2068 S. S. Kumar et al.

: Effect of Antioxidants on Critical Properties of Natural Esters for Liquid Insulations

Effect of Antioxidants on Critical

Properties of Natural Esters for Liquid Insulations
S. Senthil Kumar, M. Willjuice Iruthayarajan, M. Bakrutheen
Department of Electrical and Electronics Engineering, National Engineering College,
Kovilpatti, Tamilnadu, India.

S. Gowthama Kannan
G.E.T. Power Limited,
Chennai, Tamilnadu, India

ABSTRACT
This work is focused towards identifying alternate insulating medium for replacing the
mineral oil. With this aim, investigations are carried out with natural esters based
vegetable oils which are considered as environmental friendly and biodegradable
products. This work also extends to analyze the properties of vegetable oils with the
antioxidants for enhanced insulating medium of transformer applications. The natural
esters based vegetable oils such as honge oil, neem oil, mustard oil, punna oil and castor
oil are considered as samples for the investigations. The butylated hydroxy toluene,
butyalted hydroxy anisole and gallic acid are picked as the investigating antioxidants.
Different particle volume fraction ranges from 0% to 1% of antioxidants are included
for studying the performance of natural esters. The performances of natural esters
without and with antioxidants are examined according to the international standards.
From the investigation results, it is found that the natural esters based vegetable oils
without and with antioxidants have the potential to replace the mineral oil as the
insulating medium in the transformers. The mathematical functions for properties are
developed based on the results obtained for various concentration of antioxidant. These
functions are used to estimate the intermediate values of properties for different
antioxidant concentrations.
Index Terms - Dielectric breakdown, oil insulation, transformers, natural esters,
antioxidants.

1 INTRODUCTION Petroleum product based mineral oil is used as the liquid

insulation for more than a century. The traditional mineral oil
IN every field of power system network, transformers are
is used as insulating medium for their superior nature in their
the crucial equipment in determining the continuity of power
properties such as high dielectric strength, medium viscosity,
supply [1, 2]. The important component of transformers is the
good heat transfer capacity etc. [4]. Even though it has better
insulating medium used inside it which decides the life time of
characteristics, there are lots of issues with the mineral oil
the transformer [3]. Major functions of insulating medium in
such as poor biodegradation, scarcity of availability in future
transformers are providing the electrical isolation between
etc. [6-16]. Silicone based oil is also used in some special
different electrical parts, mechanical support and cooling [4].
applications in transformers. But their flammability and
The solid insulations (such as press board, kraft paper and
physical properties are totally different from the mineral oil.
etc.) and liquid insulation (oil) are majorly used as insulating
Their cost is also much higher than the mineral oil [16].
medium. The primary functions of liquid insulation medium
Disposal of mineral oil is also a major problem because it
are electrical insulation between the coils and winding as well
pollutes the environment [14, 15].
as removal of heat produced inside the transformer [5].
By considering the above facts, there is a need of
Petroleum products dominate the entire world’s critical
development of superior insulations for the high voltage
power sectors applications. The petroleum based mineral oil is
applications [17]. Natural esters are the major concern for the
used for the purpose of insulation as well as a cooling medium
future among the researchers in various aspects. The
in the transformers of power system networks [2, 5].
biodegradability and availability of natural esters are much
Manuscript received on 25 February 2015, in final form 7 April 2016, higher than the traditional mineral oil. The natural esters are
accepted 7 April 2016. also considered for the future with the aspects of slower

DOI: 10.1109/TDEI.2016.005243
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No. 4; August 2016 2069

ageing rate, less operating cost and recyclability [7, 16, 17]. The oils are chemically stable when the oils have high content
Environtemp®, FR3TM, BIOTEMP® and Biovolt are some of saturated fatty acids, but they have higher viscosity. The
of the commercial vegetable oil based insulation products poly unsaturated fatty acids show the low viscosity value and
available in the market [18-20]. unstable chemical nature in the oils [38]. The investigated
Oxidation stability is one of the important property in base oils (vegetable oils) along with their percentage of fatty
determining the life time and quality of oil [21-24]. acids are given in Table 1. All the natural esters in the refined
Antioxidants are used as free radical reducing agents in many form along with fatty acids data were bought from the local
research works. Oxidative stability of oil is improved with the manufacturers.
addition of antioxidants [25-37]. Among the different
Table 1. Investigating Base Oil Samples.
antioxidants, synthetic antioxidants and synergists showed the
Vegetable Percentage of fatty acids compositions (%)
better oxidative stability after the addition of insulating oils Samples
oils Mono Poly
[34, 35, 37]. The oil properties are also changed after the Saturated
unsaturated unsaturated
addition of antioxidants in oil samples. In order to develop Base Sample 1 Honge Oil
alternate eco friendly insulating medium with superior 21.4 62.1 16.5
(BS1) (HO)
properties such as high breakdown voltage, flash point, fire Base Sample 2 Neem Oil
40 20.9 39.1
point and viscosity of natural esters are required. The natural (BS2) (NO)
Base Sample 3 Mustard
and synthetic antioxidants are used to develop the (BS3) Oil (MO)
12.9 64.5 22.6
environmental friendly liquid insulation [29]. Base Sample 4 Punna Oil
39 58.9 2.1
(BS4) (PO)
Various properties of oil determine the ability of oil as good Base Sample 5 Castor Oil
insulating liquids. The properties such as breakdown voltage, 1.1 97.8 1.1
(BS5) (CO)
loss factor, dielectric dissipation factor, interfacial tension,
acidity, volume resistivity, flash point, fire point, viscosity etc. 2.2 ANTIOXIDANTS
are investigated for checking the suitability of oil samples as
liquid insulation. Among this, the breakdown voltage, flash Oxidation processes are delayed or slowed down by using
point, fire point and viscosity are considered as critical the components of antioxidants. Antioxidants are used to
properties for selecting insulating liquid in primary avoid oxidation and peroxide formation by reducing the free
investigation [4, 29, 41]. radical quantity present in the oil. They are acting as a free
radical scavengers and have the higher performance to
For achieving the green liquid insulation medium with good improve oxidation stability of the oil [37]. Antioxidants
dielectric nature, good heat transfer properties, good oxidative influence in reduction of free alkyl radicals and act as
stability, high safety nature, non-toxic nature etc., the natural hydrogen donor which leads towards elimination of the
esters based vegetable oils are carefully selected based on the diffusion of free radical chain. Antioxidants reacts with alkyl
availability and biodegradability. The antioxidants additives radical (R·), alkoxy radical (RO·), peroxy radical (ROO·) of
are included with natural esters for analyzing changes in the fatty acid and produces the fatty acid RH, ROH, ROOH and
properties of oil. In this paper, the mineral oil and natural antioxidant radical (A·). This is given in below reaction
esters with additives such as butylated hydroxy toluene equations 1-3.
(BHT), butyalted hydroxy anisole (BHA) and gallic acid (GA)
are investigated. Also an effort is made to develop the R· + AH → RH+A (1)
mathematical functions (nonlinear polynomial regressions) for RO· + AH → ROH+ A· (2)
critical properties of vegetable oils with antioxidants which
are investigated in this work. ROO· + AH → ROOH+ A· (3)
In this paper, section 2 gives the short notes on the natural The antioxidant radical’s reaction with alkyl radical, alkoxy
esters and antioxidants. The section 3 elaborates the radical and peroxy radical gives a non-radical product such as
methodology of this work. Experimental procedures are RA, ROA and ROOA. This is explained as below reaction
explained in the section 4. The discussions on the equations 4-6. In the progression towards neutralizing the free
experimental results are provided in section 5. The developed radicals of fatty acids, the antioxidants turn into oxidized
mathematical modeling of properties for various antioxidant antioxidants (Given in equation 7).
concentrations are discussed in section 6. The section 7
concludes with the finding of this paper. R· + A· → RA (4)
RO· +A· → ROA (5)
2 MATERIALS
ROO· + A· → ROOA (6)
2.1 NATURAL ESTER BASED VEGETABLE OILS
Antioxidant+O2 → Oxidized Antioxidant (7)
Natural esters (Vegetable oils) are the derivatives from the
naturally available plants and seeds of the plants. Natural Butylated Hydroxy Anisole (BHA), Butylated Hydroxy
esters have the triglyceride fatty acids which are classified as Toluene (BHT) and Gallic Acids (GA) are regularly used
the saturated, mono unsaturated and poly unsaturated. The antioxidants which donate hydrogen to the free radicals and
characteristics of natural esters mainly depends on the fatty form as a compound between a lipid radical and the
acids compositions [29]. The vegetable oils have the ability of antioxidant radical [34, 36-37]. The Antioxidants are
better biodegradable in nature and environmental eco friendly. categorized as natural antioxidants, synthetic antioxidants and
2070 S. S. Kumar et al.: Effect of Antioxidants on Critical Properties of Natural Esters for Liquid Insulations

synergists [29]. The selected antioxidants, their nature, Breakdown voltage is one of the important properties which
chemical formula and density are given in the Table 2. determine the ability of insulating medium to withstand the
high voltage stresses. The breakdown voltage of any insulating
Table 2. Investigating Antioxidants. medium depends on the purity of oil and free from
Nature of the Chemical Density
Melting contaminants [39-41]. International standard of Internal
Antioxidants Temperature Electrotechnical Commission IEC 60156 explains the
Antioxidants Formula (g/cm3)
(OC)
Butylated procedure for measurement of breakdown voltage [42].
Synthetic According to this standard, the measurements are made for
Hydroxy Toluene C15H24O 1.05 265
Product
(BHT) determining the breakdown voltage of oil samples. The
Butylated standard oil test kit with two 2.5mm gapped spherical
Synthetic
Hydroxy Anisole C11H16O2 1.06 264
(BHA)
Product electrodes is used to measure the breakdown voltage under the
Natural room temperature and pressure. The voltage varies at the rate
Gallic Acid (GA) C7H6O5 1.70 260
Product of 2kV/s while measuring the breakdown voltage. The five set
of readings are taken with the equal time space between each
3 METHODOLOGY measurement. The breakdown voltage of oil sample is the
mean of those five readings.
For identifying the alternate insulating medium for
Flash point and fire point temperatures are used to indicate
replacing the mineral oil, the different vegetable oils in Table
the temperature ranges upto which the oil can’t produce the
1 are considered as investigating samples. Their properties are
flammable vapour or fire [39-41]. The lowest temperature at
analyzed without and with the addition of the selected
which oil starts to produce ignitable vapour mixture in the air
antioxidants in Table 2. The quantity of antioxidants required
is called as flash point. The fire point is the temperature at
for the investigations are determined by the particle volume
which the oil gets fire in the air when the ignition source is
fraction, density of antioxidants and volume of oil samples.
introduced. These temperatures are measured according to the
Different particle volume fractions considered in this work are
standard specified by the American Society for Testing and
0.25, 0.5, 0.75 and 1%. 500ml of oil is used for preparation of
Materials ASTM D93 [43]. Pensky Martins closed cup
all oil samples. Investigations are made with the measurement
apparatus was used for measurement of flash and fire point
of breakdown voltage, flash point, fire point and viscosity of
temperature. By introducing test flame in the test setup, the
all oil samples prepared without and with antioxidants. For the
flash point and fire point temperature are measured.
purpose of comparison, the traditional mineral oil is also
investigated as reference oil sample. Viscosity is the measure of oil flow resistance. The
viscosity also indirectly constitutes the cooling of oil inside
4 EXPERIMENTAL PROCEDURE transformer [39-41]. Based on the American Society for
Testing and Materials standards ASTM D445 and ASTM
Base oils samples are natural ester based vegetable oils and D3828, the measurement of viscosity is carried out with the
the reference oil is petroleum based mineral oil which is used help of Redwood Viscometer [44, 45]. The time taken for the
as insulating liquid in the transformers. The properties of flow of 50ml of oil through the orifice is noted for calculating
natural esters are compared with the reference oil for the oil viscosity.
investigating the suitability of natural esters as potential
replacement to transformer oil. For every oil samples 500 ml
quantity is taken for investigations purpose. All the oil
5 RESULTS AND DISCUSSIONS
samples are exposed to heat up to 100 OC for half an hour to Experimental results of properties for natural esters based
bring back to normal room temperature for minimizing the vegetable oils without and with antioxidants are discussed in
effect of moisture in measurement of oil properties this section.
For analyzing the performance of natural esters with 5.1 PROPERTIES OF REFERENCE AND BASE OIL
antioxidants, the base oil samples are mixed with the SAMPLES
antioxidants at different particle volume fractions. The Samples (reference oil and base oil) are prepared without the
required quantity of antioxidants corresponding to the particle addition of antioxidants and their properties are measured as
volume fractions are added with base oil samples. For per the specified standards. Their properties are tabulated in
complete dispersion of antioxidants in the 500ml oil sample, the Table 3.
the antioxidants are heated upto its melting point temperature
and then melted antioxidants are mixed with oil sample by Table 3. Properties of Reference and Base Oils.
using the ultra sonicator. The mixing process is carried out for
10-15 minutes with constant speed and constant temperature. Flash Fire
Breakdown Viscosity
Oil Samples point Point
Characteristics of liquid insulations are analyzed by Voltage (kV) (cSt)
(OC) (OC)
measuring the electrical, physical and chemical properties [4, Mineral Oil (TO) 28.4 175 190 27.04
39-41]. The properties such as breakdown voltage, flash point Honge Oil (HO) 42.8 298 310 116.62
temperature, fire point temperature and viscosity are measured Neem Oil (NO) 43 288 297 108.79
as the investigating parameters in this work. All the Mustard Oil (MO) 41.6 289 300 95.74
measurements are carried out at the room temperature and Punna Oil (PO) 42.3 280 305 129.66
pressure (RTP). Castor Oil (CO) 31 280 290 155.71
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No. 4; August 2016 2071

From analyzing reference and base oil samples, the

following points are inferred.
 All base oil samples (natural esters) have high value
of breakdown voltage, flash point, fire point and
viscosity than reference oil (mineral oil).
 Only problem with the base oil samples is high value
of viscosity. Insulating oil should have medium value
of viscosity. High value of viscosity is due to higher
fatty acid composition of natural esters.
 Generally viscosity has decreasing nature as
temperature increases. The natural esters are also
having the same tendency.
 Among the investigated base oil samples, castor oil
has lower relative merits than other natural esters.
This may be due to presence of more mono
unsaturated fatty acids in castor oil.

5.2 BREAKDOWN VOLTAGE

Breakdown voltage of natural esters with the different
antioxidants and different particle volume fractions are given
in the Table 4. The effect of particle volume fraction on
breakdown voltage of natural esters added with BHT, BHA
and GA antioxidants are shown in Figure 1.
From the experimental results of breakdown voltage of
natural esters with antioxidants, it is revealed that
 All natural esters with antioxidants have the higher
breakdown voltage than the traditional mineral oil
(reference oil).
 Breakdown voltages of most of the natural esters
with antioxidants show the improved results than that Figure 1. Breakdown voltage variations of natural esters for different particle
volume fractions of antioxidants
of natural esters without antioxidants. (a) For BHT, (b) For BHA and (c) For GA
 As the particle volume fraction increases, the
breakdown voltage of antioxidants added natural
esters has shown the reduction in their values. This  Changes in the breakdown voltage after the addition
may be due to the fact of more percentage of of antioxidants may be due to the reaction with fatty
antioxidants mixed with vegetable oil leads to more acid component.
presence of suspended particles.  Also the removal of free radical particles from oil
may be the reason for the changes in the breakdown
Table 4. Breakdown Voltage of Natural Esters with Antioxidants. voltage of natural esters.
Particle
Breakdown Voltage (kV)  Oil samples treated with antioxidants have less
volume For For For For For tendency of formation of carbon and regain their
Antioxidants Base Base Base Base Base
fraction
Sample Sample Sample Sample Sample
dielectric properties in short duration after
(%) breakdown.
1 2 3 4 5
0 42.8 43 41.6 42.3 31  Natural esters treated with the antioxidants would be
0.25 43 43 39 41 41
suitable choice to higher rating applications (where
BHT 0.5 45 46 48.8 44 43
high dielectric strength requires) in high voltage
0.75 46 49.5 38 48 45
fields.
1 38 45 34 45 42
0 42.8 43 41.6 42.3 31
0.25 44 43 46.4 49 39 5.3 FLASH POINT AND FIRE POINT
BHA 0.5 46 45 52 51 46 Flash point and fire point of insulating medium determine
0.75 42 47 54 45 48
1 39 38 49 42 37 the temperature withstand capability. The measured flash
0 42.8 43 41.6 42.3 31 point and fire point temperature are tabulated in the Table 5
0.25 47 44 52 43 47 and Table 6 respectively. The variations in flash point and
GA 0.5 48 48 45 51 51 fire point of natural esters for various particle volume
0.75 39 40 41 38 40 fractions of antioxidants are shown in the Fig. 2 and Fig. 3
1 35 36 37 34 37 respectively.
2072 S. S. Kumar et al.: Effect of Antioxidants on Critical Properties of Natural Esters for Liquid Insulations
Table 5. Flash Point of Natural Esters with Antioxidants.  Enhancement in the temperatures of oil samples after
Particle
Flash Point (OC) the addition of antioxidants may be due the nature of
volume For For For For For antioxidants which protect the oil from the
Antioxidants Base Base Base Base Base
fraction consequence of heating by countering the free
(%) Sample Sample Sample Sample Sample
1 2 3 4 5 radicals and peroxides formations.
0 298 288 289 280 280
0.25 299 299 299 288 288
BHT 0.5 302 306 310 296 290
0.75 308 308 296 314 298
1 278 298 288 308 290
0 298 288 289 280 280
0.25 298 288 306 312 289
BHA 0.5 306 298 312 316 292
0.75 292 305 310 299 298
1 293 280 306 296 294
0 298 288 289 280 280
0.25 299 300 312 296 304
GA 0.5 305 312 308 298 318
0.75 284 291 300 292 296
1 275 280 290 283 287

Table 6. Fire Point of Natural Esters with Antioxidants

Fire Point (OC)
Particle
volume For For For For For
Antioxidants Base Base Base Base Base
fraction
(%) Sample Sample Sample Sample Sample
1 2 3 4 5
0 310 297 300 305 290
0.25 312 318 312 307 298
BHT 0.5 320 320 330 310 302
0.75 328 338 308 330 318
1 292 318 299 328 301
0 310 297 300 305 290
0.25 328 320 327 335 301
BHA 0.5 320 315 330 342 303
0.75 310 325 330 304 312
1 310 298 325 318 306
0 310 297 300 305 290 Figure 2. Flash point temperature variations of natural esters for different
0.25 330 316 333 314 320 particle volume fractions of antioxidants
GA 0.5 325 325 320 318 332 (a) For BHT, (b) For BHA and (c) For GA
0.75 301 303 310 304 312
1 290 296 302 294 301
5.4 VISCOSITY
Viscosity of oil insulating medium shows the flow nature of
Flash point and fire point measurement provides the the oil. It indirectly constitutes the heat transfer ability of oil.
following results for the investigations of natural esters with The experimental result of viscosity is provided in the Table 7.
the addition of antioxidants. The variations in viscosity of natural ester oil samples with
 Most of the results show the increment in the flash different particle volume fractions of antioxidants are
point and fire point temperatures of natural esters illustrated in Fig. 4.
after the addition of antioxidants. Viscosity profile of natural esters after the addition of
 All the antioxidants show the low percentage of antioxidants provides the following information,
enhancement in flash point and fire point temperature  Viscosity of most of the oil samples has increased
at the higher particle volume fractions. after the inclusion of antioxidants. But the values are
 Flash and fire point temperatures will be improved by in the optimal range.
the addition of less amount of antioxidants which  This increment may be due the effect of inclusion of
indicates that the antioxidants enhance the thermal antioxidants which may offer more resistance flow of
stability of oil samples. oil.
 For the addition of higher concentration of  There is more possibility of increment in viscosity at
antioxidants in the base oil samples, the temperature elevated temperature due to the formations of sledges
stability has decreased. This is due to formation of and peroxides in the oil samples. But the addition of
higher ignition combination and leads to decrease in antioxidants reduces the effect of sledges and
thermal characteristics. peroxides.
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No. 4; August 2016 2073

different particle volume fractions are given in the Table 8-11.

The distributions of enhancement/decrement in the properties
are pictorially given in Figure 5–8 for breakdown voltage,
flash point, fire point and viscosity respectively.

Figure 3. Fire point temperature variations of natural esters for different

particle volume fractions of antioxidants
(a) For BHT, (b) For BHA and (c) For GA

Table 7. Viscosity of Natural Esters with Antioxidants.

Viscosity (cSt)
Particle
For For For For For
volume
Antioxidants Base Base Base Base Base
fraction
Sample Sample Sample Sample Sample
(%)
1 2 3 4 5
0 116.62 108.79 95.74 129.66 155.71 Figure 4. Viscosity variations of natural esters for different particle volume
0.25 114.01 145.81 103.57 103.57 210.39 fractions of antioxidants
BHT 0.5 108.79 147.90 114.01 105.66 202.58 (a) For BHT, (b) For BHA and (c) For GA
0.75 114.01 129.66 104.88 108.27 205.18
1 99.65 127.57 116.62 108.36 184.36
0 116.62 108.79 95.74 129.66 155.71
0.25 114.01 85.28 85.28 116.62 218.20
BHA 0.5 108.79 93.12 103.57 124.44 202.58 Table 8. Average Enhancement of Breakdown Voltage for Different Particle
0.75 124.44 103.57 106.70 126.53 206.74 Volume Fractions of Antioxidants.
1 106.18 124.44 98.35 87.89 218.20
Particle Enhancement Percentage in Breakdown Voltage
0 116.62 108.79 95.74 129.66 155.71
volume (%)
0.25 124.44 109.65 98.35 114.01 210.39 Antioxidants
fraction
GA 0.5 121.83 110.88 101.48 110.88 207.79 (%) For For For For For
0.75 122.36 110.36 103.05 114.01 210.91 BS1 BS2 BS3 BS4 BS5
1 124.44 112.70 105.14 116.10 212.47 0.25 0.47 0.00 -6.25 -3.07 32.26
0.5 5.14 6.98 17.31 4.02 38.71
BHT
0.75 7.48 15.12 -8.65 13.48 45.16
1 -11.21 4.65 -18.27 6.38 35.48
5.5 ANALYSIS OF ENHANCEMENT IN PROPERTIES 0.25 2.80 0.00 11.54 15.84 25.81
WITH ANTIOXIDANTS 0.5 7.48 4.65 25.00 20.57 48.39
BHA
0.75 -1.87 9.30 29.81 6.38 54.84
In this part, the enhancements in the properties of base oil 1 -8.88 -11.63 17.79 -0.71 19.35
samples (natural esters) with antioxidants are discussed. Most 0.25 9.81 2.33 25.00 1.65 51.61
of the properties of natural esters are changed with the 0.5 12.15 11.63 8.17 20.57 64.52
GA
addition of antioxidants. The enhancement percentage in the 0.75 -8.88 -6.98 -1.44 -10.17 29.03
properties of natural esters with investigated antioxidants for 1 -18.22 -16.28 -11.06 -19.62 19.35
2074 S. S. Kumar et al.: Effect of Antioxidants on Critical Properties of Natural Esters for Liquid Insulations
Table 9. Average Enhancement of Flashpoint for Different Particle Volume
Fractions of Antioxidants
Enhancement Percentage in Flash Point
Particle (%)
Antioxidants volume
fraction (%) For For For For For
BS1 BS2 BS3 BS4 BS5
0.25 0.34 3.82 3.46 2.86 2.86
0.5 1.34 6.25 7.27 5.71 3.57
BHT
0.75 3.36 6.94 2.42 12.14 6.43
1 -6.71 3.47 -0.35 10.00 3.57
0.25 0.00 0.00 5.88 11.43 3.21
0.5 2.68 3.47 7.96 12.86 4.29
BHA
0.75 -2.01 5.90 7.27 6.79 6.43
1 -1.68 -2.78 5.88 5.71 5.00
0.25 0.34 4.17 7.96 5.71 8.57
0.5 2.35 8.33 6.57 6.43 13.57
GA
0.75 -4.70 1.04 3.81 4.29 5.71
1 -7.72 -2.78 0.35 1.07 2.50

Table 10. Average Enhancement of Fire Point for Different Particle Volume
Fractions of Antioxidants.

Particle Enhancement Percentage in Fire Point(%)

Antioxidants volume
fraction (%) For For For For For
BS1 BS2 BS3 BS4 BS5 Figure 5. Enhancement in Breakdown Voltage of natural esters for different
0.25 0.65 7.07 4.00 0.66 2.76 particle volume fractions of antioxidants
0.5 3.23 7.74 10.00 1.64 4.14 (a) For BHT, (b) For BHA and (c) For GA
BHT
0.75 5.81 13.80 2.67 8.20 9.66
1 -5.81 7.07 -0.33 7.54 3.79
0.25 5.81 7.74 9.00 9.84 3.79
0.5 3.23 6.06 10.00 12.13 4.48
BHA
0.75 0.00 9.43 10.00 -0.33 7.59
1 0.00 0.34 8.33 4.26 5.52
0.25 6.45 6.40 11.00 2.95 10.34
0.5 4.84 9.43 6.67 4.26 14.48
GA
0.75 -2.90 2.02 3.33 -0.33 7.59
1 -6.45 -0.34 0.67 -3.61 3.79

Table 11. Average Decrement of Viscosity for Different Particle Volume

Fractions of Antioxidants.
Particle Decrement Percentage in Viscosity (%)
volume
Antioxidants
fraction For For For For For
(%) BS1 BS2 BS3 BS4 BS5
0.25 -2.24 34.03 8.18 -20.12 35.12
0.5 -6.71 35.95 19.08 -18.51 30.10
BHT
0.75 -2.24 19.18 9.55 -16.50 31.77
1 -14.55 17.26 21.81 -16.43 18.40
0.25 -2.24 -21.61 -10.93 -10.06 40.13
0.5 -6.71 -14.40 8.18 -4.03 30.10
BHA
0.75 6.71 -4.80 11.45 -2.41 32.77
1 -8.95 14.39 2.73 -32.22 40.13 Figure 6. Enhancement in Flash Point of natural esters for different particle
0.25 6.71 0.79 2.73 -12.07 35.12 volume fractions of antioxidants. (a) For BHT, (b) For BHA and (c) For GA.
0.5 4.47 1.92 6.00 -14.48 33.45
GA
0.75 4.92 1.44 7.64 -12.07 35.45 From the enhancement analysis, the following points are
1 6.71 3.59 9.82 -10.46 36.45 inferred,
IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No. 4; August 2016 2075

 All the properties have shown nonlinear behavior  Viscosities of castor oil based samples have very high
with the additions of different particle volume increment than the base oil sample with all antioxidants.
fraction and antioxidants.  Based on average percentage of enhancement and
decrement, BHA has the better enhancement
percentage in the breakdown voltage, flash point, fire
point and the viscosity
 In general the variation in properties depends on the oil
sample and particle volume fraction of antioxidants.
 Most of the parameters have shown decreasing nature
for particle volume fraction 1% of antioxidants.
 Reason for enhancement in the properties may be the
nature of antioxidants such as prone to formation of
peroxides, cut the chain oxidation and eliminate the
effects of free radicals.
 Based on the requirement of properties for insulating
oil, the quantity (Particle volume fraction) of any
antioxidants and for any investigated oil samples can
be chosen for any particular applications from the
distribution diagram of enhancement/decrement in
properties (Figures 5-8).

6 MATHEMATICAL FUNCTIONS OF
PROPERTIES
For developing mathematical functions of properties,
regression analysis is used as one of the tool. Regression
analysis is the tool for determining the relations between the
variables. It is the statistical analysis procedure used to create
Figure 7. Enhancement in Fire Point of natural esters for different particle
the relations between the two variables. This method is used to
volume fractions of antioxidants. (a) For BHT, (b) For BHA and (c) For GA. find out the change of one variable with respect to the change
in another variable [40]. In regression analysis relations
between the two variables are measured in terms of linear
correlation coefficients (r) and coefficient of determination
(r2). Regression analysis is classified as linear and nonlinear
regression based on the technique to find the best fitting curve
for a set of data. For nonlinear regression, only coefficient of
determination exists. The value for coefficient of
determination has the values from 0 to 1. It measures accuracy
of curve fitting with set of data. For better curve fit, the
coefficient of determination has value nearer to 1 [46, 47].
In this work, the mathematical functions are developed from
the nonlinear regression curves. The mathematical model is
developed for all properties with respect to quantity of
antioxidants. In the regression analysis, the actual
measurement values of properties except breakdown voltage
are considered for the development of mathematical model.
For breakdown voltage related equations, the average value of
five set of measurement values for each samples are used due
to the specification as per the standard.
The functions are developed for each base oil samples with
all antioxidants. The properties (Breakdown voltage – V,
Flash point – FL, Fire point – FI and Viscosity – VI) and
particle volume particle volume fraction (x) of antioxidants
are taken as two variables.
Figure 8. Enhancement in Viscosity of natural esters for different particle
For developing functions, the properties for particle volume
volume fractions of antioxidants fractions of ranges 0%, 0.25%, 0.5%, 0.75% and 1% are given
(a) For BHT, (b) For BHA and (c) For GA as input to regression analysis tool. For each base samples and
2076 S. S. Kumar et al.: Effect of Antioxidants on Critical Properties of Natural Esters for Liquid Insulations

antioxidants, the mathematical functions for breakdown Table 12, 13, 14and 15 respectively. From these functions
voltage, flash point, fire point and viscosity are tabulated in intermediate values of proprieties can be calculated.

Table 12. Mathematical Functions for Breakdown Voltage.

Anti Coefficient of
Base samples Mathematical Functions
oxidants Determination (r2)
BS1 1 V = -0.216x + 1.7x - 3.883x2 + 3.2x + 42
4 3

BS2 1 V = -0.25x4 + 2.083x3 - 4.75x2 + 3.416x + 42.5

BHT BS3 1 V = 2.516x4 - 30.66x3 + 127.2x2 - 207.5x + 150
BS4 1 V = -0.195x4 + 1.408x3 - 1.404x2 - 4.008x + 46.5
BS5 1 V = -0.541x4 + 6.75x3 - 30.95x2 + 63.75x - 8
BS1 1 V = 0.575x4 - 6.883x3 + 27.32x2 - 41.21x + 63
BS2 1 V = -0.375x4 + 3.416x3 - 10.12x2 + 12.08x + 38
BHA BS3 1 V = 0.041x4 - 1.15x3 + 6.258x2 - 6.55x + 43
BS4 1 V = 0.595x4 - 6.508x3 + 21.80x2 - 22.09x + 48.5
BS5 1 V = -0.166x4 + 1x3 - 2.333x2 + 10.5x + 22
BS1 1 V = 0.908x4 - 10.21x3 + 36.99x2 - 48.88x + 64
BS2 1 V = 1.291x4 - 15.41x3 + 61.70x2 - 95.58x + 91
GA BS3 1 V = -0.975x4 + 13.15x3 - 63.22x2 + 122.6x - 30
BS4 1 V = 2.429x4 - 29.00x3 + 116.9x2 - 183.5x + 135.5
BS5 1 V = 1.083x4 - 11.33x3 + 34.91x2 - 25.66x + 32

Table 13. Mathematical Functions for Flash Point

Coefficient of
Antioxidants Base samples Mathematical Functions
Determination (r2)
BS1 1 FL = -1.666x4 + 16.83x3 - 58.33x2 + 83.16x + 258
BS2 1 FL = -0.25x4 + 2.333x3 - 9.75x2 + 27.66x + 268
BHT BS3 1 FL = 2.375x4 - 28.08x3 + 109.6x2 - 157.9x + 363
BS4 1 FL = -1.833x4 + 20x3 - 74.16x2 + 118x + 218
BS5 1 FL = -1.416x4 + 16.16x3 - 64.58x2 + 109.8x + 220
BS1 1 FL = 2.791x4 - 32.91x3 + 131.7x2 - 206.5x + 403
BS2 1 FL = -0.666x4 + 4.5x3 - 5.333x2 - 5.5x + 295
BHA BS3 1 FL = 0.125x4 - 0.75x3 - 4.125x2 + 32.75x + 261
BS4 1 FL = 1.166x4 - 10.5x3 + 19.83x2 + 28.5x + 241
BS5 1 FL = -0.916x4 + 10.66x3 - 44.08x2 + 80.33x + 234
BS1 1 FL = 2.958x4 - 34.91x3 + 138.0x2 - 213.0x + 405
BS2 1 FL = 3.166x4 - 37.16x3 + 143.8x2 - 206.8x + 385
GA BS3 1 FL = -0.875x4 + 12.58x3 - 67.12x2 + 149.4x + 195
BS4 1 FL = -0.041x4 + 1.416x3 - 14.45x2 + 50.08x + 243
BS5 1 FL = 3.125x4 - 35.58x3 + 130.3x2 - 164.9x + 347

Table 14. Mathematical Functions for Fire Point

Coefficient of
Antioxidants Base samples Mathematical Functions
Determination (r2)
BS1 1 FI = -1.583x + 14.83x - 46.41x2 + 61.16x + 282
4 3

BS2 1 FI = -3.708x4 + 42.91x3 - 174.2x2 + 299.0x + 133

BHT BS3 1 FI = 4.125x4 - 48.91x3 + 193.3x2 - 287.5x + 439
BS4 1 FI = -2.291x4 + 25.58x3 - 95.70x2 + 144.4x + 233
BS5 1 FI = -2.541x4 + 28.08x3 - 106.9x2 + 170.4x + 201
BS1 1 FI = -0.5x4 + 9x3 - 54.5x2 + 126x + 230
BS2 1 FI = -3.958x4 + 46.75x3 - 195.5x2 + 341.7x + 108
BHA BS3 1 FI = -0.958x4 + 13.08x3 - 66.54x2 + 149.4x + 205
BS4 1 FI = 4.958x4 - 53.25x3 + 184.0x2 - 223.7x + 393
BS5 1 FI = -1.583x4 + 18.5x3 - 75.91x2 + 133x + 216
BS1 1 FI = 1.083x4 - 9.833x3 + 19.41x2 + 14.33x + 285
BS2 1 FI = 2.791x4 - 31.41x3 + 113.7x2 - 144.0x + 356
GA BS3 1 FI = -2.083x4 + 29x3 - 144.9x2 + 296x + 122
BS4 1 FI = 1.458x4 - 16.75x3 + 61.54x2 - 80.25x + 339
BS5 1 FI = 2.291x4 - 25.25x3 + 85.20x2 - 83.25x + 311
 IEEE Transactions on Dielectrics and Electrical Insulation Vol. 23, No. 4; August 2016 2077
Table 15. Mathematical Functions for Viscosity
Coefficient of
Antioxidants Base samples Mathematical Functions
Determination (r2)
BS1 1 VI = -1.794x4 + 20.12x3 - 77.16x2 + 114.9x + 60.5
BS2 1 VI = 0.911x4 - 6.683x3 - 0.156x2 + 70.59x + 44.12
BHT BS3 1 VI = 2.609x4 - 29.78x3 + 114.8x2 - 167.2x + 175.3
BS4 1 VI = 1.025x4 - 14.86x3 + 77.65x2 - 170.3x + 236.2
BS5 1 VI = -4.447x4 + 56.62x3 - 259.7x2 + 504.4x - 141.0
BS1 1 VI = -3.260x4 + 36.52x3 - 138.9x2 + 207.3x + 14.88
BS2 1 VI = 1.522x4 - 20.01x3 + 97.71x2 - 199.3x + 228.9
BHA BS3 1 VI = 1.982x4 - 27.14x3 + 127.6x2 - 233.2x + 226.4
BS4 1 VI = -0.350x4 - 0.927x3 + 24.75x2 - 75.55x + 181.7
BS5 1 VI = -4.598x4 + 62.30x3 - 297.9x2 + 589.0x - 193.1
BS1 1 VI = -0.631x4 + 8.578x3 - 40.89x2 + 79.92x + 69.64
BS2 1 VI = 0.280x4 - 3.157x3 + 12.12x2 - 17.60x + 117.1
GA BS3 1 VI = 0.173x4 - 2.08x3 + 8.406x2 - 10.65x + 99.89
BS4 1 VI = -0.043x4 - 0.61x3 + 11.00x2 - 43.74x + 163.0
BS5 1 VI = -2.928x4 + 39.78x3 - 194.1x2 + 402.5x - 89.53

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