functional groups as
functional groups asaafunction
functionofofthe
theaverage
averagechain
chain
scissions of paper samples at aging temperatures of (a) 120 ◦°C (b)
scissions of paper samples at aging temperatures of (a) 120 C (b) 150 C. 150 ◦°C.

Table 6 shows the value of R2 from the correlation between the functional group and the average
number of chain scissions of transformer paper. R2 is the coefficient of determination, which has a
range of 0–1 and measures the closeness of the data to the regression line. A value of R2 of 1 means
that the correlation has a linear relationship. This result gives initial information that there is a
correlation between the structural changes of transformer paper during thermal aging with the
Energies 2018, 11, 364 10 of 12

Table 6 shows the value of R2 from the correlation between the functional group and the average
number of chain scissions of transformer paper. R2 is the coefficient of determination, which has a range
of 0–1 and measures the closeness of the data to the regression line. A value of R2 of 1 means that
the correlation has a linear relationship. This result gives initial information that there is a correlation
between the structural changes of transformer paper during thermal aging with the average number
of chain scissions.

Table 6. The value of R2 from the correlation between the average number of chain scissions and the
functional groups of the transformer paper.

Sample Testing Method Parameter R2

120 Intensity of absorbance peak of O–H 0.949
FTIR (3329 cm−1 ) functional group
150 0.9993
120 Intensity of absorbance peak of C–H 0.9889
FTIR (2922 cm−1 ) functional group
150 0.9804
120 Intensity of absorbance peak of C–H 0.9937
FTIR (2854 cm−1 ) functional group
150 0.9793
120 Intensity of absorbance peak of C=O 0.9968
FTIR (1745 cm−1 ) functional group
150 0.9115

4. Conclusions
Accelerated thermal aging experiments on transformer paper in mineral oil was conducted under
aging temperatures of 120 ◦ C and 150 ◦ C with durations of up to 1008 h. Visually the paper samples
became darker as time elapsed, which indicates the structural changes of the cellulose paper after
thermal aging. The chemical structure of transformer paper in mineral oil was identified using Fourier
transform infrared (FTIR) spectroscopy analysis. FTIR spectra of new cellulose paper show absorbance
peaks located close to 3329 cm−1 that represents an O–H functional group, located close to 2922 and
2854 cm−1 that represent a C–H functional group, and located close to 1050 cm−1 that represents
a C–O functional group. These functional groups are consistent with the basic structure of cellulose.
The intensity of the peak absorbance at 3329 cm−1 , which is a typical characteristic of cellulose, decreased
with aging due to oxidation processes. The intensity of the absorbance peaks located close to 2922 cm−1
and 2854 cm−1 , which represent a C–H functional group, increased with aging due to the adsorption
process of mineral oil to the paper surface during aging. The reaction between the carboxylic acids in the
mineral oil with hydroxyl groups on the cellulose paper was the cause of the increased C–H functional
group of the cellulose paper after moving a hydrocarbon group (-R) in mineral oil to the cellulose paper.
The intensity of this absorbance peak at 1745 cm−1 increased with aging, which represents a C=O
functional group. This peak emerged on the cellulose paper after thermal aging in mineral oil. There
was no absorbance peak at this functional group region for new transformer paper. The emergence of
the C=O functional group was due to the interaction between the low molecular weight acids dissolved
in mineral oil and the cellulose. Carboxylate of the carboxylic acid (RCOO-) in mineral oil binds to
cellulose, which creates the emergence of the C=O functional group on the cellulose paper surface.
The intensity of the peak absorbances of the functional groups within the transformer paper that change
with aging correlates with the aging mechanisms during thermal aging. The value of R2 > 0.9 from the
correlation between functional groups and the average number of chain scissions of transformer paper
gives direct evidence that transformer paper performance, which has a direct correlation with the life of
transformers, can be investigated by using spectroscopy techniques.

Acknowledgments: This research was carried out with financial support from 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.
Energies 2018, 11, 364 11 of 12

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