Journal of Molecular Liquids 339 (2021) 116825

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Dielectric behavior of natural ester based mineral oil blend dispersed

with TiO2 and ZnO nanoparticles as insulating fluid for transformers
Zaid B. Siddique a, Soumen Basu b, Prasenjit Basak c,⇑
a
Electrical and Instrumentation Engineering Department, Thapar Institute of Engineering and Technology, Patiala, India
b
School of Chemistry and Biochemistry, Thapar Institute of Engineering and Technology, Patiala, India
c
Electrical and Instrumentation Engineering Department, Thapar Institute of Engineering and Technology, Patiala 147004, India

a r t i c l e i n f o a b s t r a c t

Article history: Mineral oil being the most extensively used oil in transformers still has some associated drawbacks like
Received 21 April 2021 non-biodegradability and low fire point. Bio-degradable, non-toxic and fire-resistant vegetable-based
Revised 28 May 2021 ester oils are considered as second-generation insulating fluids. These oils are continuously being tested
Accepted 24 June 2021
in order to replace the conventional mineral oil for insulation purposes. The dielectric properties of these
Available online 28 June 2021
vegetable oils are further improved by adding various types of nanomaterials. This paper focuses on
preparing a mixture of natural ester oil and mineral oil blend as a base fluid and studying the dielectric
Keywords:
behavior of this fluid after being dispersed with TiO2 and ZnO nanoparticles. Results indicated that dis-
Transformer insulation
Ester oil
persion of both nanomaterials resulted in an overall enhancement in the dielectric properties of nanoflu-
Nanofluids ids. The breakdown voltage of TiO2 dispersed nanofluid is reported to be about 30% greater than pure
Dielectric properties mineral oil, 24% greater than pure ester oil, and 17% greater than the oil-blend. Likewise, the breakdown
Weibull distribution voltage of ZnO dispersed nanofluid is observed to be around 28% greater than pure mineral oil, 19%
Breakdown voltage greater than pure ester oil, and 16% greater than the oil-blend. Moreover, in terms of cooling, TiO2 dis-
persed oil-blend shows better performance as a coolant. Thus, both types of nanofluids can be used as
insulating oils in the transformer depending upon the requirements expected to be met by the
transformers.
Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction of prime concern to work on the reliability of these existing units.

The available statistics have shown that the average service life of
The developments in electrical power systems have increased those transformers which fail as a result of some insulation prob-
the demands of performance and reliability of various power sys- lems is 17.8 years, almost half of the expected life of 35–40 years.
tem components. Transformer is, undoubtedly, the most important In case of high voltage transformers, around 75% of these trans-
component of any electrical power system; be it at the generation former collapses are reported because of their insulation related
level or at the transmission level. The consistent increase in the issues [1–3]. Thus, it is very much evident that the operational reli-
consumption of electrical power on industrial as well as domestic ability, as well as the lifetime of any transformer, depend mainly
scale has led to an increase in the ratings of transformers. Increas- on its insulting system [4,5]. Transformer oil is the major compo-
ing the rating of a transformer means to increase the load on a nent of transformer insulating system. So, it becomes of utmost
transformer. This directly leads to an increased electric stress along necessity to have a reliable insulating fluid for the smooth func-
with the increased thermal stress in the transformer windings as tioning of the transformer. The most extensively used dielectric
well as in its insulation structure. These factors altogether put insulating oil in any transformer is the mineral oil [6,7]. The reason
the transformer into a danger zone where it gets prone to threats behind such a wide usage of mineral oil in transformers is its good
of transformer failures. Any potential result of transformer failure dielectric and cooling properties [8–11]. However, due to its non-
can cause serious damage to the entire system. A large number biodegradability and fast rate of depletion of oil reserves, it
of transformers in operation around the globe are approaching becomes necessary to search for other alternative oils [7,12,13].
their design life and some of them are even beyond it; thus, it is In recent years, a lot of attention has been given to alternative insu-
lating oils such as natural ester oils [11,14,15]. These oils are gen-
erally vegetable oils that are extracted from the crop production
⇑ Corresponding author.
and refined accordingly [16]. Vegetable oils, also known as natural
E-mail address: [email protected] (P. Basak).

https://doi.org/10.1016/j.molliq.2021.116825
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

ester oils, are derived from bio-degradable sources and named 400 ml of ethanol and stirred for 30 min at 60 °C. In another bea-
after them like sunflower oil, rapeseed oil, coconut oil, palm oil, ker, 17 g of oxalic acid (C2H2O4) was dissolved in 250 ml ethanol
etc. The very first commercially produced vegetable insulating and the resulting solution was stirred for 30 min at 60 °C. Both
fluid was BIOTEMP, which was patented by ABB in the US in the solutions were mixed together and stirred further for 4 h at a
September 1999 [17]. The main component in this vegetable fluid temperature of 70 °C resulting in a thick white residue. The residue
was oleic oil. The BIOTEMP insulating fluids are being used in dis- was centrifuged to get the white zinc oxide precipitate. This white
tribution transformers in a few sensitive areas. In 1999, another precipitate was dried overnight in an oven at 40 °C to obtain dry
patent was issued to Waverly Light & Power in Iowa who devel- powdered ZnO nanoparticles. Commercial TiO2 was purchased as
oped a transformer fluid from soyabean oil [18]. In 2000, another TiO2 P25 from Evonik Industries AG, Germany.
type of vegetable-based transformer insulating fluid was devel-
oped by the Cooper Industries, Inc in Milwaukee. This insulating 2.2. Surface modification of nanomaterials
oil was developed under the trademark Envirotemp FR3 using var-
ious types of standard grade oleic oils [19]. Envirotemp FR3 started In order to avoid agglomeration as well as to increase dispersion
a revolution in the research of vegetable-based insulating oils. of nanomaterials in oil, these nanomaterials were surface modified
Various dielectric properties of natural ester fluids are compara- using oleic acid (C18H34O2). About 1 g of TiO2 powder was put into
ble to those of mineral oils [20]. Bio-degradability and fire resis- 20 ml of ethanol and the mixture was sonicated for 30 min to form
tance properties of vegetable ester oils are making these oils a a homogenous slurry. About 0.6 g of oleic acid (OA) was added into
preferred choice over the conventional transformer oil. The higher the solution and the resultant solution was heated at 60 °C for
permittivity of ester oils (3.1–3.2) as compared to the mineral oil 30 min under reflux conditions. Thereafter, the solution was cen-
makes it easier to match with the permittivity of solid insulation trifuged and the mixture was dried in an oven at 40 °C to obtain
used in the transformers to reduce the electric stress at higher load oleic acid modified TiO2 (OA-TiO2) powder. The same method
conditions. Vegetable-based ester oils have a comparatively lower was followed for ZnO nanomaterials to obtain oleic acid modified
coefficient of expansion and an overall improved insulation life of ZnO (OA-ZnO) powder.
5–8 times when compared with the mineral oil. But due to a higher
viscosity as compared to the mineral oil, some vegetable oils have
2.3. Fabrication of nanofluids
poor flow rate resulting in a poor thermal conduction [21]. In the
areas subjected to high temperatures, the ester oil filled transform-
First of all, six oil-blend (OB) samples were prepared with soy-
ers with high ratings need to be modified accordingly in order to
abean extracted natural ester oil (EO) as the primary oil and the
provide adequate cooling needed to keep the transformer in proper
conventional mineral oil (MO) as the secondary oil. The oil volume
working conditions. However, the dielectric properties of these
proportions in the OB samples in terms of MO:EO ratios were
vegetable oils can further be enhanced by dispersing suitable
100:0, 80:20, 60:40, 40:60, 20:80, and 0:100. Out of these six OB
nanomaterials. After the conceptual introduction of nanotechnol-
samples, the one with the optimum value of BDV corresponding
ogy in 1990s, these nanofluids have attained a phenomenal atten-
to the greater volume content of EO was selected as the final OB
tion due to the recent advancements in nanotechnology [22].
sample which would be used to make the nano-fluid (NF) samples
Researches have shown that dispersion of various nanomaterials
by mixing the synthesized nanomaterials in it. For both types of
like Fe3O4 [23], SiO2 [24], Al2O3 [25,26] in transformer insulating
nanomaterials, five NF samples were made by mixing the nanoma-
oil has resulted in the enhancement of the dielectric strength as
terials in five different concentrations, i.e. 0.001 g/L, 0.003 g/L,
well as the heat transfer capacity of the oil. The behavioral studies
0.005 g/L, 0.007 g/L and 0.009 g/L. The resultant NF samples were
of these nanofluids reported improved thermal as well as insulat-
named on the basis of the type and concentration of nanomaterials
ing properties [27]. This makes it possible to further increase the
dispersed in the oil blend. For TiO2 dispersed NF samples, the pre-
rating as well as the load handling capacity of the transformers
pared NF samples were named as TNF1, TNF3, TNF5, TNF7 and
which can be the prime reason to overall enhance the efficiency
TNF9 for the concentration of 0.001, 0.003, 0.005, 0.007 and
and reliability of any given electrical power system. However,
0.009 g/L, respectively. Similarly, for ZnO dispersed NF samples,
there is no adequate research available to show the comparative
NF samples were named as ZNF1, ZNF3, ZNF5, ZNF7 and ZNF9.
analysis of the dielectric behavior of a mixed mineral oil and ester
oil blend dispersed with conductive and semi-conductive
nanomaterials. 3. Results and discussions
For this research, a vegetable oil-based blend is used as the base
oil for the dispersion of the nanomaterials. The reason behind 3.1. Characterization of nanomaterials
choosing a mix-blend is to keep the dielectric as well as physio-
thermal properties of the insulating fluid at an optimum level. Vis- 3.1.1. XRD
cosity of vegetable oils is comparatively higher than mineral oil. The XRD pattern of OA-TiO2 and OA-ZnO nanoparticles are
Two types of nanomaterials are selected based on their electrical shown in Fig. 1a and 1b, respectively. In XRD pattern of OA-TiO2,
conductivity: TiO2, which is semi-conductive, and ZnO, which is a the diffraction peaks at 2h = 25.3° (1 0 1), 37.8° (0 0 4), 48° (2 0 0),
conductive nanomaterial. This research focuses on studying the 55.1° (2 1 1), 62.7° (2 0 4) and 69.1° (1 1 6) confirm the anatase
effects of these nanomaterials on natural ester oil-based blend structure of the TiO2 (JCPDS card no. 21-1272). The intensity of
and thereby making a comparative analysis of the modified prop- the XRD peaks also represents the crystalline nature of TiO2 sam-
erties of the insulating nanofluid. ple. In case of synthesized OA-ZnO nanoparticles, the diffraction
peaks at 2h = 30.5° (1 0 0), 33.5° (0 0 2), 35.5° (1 0 1), 47.5° (1 0 2),
52° (1 1 0), 62.5° (1 0 3) and 68° (1 1 2) indicate the hexagonal wurt-
2. Synthesis of materials zite structure of ZnO (JCPDS Card No. 36-1451).

2.1. Nanomaterials 3.1.2. FTIR

The presence of various functional groups in a synthesized com-
ZnO nanoparticles were synthesized by using sol-gel method. pound is found out using FTIR spectroscopy technique so that the
As a precursor, 14 g of zinc acetate (ZnC4H6O4) was taken in composition of the compound can be determined. FTIR spectra of
2
Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

(a) (b)

(101)

(100)
Intensity (a.u)

(002)
(200)
(004)

(211)
(105)

(204)

(102)
(101)

(110)
(116)

(112)
(103)
20 30 40 50 60 70 30 40 50 60 70
2θ (deg) 2θ (deg)
TiO2 -1 ZnO
OA
(c) (d) -1
1360 cm
OA
-1 1620 cm
OA-TiO2 3370 cm
OA-ZnO

Transmittance (%)
Transmittance (%)

-1
-1 1409 cm -1 -1 -1
-1
2918 cm
2847 cm
-1 -1 680 cm 2918 cm 2847 cm -1 830 cm
1709 cm 1709 cm

-1 -1
715 cm -1 1409 cm -1
1709 cm 715 cm

-1
-1 -1 1360 cm
-1 1621 cm 680 cm
3400 cm -1 -1 -1 830 cm-1
3370 cm 1620 cm 1709 cm

3500 3000 2500 2000 1500 1000 500 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1) Wavenumber (cm-1)

Fig. 1. (a) XRD pattern of OA-TiO2 nanoparticles, (b) XRD pattern of OA-ZnO nanoparticles, (c) comparative FTIR spectrum of TiO2 and OA-TiO2, and (d) comparative FTIR
spectrum of ZnO and OA-ZnO.

pure TiO2 and ZnO nanoparticles are shown in Fig. 1c and 1d surface area and the porosity of the three nanomaterials is shown
respectively. A broad peak between 3400 cm
1 and 3200 cm
1 is in Table 1.
due to the presence of absorbed water molecules and represents
the hydroxyl group (OH). The peak at 1620 cm
1 represents the
C=C stretching of the unoxidized graphite residue. The peak at
1727 cm
1 is due to the C=O stretches of carboxyl group and the
3.1.4. TGA
peak at 1170 cm
1 is due to C-O stretching in alcoholic group
Thermo-gravimetric analysis was done for OA-TiO2 and OA-ZnO
[19]. The peak at 1050 cm
1 represents C-O stretching vibrations
in order to study the decomposition behavior of synthesized nano-
of C-O-C group. In case of oleic acid, the band between
materials. Fig. 2c shows the TGA graph of the synthesized nanoma-
3012 cm
1 and 2500 cm
1 is due to the COOH bond. The peaks at
terials. Both the nanomaterials were found to be thermally stable
2918 cm
1 and 2847 cm
1 correspond to the angular deformation
within the temperature range of any working transformer, i.e.,
of C-O-H bond. For synthesized TiO2, the peak at 680 cm
1 is rep-
from 25 °C to 90 °C which correspond to the normal working con-
resenting the O–Ti–O bond. The peaks at 1621 cm
1 and
ditions and overload working conditions of any transformer,
3400 cm
1 are due to the surface absorbed water molecule as well
respectively. However, overall stability of OA-ZnO was compara-
as the presence of hydroxyl groups. The effect of surface modifica-
tively higher than that of OA-TiO2.
tion of TiO2 by OA can be seen as extra induced peaks in OA-TiO2
compared with the peaks in OA. For ZnO, a peak at 3370 cm
1 rep-
resents the stretching mode of hydroxyl group (OH). The peaks
seen at 1620 and 1360 cm
1 are due to the stretching of C=O and
C-O in zinc carboxylate respectively. This suggests the presence 3.1.5. FE-SEM
of impurities near ZnO surfaces. The peak at 1309 cm
1 is attribu- FE-SEM images of unmodified and modified TiO2 and ZnO
ted to the in-plane bending of primary and secondary alcohol. The nanoparticles are shown in Fig. 3. It can be seen that, before the
peak at 830 cm
1 represents the bending of C-O bond. surface modification, TiO2 nanoparticles have merged to form a
crystalline structure. However, after modifying the nanoparticles
with oleic acid, these OA-TiO2 nanoparticles have further merged
3.1.3. BET surface area analysis to form a larger structure. It can be due to the re-crystallization
BET and BJH analysis are done to study the N2 adsorption- of the nanoparticles during the heating treatment involved in the
desorption isotherms as well as pore size distribution of the nano- process of surface modification. In the case of ZnO, a huge mesh
materials. Fig. 2a shows the absorption-desorption pattern of OA- of scattered grain like structures of ZnO nanoparticles can be seen.
TiO2 as well as OA-ZnO nanoparticles. However, after their surface modification, the morphology of nano-
Both the nanomaterials exhibited Langmuir type-IV isotherms material changed slightly. A cluster of ZnO nanorods of shorter
having the characteristics of mesoporous nature. OA-TiO2 nanopar- lengths can be seen. These structures are similar to the grain like
ticles showed a comparatively greater specific surface area as com- structures resembling the broken rods of unmodified ZnO
pared to OA-ZnO nanoparticles. The details about the specific nanomaterial.
3
Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

250 0.035
OA-TiO2
OA-TiO2 (a) (b)
Adsorbed Volume (cm3/g) OA-ZnO 0.030 OA-ZnO

Pore Volume (10-3m3/kg)

200
0.025
150 0.020

0.015
100
0.010
50 0.005

0.000
0
0.0 0.2 0.4 0.6 0.8 1.0 0 5 10 15 20 25
Relative Pressure (p/po) Pore Size (nm)

(c) OA-TiO2
100 5.4%
7.3% OA-ZnO
14.2%
80
Weight Loss (%)

60

40

20

0
0 200 400 600 800 1000
Temperature (oC)
Fig. 2. (a) Adsorption-desorption pattern, (b Pore size distribution, and (c) TGA of OA-TiO2 and OA-ZnO nanoparticles.

Table 1
Surface area and porosity details of OA-TiO2 and OA-ZnO.

Samples Specific Surface Area (m2/g) Mean Pore Diameter (nm) Mesopore Volume (cm3/g) Total Pore Volume (cm3/g)
OA-TiO2 48.7 29.6 0.34 0.36
OA-ZnO 17.9 29.5 0.12 0.132

3.2. Dielectric properties decrease in the BDV value of the oil-blend. OB80 is chosen as the
base oil for dispersing the nanomaterials in order to prepare the
3.2.1. AC breakdown voltage (BDV) nanofluid samples. The BDV of the five NF samples have been plot-
The BDV of prepared OB as well as NF samples were measured ted in Fig. 4b and 4c using 1-way ANOVA method keeping the sig-
according to the IEC 60156 standards using a semi-automated BDV nificance level at 0.05. The data shows that at both temperature
test machine with 100 kV as maximum limit voltage. The test cell values, BDV of NF increases on dispersing the TiO2 as well as ZnO
used for handling the fluid sample consisted of two semi-spherical nanoparticles in OB80. With further increase in the concentration
electrodes made up of stainless-steel material. The body diameter of nanoparticles, the BDV keeps on increasing till it reaches its
of these electrodes was 50 mm and the distance between two elec- maximum value in NF5 sample for both types of NFs. TNF samples
trodes was maintained at 2.5 mm. The step voltage applied to the show a slightly more increase in overall BDV as compared to the
test cell was increasing at a rate of 2 kV/sec. ZNF samples.
Fig. 4a shows the plotted data of BDV of OB samples at 25 °C and Table 2 shows the peak BDV values of NF samples with corre-
90 °C. The BDV of the OB is found to be proportional to the quantity sponding percentage enhancement in their BDV values when com-
of EO in the blend. The pure mineral oil has a BDV of 45 kV at 25 °C pared to pure mineral oil, ester oil and base oil-blend.
and 46 kV at 90 °C. The pure ester oil has a BDV of 50 kV at 25 °C
and 55 kV at 90 °C. The peak value of BDV is achieved in oil blend 3.2.2. Impulse breakdown voltage (IBDV)
having 80% of ester oil, thus named as OB80, which is around 55 kV IBDV values of prepared OB as well as NF samples were mea-
at 25 °C and 56 kV at 90 °C. Further addition of EO results in a sured according to IEC 60897 standards. Standard positive
4
Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

Fig. 3. FE-SEM image of (a) TiO2 nanoparticles, (b) OA-TiO2 nanoparticles, (c) ZnO nanoparticles, and (d) OA-ZnO nanoparticles.

70
(a) 25oC
90oC
65
Breakdown Voltage (kV)

60

55

50

45
MO OB80 EO
40
0 20 40 60 80 100
Ester Oil Content (%)
75 75
(b) 25oC 25oC
(c)
90oC 90oC
70 70
Breakdown Voltage (kV)

Breakdown Voltage (kV)

65 65

60 60

55 55

50 50
45 45
OB80 TNF1 TNF3 TNF5 TNF7 TNF9 OB80 ZNF1 ZNF3 ZNF5 ZNF7 ZNF9
40 40
0 0.001 0.003 0.005 0.007 0.009 0 0.001 0.003 0.005 0.007 0.009
TiO2 Concentration (g/L) ZnO Concentration (g/L)

Fig. 4. BDV of (a) different oil blends, (b) TNF samples, and (c) ZNF samples.

impulses of 1.2/50 ms rating were applied to the test cell to imitate values of TNF as well as ZNF samples are plotted in Fig. 5b using 1-
the lightning strikes. The values of IBDV for OB samples are plotted way ANOVA with a 0.05 significance level. Addition of both TiO2 as
in Fig. 5a. The IBDV of OB increases with the increase in the quan- well as ZnO leads to an increase in the IBDV of NF samples up to a
tity of the EO in the blend. At 80% content of EO which corresponds particular concentration. The highest value of IBDV for both types
to OB80 sample, the maximum value of IBDV is attained. A further of NFs are recorded in case of NF5 samples which correspond to the
addition of EO causes a slight dip in the IBDV of OB samples. IBDV 0.005 g/L concentration of nanoparticles in the oil-blend.

5
Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

Table 2
Percentage enhancement in BDV values of NF samples.

NF Type Max BDV achieved (kV) % Increase with respect to

MO EO OB80
25 °C 90 °C 25 °C 90 °C 25 °C 90 °C 25 °C 90 °C
TNF 64.2 68.2 29.1 30 22.1 24.4 17.5 17.8
ZNF 62.9 67.2 27.6 29 20.5 18.4 13.2 16.7

85 TiO2
(a) (b)
80 100 ZnO

75
Impulse BDV (kV)

Impulse BDV (kV)

90
70
65
80
60
55 70
50
MO OB80 EO OB80 NF1 NF3 NF5 NF7 NF9
45 60
0 20 40 60 80 100 0 0.001 0.003 0.005 0.007 0.009
Ester Oil Content (%) Nanoparticle Concentration (g/L)
Fig. 5. IBDV values of (a) prepared OB samples, and (b) TNF and ZNF samples.

Increasing the nanoparticle concentration beyond this value leads 3.2.3. Relative permittivity and dissipation factor
to a decrease in the IBDV values of both NFs. The maximum values Relative permittivity and dissipation factor of NF samples was
of IBDV attained by the NF samples and their corresponding measured as per the ASTM D924 specifications. Fig. 7a shows the
increase with respect to the pure mineral oil, pure ester oil and relative permittivity of TNF samples at 25 °C and 90 °C. Fig. 7b
base oil-blend are tabulated in Table 3. shows the relative permittivity of ZNF samples at 25 °C and
In Fig. 6, both the BDV and IBDV data of TNF as well as ZNF sam- 90 °C. The dielectric constant of OB80 was measured to be 1.9 at
ples have been modelled and plotted as per the 2-way parameter 25 °C and 2.3 at 90 °C. by adding the TiO2 and ZnO nanoparticles
Weibull distribution technique at a confidence band of 95% which in OB80, the values of dielectric constant for both types of NFs
can be explained as per the equation: were increased up to a certain concentration. For TiO2 dispersed
NF samples, the maximum value of dielectric constant at both tem-
peratures was achieved for TNF3 which was 2.7 at 25 °C and 2.9 at
FðxÞ ¼ 1
expð
ðx=aÞb Þ ð1Þ 90 °C. Likewise, in case of ZnO dispersed NF samples, its maximum
value at both temperatures was recorded for ZNF5 which was 2.8
at 25 °C and 2.9 at 90 °C. A further increase of nanoparticles in both
where, a is called as scale parameter. It defines the range of distri-
NF samples resulted in a considerable decrease in their dielectric
bution of the function. The greater the scale parameter, the wider
constant values, especially in TNF samples for which the dielectric
the spread of the distribution of function. In other words, the scale
constant values deteriorated at higher concentration levels and
parameter gives the details of the scattering of data. It also gives a
dropped below the values corresponding to the base oil-blend,
fair idea about the degree of failure of the function. ‘b’ is called as
i.e. OB80.
shape parameter or the Weibull slope because of the fact that it
Dissipation Factor is also known as loss tangent of the insulator.
equals the slope of the line of the function in the probability plot.
The loss tangent of the base oil-blend was measured to be 0.08 at
The BDV values of NF samples at 25 °C and 90 °C have been
25 °C and 0.149 at 90 °C. The loss tangent of TNF and ZNF samples
combined in one data plot for Weibull distribution in order to
are plotted in Fig. 7c and 7d.
get a better diversity of the breakdown probability over the entire
It can be seen that by dispersing the nanoparticles in the oil-
working range of transformers under normal and overload working
blend, the dissipation factor for both types of NFs was found to
conditions. Table 4 and Table 5 show the minimum and maximum
decrease up to a certain concentration level, after which its value
values of BDV and IBDV of OB80 and NF samples respectively at
started to increase with the increase in the nanoparticles concen-
50% probability along with the scale and shape parameters.
tration. In case of TNF samples, the minimum value was achieved
for TNF3 which was 0.059 at 25 °C and 0.09 at 90 °C. Whereas for
Table 3 ZNF samples, the minimum value of dissipation factor was calcu-
IBDV values of synthesized NF samples. lated corresponding to ZNF5 sample and it was recorded to be
0.054 at 25 °C and 0.089 at 90 °C. For any particular insulating
NF Type Max IBDV achieved (kV) % Increase with respect to
material, the values of its dielectric constant as well as its dissipa-
MO EO OB80
tion factor are interrelated. The greater the dielectric constant, the
TNF 92 41.6 21.3 18 more the capacity of the insulator to withhold the charge in itself,
ZNF 98 45.2 26.1 23
which further leads to the lower dissipation factor. This can also be
6
Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

99.9 OB80 (a) 99.9 OB80 (b)

99 TNF1 99 ZNF1
90 TNF3 90 ZNF3
TNF5 ZNF5
50 TNF7 50 ZNF7
Probability

TNF9 ZNF9

10 10
5 5

1 1

40 50 60 70 80 40 50 60 70 80
Breakdown Voltage (kV) Breakdown Voltage (kV)
99.9 OB80 (c) 99.9 OB80 (d)
99 TNF1 99 ZNF1
90 TNF3 90 ZNF3
TNF5 ZNF5
50 TNF7 50 ZNF7
Probability

TNF9 ZNF9

10 10
5 5

1 1

50 60 70 80 90 100 110 50 60 70 80 90 100 110

Impulse BDV (kV) Impulse BDV (kV)

Fig. 6. Weibull distribution of BDV values of (a) TNF samples, (b) ZNF samples and Weibull distribution of IBDV of (c) TNF samples and (d) ZNF samples.40.

Table 4
Upper and lower limits at 50% probability along with shape and scale parameters for OB80 sample.

Sample U50
BDV IBDV
Min Max a b Min Max a b
OB80 54.1 57.9 57.1 17.8 73.5 78.4 77.4 18.5

Table 5
Upper and lower limits at 50% probability along with shape and scale parameters for TNF and ZNF samples.

Concentration Level U50

TiO2 ZnO
BDV IBDV BDV IBDV
Min Max a b Min Max a b Min Max a b Min Max a b
NF1 60.9 63.7 63.1 26.5 79.2 81.1 80.7 50.1 60.4 62.5 62.1 33.5 79.4 82.9 82.2 27.5
NF3 62.9 65.9 65.3 25.8 85.2 86.4 86.1 85.4 62.1 64.8 64.3 27.8 87.4 89.4 89 53.1
NF5 65.3 67.3 67.4 30.1 91.2 93.2 92.8 55.5 64.3 66.5 66.1 35 97.2 99.3 98.9 54.8
NF7 57.8 60.6 60 25.6 89 91.5 91 43.5 60.6 65.1 64.2 16.7 96.8 98.4 98.1 74.9
NF9 56.4 59.3 58.7 23.5 86.5 88.2 87.9 63.9 58.5 63.6 62.6 14.3 90.8 92.3 92 70.2

seen by comparing the dielectric constant and dissipation factor of ZnO nanoparticles. When comparing the viscosities of a particu-
data plots of both types of NF samples. lar NF sample at a particular concentration level, the viscosity at
90 °C is very less as compared to its viscosity at 25 °C. This is due
to the increase in inter-spatial distance between the molecules of
3.2.4. Viscosity
the liquid at higher temperatures as a result of increase in their
The viscosity of TiO2 and ZnO dispersed NF samples were mea-
kinetic energies.
sured according to ASTM D445 specifications at 25 °C as well as at
90 °C and compared with the viscosity of base oil OB80 sample at
respective temperatures. The values are plotted in Fig. 8. 3.2.5. Inter-facial tension (IFT)
It is evident that the viscosity of TNF sample decreased slightly IFT values of TNF and ZNF samples were measured according to
with the addition of TiO2 nanoparticles and almost attained a con- ASTM D971 standards at 25 °C using a tensiometer working upon
stant value at higher concentration levelsOn the other hand the Du-Nouy ring principle. The comparative analysis of IFT values of
viscosity of ZNF sample is increased considerably with the addition TNF and ZNF samples has been shown in Fig. 9a. The IFT of OB80
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Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

4.0 4.0
(a) 25oC (b) 25oC
90oC 90oC
3.5 3.5
Relative Permittivity

Relative Permittivity
3.0 3.0

2.5 2.5

2.0 2.0
OB80 OB80
1.5 1.5
TNF1 TNF3 TNF5 TNF7 TNF9 ZNF1 ZNF3 ZNF5 ZNF7 ZNF9
1.0 1.0
0 0.001 0.003 0.005 0.007 0.009 0 0.001 0.003 0.005 0.007 0.009
TiO2 Concentration (g/L) ZnO Concentration (g/L)
0.30 0.30
(c) 25oC (d) 25oC
90oC 90oC
0.25 0.25
Dissipation Factor
Dissipation Factor

0.20 0.20
OB80 OB80
0.15 0.15

0.10 0.10

0.05 0.05

TNF1 TNF3 TNF5 TNF7 TNF9 ZNF1 ZNF3 ZNF5 ZNF7 ZNF9
0.00 0.00
0 0.001 0.003 0.005 0.007 0.009 0 0.001 0.003 0.005 0.007 0.009
TiO2 Concentration (g/L) ZnO Concentration (g/L)

Fig. 7. Relative permittivity of (a) TNF samples, (b) ZNF samples, and dissipation factor of (a) TNF samples, and (d) ZNF samples.

300 300
(a) 25oC 25oC (b)
90oC 90oC
250 250
Viscosity (mPa-s)

Viscosity (mPa-s)

200 200

150 150

100 100
OB80 TNF1 TNF3 TNF5 TNF7 TNF9 OB80 ZNF1 ZNF3 ZNF5 ZNF7 ZNF9
50 50

0 0
0 0.001 0.003 0.005 0.007 0.009 0 0.001 0.003 0.005 0.007 0.009
TiO2 Concentration (g/L) ZnO Concentration (g/L)
Fig. 8. Viscosity of (a) TNF samples, and (b) ZNF samples.

is 50 which is considered as good IFT for any insulating oil. How- were attained at a concentration level of NF3 for both nanomateri-
ever, this value increases further by dispersing TiO2 as well as als after which a decrease in the IFT values was noticed. However,
ZnO nanoparticles in the base oil-blend. The peak values of IFT IFT for both the NFs remained in ‘good’ category up to the

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Z.B. Siddique, S. Basu and P. Basak Journal of Molecular Liquids 339 (2021) 116825

320
(a) TiO2 (b) TiO2
Interfacial Tension (mNm-1) 60
ZnO 300 ZnO
50 280

Flash Point (oC)

OB80
40 260

240
30
220
OB80
20
200
NF1 NF3 NF5 NF7 NF9 NF1 NF3 NF5 NF7 NF9
10 180
0 0.001 0.003 0.005 0.007 0.009 0 0.001 0.003 0.005 0.007 0.009
Nanoparticle Concentration (g/L) Nanoparticle Concentration (g/L)
Fig. 9. (a) IFT values of NF samples, and (b) flash point of NF samples.

concentration level corresponding to NF5 samples, after which synthesized nanofluids up to a particular concentration limits. In
there was extremely sharp decline in the IFT values leading to case of AC breakdown voltage, the enhancement due to the addi-
the ‘poor’ oil conditions. tion of semi-conductive TiO2 nanoparticles was 2% higher than that
caused by the addition of ZnO nanoparticles in pure mineral oi, 5%
3.2.6. Flash point higher in pure vegetable oil and 1% higher in oil blend. However, in
Flash points of the samples were measured as per ASTM D93 case of impulse breakdown voltage, ZnO nanoparticles led to com-
standards. The values of flash points of NF samples are plotted in paratively higher enhancement than that caused by TiO2 nanopar-
Fig. 9b. Flash point of OB80 blend was recorded at 220 °C. Addition ticles. This can be due to the higher shallow tapping leading to
of both types of nanomaterials caused an increase in the flash point faster capability of electron trapping of conductive ZnO nanoparti-
of the oil blend. However, the increase caused by ZnO nanoparti- cles during the sudden increase in the voltage. Dispersing of TiO2
cles was more as compared to the increase caused by TiO2 slightly lowered down the viscosity of the nanofluid whereas, addi-
nanoparticles. The highest value of flash point in case of TNF sam- tion of ZnO nanoparticles led to an overall increase in the viscosity
ples was recorded as 269 °C, whereas the highest value of flash of the oil thus deteriorating the cooling property of the nanofluid.
point in case of ZNF samples was found to be 273 °C. Both the peak
values were corresponding to the NF5 concentration levels. CRediT authorship contribution statement

4. Improvement mechanism Zaid B. Siddique: Conceptualization, Methodology, Validation,

Investigation, Data curation, Writing - original draft, Visualization.
One of the most important reasons for the improvement in Soumen Basu: Conceptualization, Methodology, Validation, Inves-
dielectric properties of the NF samples when compared to the base tigation, Resources, Data curation, Writing - review & editing, Visu-
oil is the transferring of charge to the pathway served by the Gouy- alization, Supervision, Project administration, Funding acquisition.
Chapman-Stern layer which is former at an interface between the Prasenjit Basak: Conceptualization, Methodology, Validation,
oil and nanoparticles due to the by-products formed over the pas- Investigation, Resources, Writing - review & editing, Visualization,
sage of time [25]. This layer is responsible for the increased con- Supervision, Project administration, Funding acquisition.
ductive path through the interface. In NF samples, the
conduction along the interface of oil and nanoparticles can lead Declaration of Competing Interest
in higher shallow trap density. These shallow traps can be held
responsible for the accumulation of charge carriers which are gen- The authors declare that they have no known competing finan-
erated at high voltage levels. This further enhances the electron cial interests or personal relationships that could have appeared
trapping phenomenon in NFs when compared to the base oils. to influence the work reported in this paper.
These shallow traps lead to a slower de-trapping of electrons in
NFs leading to better dielectric properties. References

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