Polymer International 36 (1995) 315-324

ElectricaI Properties of an Insulating

Varnish

Augenie M. Bishai* & ltedal K. Hakim

Physics Department, National Research Center, Dokki, Cairo, Egypt

(Received 7 January 1994; revised version received 4 October 1994;accepted 31 October 1994)

Abstract: A systematic dielectric study was carried out over a frequency range
60Hz-300kHz and at temperatures between 5 and 90°C on dehydrated castor
oil mixed with different concentrations of styrene monomer to produce an insu-
lating varnish. The volume resistivity was also studied. The results show that,
when dehydrated castor oil is mixed with 10% styrene content by weight of the
oil, epoxidised and then chemically treated with melamine resin and other addi-
tives, a varnish is produced with favourable electrical insulation properties.
K e y words: dielectric properties, permittivity, loss tangent, volume resistivity,
castor oil, styrene monomer.

INTRO D U C T I ON castor oil when treated with different concentrations of

maleic anhydride (polar molecule) to obtain an insulat-
Phenolic, epoxy acrylic and amino resins are generally
ing varnish has been studied.’ The dielectric properties
used as electrical insulating varnishes.’ The physical
of castor oil may be influenced by the addition of non-
and mechanical properties of these polymers are good,
polar molecules (e.g. styrene monomer). No systematic
but their elasticity is low. Elasticity is an essential pro-
investigations have been reported in the literature
perty, especially when varnishes are used for wire coat-
regarding the effects of styrene concentration on the
ings. Thus, plasticisers are added. Castor oil is a
electrical properties of castor oil in the low frequency
vegetable product; it is a non-drying oil, and is gener-
region.
ally used as a plasticiser in synthetic resin compositions
The aim of this work is to extend previous studies’*6
and as a cooling liquid in some types of transformers. It
by investigation of the electrical properties of castor oil
possesses insulating properties together with high elas-
treated with styrene monomer to produce an insulating
ticity, but the physical and mechanical properties of its
varnish for use in the low frequency region.
film d o not meet the necessary specifications, especially
when it is used for wire coatings. It must be chemically
treated to improve its physico-mechanical properties in EXPERIMENTAL
order t o use the modified product as an insulating Castor oil was dehydrated at 270°C in an inert atmo-
varnish for wire coatings. sphere using sodium bisulphate as catalyst :
Dielectric studies of castor oil help to extend its use
in electrical applications. In fact, permittivity and loss -CH2-CH-CH2-CH-CH-
I
tangent measurements are important tools for studying OH
dielectric dispersion in a medium. These parameters I 30%
depend on the molecular structure of the material and CH2-CH-CH-CH=CH-
different dielectric relaxations are manifested at different
frequencies. The dielectric and other properties of castor CH==CH-CH2-CH-CH-
oil have been The electrical behaviour of I1 70%

* To whom correspondence should be addressed. The dehydrated castor oil (DCO) was reacted with
315
Polymer International 0959-8103/95/$09.00 0 1995 SCI. Printed in Great Britain
316 Augenie M . Bishai, Itedal K . Hakim

styrene monomer at 160°C for 16 h using benzoyl per- The varnishes were applied to tin plates at different
oxide as initiator.6 thicknesses from 10 to 50pm, and stoved at tem-
peratures from 120 to 180°C for 0.5-1.5 h to polymerise
the epoxidised styrene-reacted DCO and melamine
resin. Glossy films of good appearance were obtained.
Mechanical, physical and chemical properties were
determined.6
It was found that varnish films containing 30% mela-
mine resin and with a thickness of 30pm stoved at
160°C for 1 h gave the best mechanical properties.
Accordingly the electrical properties of these films
R2
were investigated.

Electrical measurements
The copolymerisation of styrene and DCO takes place
at the conjugated part of the latter by a 1,4 or 1,2 addi- Measurements of the permittivity, E', and loss tangent,
tion reaction; the 1,4 addition is predominant. During tan 6, were carried out in the frequency range 60Hz-
styrenation, the styrene chain may link with another oil 300kHz at temperatures from 5 to 90°C. A dielectric
molecule as follows : test bridge of the Schering type and a test cell type
K MF from Rohde and Schwarz were used for liquid
varnishes; for varnish films (solid state), the measure-
ments were carried out with a low frequency decameter
(WTW type DK05'). The decameter was composed of
a capacitance bridge of the Schering type, a frequency
generator and an oscilloscope as zero indicator. The
substitution method was utilised in the bridge. A guard
ring capacitor type NFM 5T was used. Accuracy of the
Three concentrations were used, 5%, 10% and 15% measurements amounted to f 1% in E' and 3% in tan 6.
styrene by weight of the oil. The products were further The volume resistivity of the samples investigated was
developed by subjecting them to an epoxidation measured by a power supply unit G M 4561/01 from
process. Philips, giving a stable DC voltage between 0 and 250 V
with a maximum loading current of 1 mA. The potential
difference between the plates of the condenser holding
the sample and the current flowing through it was mea-
sured using a multimeter type UR1 BN/050 from Rohde
and Schwarz.

RESULTS AND DISCUSSION

Dielectric properties of styrene-reacted DCO before

The epoxidised styrene-reacted DCO were mixed with a
and after epoxidation
melamine resin precondensate in the ratios 10, 15, and
30% by weight of the oil. A small proportion (0.75%) of
Effect of concentration. The permittivity, E', and loss
stannic chloride pentahydrate was added to the mixture,
tangent, tan 6, versus styrene concentration in DCO
which was stirred and allowed to stand until complete
measured at 1 kHz over a temperature range between
separation of bubbles occurred. A completely poly-
22 and 91°C before and after epoxidation are shown in
merised epoxidised styrene-reacted DCO molecule
Figs 1 and 2, respectively. It is clear from Fig. 1 that at
would have the following structure:
22°C E' increases when 5% styrene is added to DCO,
(V)
then it decreases with increasing styrene content and
Q-" I
HC-
I
HC-Od
HC
75
I
HC-0-
- also decreases with increase of temperature. At 22°C
tan 6 slightly increased at 5% styrene content and then
decreased with increase of styrene concentration.
I
H $ q C H 2-C" 5I H Increasing the temperature above 22"C, tan 6 is much
increased especially at 5% styrene content. The increase
in E' and tan 6 on adding 5% styrene to DCO may be
due to the movement of the styrene-reacted DCO mol-

POLYMER INTERNATIONAL VOL. 36, NO. 4, 1995

Electrical properties of an insulating varnish 317

3.6 1
€'
3.4 - 6.0

3.2 -
5.5

3.0-
I I I
0 5 10 15
0 5 10
Styrene o1
( ' I15
Styrene ( % )

0.16

0 22 "C 8 30 'C
x 46 'C 0 56 ' C
0.14
73 "C 0 90 "C
91 "C

0.12 1.2 .

3.10
w
t
a
4-

0.08

0.06

0.04

0.02 0.2
O . i

0
0 5 10
Styrene ( % )
15

Fig. 1. Permittivity E' and loss tangent tan 6 versus concen-

00t 5 10 15
Styrene ( % )

Fig. 2. E' and tan 6 versus concentration of styrene in DCO

tration of styrene in DCO before epoxidation at (0) 22"C, after epoxidation at (m) 30"C, ( 0 )5 6 T , and (0) 90°C at
( x ) 4 6 T , (A)73°C and ( 0 )91 "Cat 1 kHz. 1 kHz.

ecules becoming easier. The flexibility of the backbone that both E' and tan 6 are much higher than before
is increased by incorporation of styrene. On the other epoxidation. This is due to the increased degree of
hand, adding the non-polar monomer (styrene) to DCO freedom of the molecules after epoxidation resulting
results in a decrease of the polarity of the system. So from the reaction of the double bonds on the chain to
increasing styrene content above 5% leads to a decrease form epoxy groups. E' and tan 6 for 10% styrene are
in E' and tan 6. Figure 2 gives the effect of styrene con- higher than for 5% and 15% styrene content.
centration on E' and tan 6 after epoxidation. It is clear This can be attributed to the increased mobility of the

POLYMER INTERNATIONAL VOL. 36. NO. 4. 1995

318 Augenie M . Bishai, ltedal K . Hakim

W
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POLYMER INTERNATIONAL VOL. 36, NO. 4, 1995

Electrical properties of an insulating varnish 319

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POLYMER INTERNATIONAL VOL. 36, NO. 4. 1995

320 Augenie M . Bishai, Itedal K . Hakim

charge carriers. The low values of E' and tan 6 for 15%
styrene content may be due to hindered rotation of the
molecules as the number of epoxy groups increases.

Eflect of frequency. The data obtained for E' and tan 6 at

a frequency range from 60Hz to 300kHz and over a
temperature range from 5°C to 91°C before and after
epoxidation for styrene concentrations from 0% to 15%
are shown in Figs 3 and 4. It is clear from Fig. 3 that
there is no change in E' with frequency at all tem-
peratures, except that at 6°C there is a small decrease at
the higher frequency range for the styrene-reacted
DCO.
For the epoxidised styrene-reacted DCO (Fig. 4), no
change was observed in E' with frequency at tem-
peratures higher than 30°C. At lower temperatures and
at frequencies higher than 3 kHz, E' decreases gradually
with increase of frequency indicating a dispersion
region. As the temperature increases, E' is lower over the
whole frequency range both before and after epoxida-
tion. The decrease in E' with increase in temperature is
temp;^
due to a greater randomness of motion of dipoles which
reduces their mean orientation along the electric field. Fig. 5. Volume resistivity p versus temperature for (0) 5%
At the lower frequencies tan 6 decreases with increase and ( 0 )15% styrene-reactedDCO before epoxidation.
of frequency and increases with increase of temperature,
while at the higher frequency range, especially for the of the absolute temperature, T, as shown in Fig. 7 using
epoxidised samples, tan 6 increases with decrease of the equation'
temperature; this is clear in Fig. 4. The tail of an
absorption region whose maximum could be higher
than 300 kHz is observed at 5°C. This absorption region
shifts to higher frequencies with increase of temperature.
where R is the gas constant. It is found that AH is 8.1
This high frequency absorption region corresponds to
and 8.7kcal/mol for 5% and 15% styrene content
relaxation processes which can be attributed to the
before epoxidation. After epoxidation, AH is 12.6 and
orientation of the polar epoxide groups. The increase in
13.0kcal/mol for 5% and 10% styrene content.
tan 6 with increase of temperature at lower frequencies
From the above study it is clear that the epoxidation
may be due to direct current conductivity. To confirm
process does not have a good effect on the electrical
this, the volume resistivity for each sample was mea-
properties of the oil, but from the chemical, physical
sured by application of Ohm's law to direct current
and mechanical points of view, epoxidation must be
flowing through the sample at 250 V. The measurements
carried out to improve these properties, especially adhe-
were carried out from room temperature to 95°C. The
sion, as the varnishes produced are intended to be used
variations of the volume resistivity, p , versus tem-
for wire coatings. The electrical properties will be
perature before and after epoxidation are shown in Figs
improved after a drying process where the epoxide
5 and 6.
groups are consumed during a polymerisation reaction
It is interesting to note that the volume resistivity for
and CO, is split off, leading to a varnish of much
5% styrene content is lower than that for 15% before reduced polarity.
epoxidation, while after epoxidation the volume resis-
tivity for 5% styrene content is higher than that for
10%. This is in agreement with the results for tan 6 Dielectric properties of varnish films
shown in Figs 1 and 2 where tan 6 is higher for 5%
styrene content before epoxidation and lower after The frequency dependence of E' and tan 6 at tem-
epoxidation. We can say that the mobility of charge peratures from 20 to 54°C for two samples of varnish
carriers for 5% styrene content before epoxidation and films (polymerised epoxidised styrene-reacted DCO)
for 10% after epoxidation is responsible for the increase having concentrations of 10% and 15% styrene are
in tan 6 in both cases. illustrated in Fig. 8. E' decreases with increase of fre-
To calculate the apparent activation energy, AH, the quency and increases with increase of temperature. The
volume resistivity log p is plotted again the reciprocal decrease in E' with frequency has been discussed before.

POLYMER INTERNATIONAL VOL. 36, NO. 4, 1995

Electrical properties of an insulating varnish 32 1

4 .O

3.5

3 .O

h
2.5
2
'0
c

2.c
V
I
x
I
0
Y

Q 1.5

1 .c

0.Z

(
0 20 40 60 80 100
Temp., "C
Fig. 6. Volume resistivity p versus temperature for (0)
5% and ( 0 )10% styrene-reacted DCO after epoxidation.

The increase in E' with temperature can be attributed to the molecules, which reduces orientational freedom and
polarisation of the local space charges resulting from thus tends to reduce E'. tan 6 decreases with increase in
mobile carriers. It should be noted that E' for varnish temperature over the whole frequency range except that
films is higher than for the styrene-reacted DCO before at 54°C it is high in the lower frequency region. Small
and after epoxidation. This is due to the increased variations in tan 6 with frequency are shown, giving
density of the varnish, the formation of crosslinks broad absorption curves at all temperatures. This can
between the chains after polymerisation and consequent be attributed to a number of relaxation processes
prevention of mutual cancellation of the dipoles in the involving orientation of large crosslinked aggregates
molecules. with corresponding large relaxation times. For 15%
For varnish films containing 10% styrene, E' is lower styrene tan 6 is found to decrease with temperature.
than for 15% styrene content. This may be due to the Above 30°C its value is increased in the lower frequency
fact that the first sample is more compatible with the range.
melamine and other additives. This increases binding of Two absorption curves are shown, a low frequency

POLYMER INTERNATIONAL VOL. 36, NO. 4, 1995

 Augenie M . Bishai, Itedal K . Hakim

10.6 -
-
10.4 -

-
10.2 -
-

10.0 -
-
i
Log 4

9.8 -
O'O* t ' OO,r

\
0.07
z
uI ..
z 0.06 O0 o06
71

9.6 - LQ

Y
-5 0.05-
Q -
0 0.04-
0
-I 9.4-
0.03-
-

9.2 -
- 3 1 5
Log f Log i

9.0 - Fig. 8. Variation of e' and tan 6 versus frequency for 10% and
15% polymerised epoxidised styrene-reacted DCO (varnish
- films) at ( 0 )20'32, (0)
30T, ( x ) 40°C and (A) 54°C.

8.8 -
Maxwell Wagner polarisation. This polarisation occurs
- in heterogeneous dielectrics as a result of the accumula-
tion of virtual charge at the interface of two media
8.61 f; 1 I I I I I 1 I I
having different permittivities and/or conductivities.
2.6 2.8 3.0 3.2 3.4
The heterogeneity of this sample could be due to the
1000 I T , K - '
presence of some residual styrene monomer and the
Fig. 7. log p versus 1000/T for (0) 5% and ( 0 )10% epoxi- catalysts used. It is clear from the sharp increase' in E'
dised styrene-reacted DCO. in the lower frequency range at 54°C.
The volume resistivity p for the two varnish films was
one whose maximum is at frequencies lower than measured from room temperature to 85°C and the data
100 Hz, and another absorption region in the higher fre- are shown in Fig. 9. It is clear from this figure that the
quency range. The broad absorption curves shown at 20 volume resistivity for the 10% sample is much higher
and 30°C for 15% styrene film may be due to relaxation than for the 15% sample.
processes of large crosslinked aggregates. As the tem- The activation energies for the two varnish films with
perature increases to 4O"C, the large aggregates may be 10% and 15% styrene content were calculated as before
broken into smaller ones having short relaxation times. and were found to be 16 and 19 kcal/mol, respectively.
By increasing the temperature to 54°C these aggregates Figure 10 gives a complete picture of the effect of
are further broken down, and the absorption curve each treatment of the styrene-reacted DCO on the
becomes narrower and shifts to higher frequencies with dielectric properties for samples containing 10 and 15%
a maximum at about 40 kHz. The low frequency losses styrene at different frequencies and at 30°C. It is clear
at high temperatures can be attributed to a contribution that epoxidation of the styrene-reacted DCO increases
from steady state direct current conductivity and/or both E' and tan 6.

POLYMER INTERNATIONAL VOL. 36, NO. 4. 1995

Electrical properties of an insulating varnish 323

260 -

2LO -

220 -

200 -

180 -

-
0
160-

0
* 140-
4
f 120-
0
9
100 -

80 - co

60 -
-
5

0.06-

40 -
0.04-

20 -

0 20 40 60 80 100
Temp ,'C

Fig. 9. Volume resistivity p versus temperature for (0) 10% Log f

and ( 0 )15% styrene varnish films, and log p versus 1000/T.
Fig. 10. E' and tan 6 versus logf for 10% (.....#- .) and
15% (..O..O..) styrene-reacted DCO at 30°C; 10%
(--@--@--) and 15% (--O--O--) styrene reacted after
After polymerization, E' of the epoxidised styrene- epoxidation; 10% @ -( )-. and 15% (-0-0-1
reacted DCO (varnish films) is much increased, while styrene varnish films.
tan 6 is decreased in the low frequency region and has
approximately the same value over the whole frequency resistivity is 3 x 10" Rcm at the same temperature.
range. Also, tan 6 for 10% styrene films is lower over the
From the above study, it is clear that varnish film
whole frequency range under test and at temperatures
containing 10% styrene has lower dielectric losses over higher than 50°C, while for 3% maleic anhydride
the frequency range tested and at temperatures up to varnish film it was found that tan 6 is low only at tem-
54°C. Also it has higher resistivity and lower activation peratures below 30"C, and at higher temperatures it
energy than 15% styrene film. Therefore it can be increases rapidly as shown in Fig. 11.
recommended as a good insulator for wire coatings.
As far as electrical insulation properties are con-
cerned, it is interesting to compare the electrical proper- CONCLUSION
ties of 10% styrene varnish film with those obtained
previously5 for 3% maleic anhydride varnish film. It is To prepare varnishes from castor oil with good electri-
found that the 10% styrene film possesses better electri- cal insulation properties, it is preferable to treat castor
cal properties. The volume resistivity of styrene varnish oil with non-polar molecules such as styrene monomer
film is 25 x 10" Rcm at 30°C which is much higher at concentrations of 10% styrene by weight of the oil.
than that of 3% maleic anhydride varnish film whose The experimental data indicate that the main dielectric

POLYMER INTERNATIONAL VOL. 36, NO. 4, 1995

324 Augenie M . Bishai, ltedal K . Hakim

higher frequencies and lower temperatures a dielectric

0.2 0 relaxation is observed in the epoxidised system.

0.15
/
P ACKNOWLEDGEMENT

/ This work is part of the project ‘Improvement of electri-

cal insulating materials’ and was supported financially
u)
by the Egyptian Academy of Science and Technology.
‘C 0.10
c
a

REFERENCES
0.05
1 Carroll, B., Physical Methods in Macromolecular Chemistry, Vol. 1.
Marcel Dekker, New York, London, 1969, p. 166.
2 Mammotty, K. P. & Ramu, T. S., IEEE Trans. Electric Insul., EI-16
(1981)417.
0 I 1 I 1 3 Rarnu, T. S., IEEE Trans. Electric Insul., EL14 (1979) 136.
4 Abd-El-Now, K. N. & Hanna, F. F., J. Polym. Sci., Polym. Lett.
Temp. ,‘C Ed., 21 (1983) 723.
5 Bishai, A. M. & Hakim, 1. K., Plaste Kautschuk, 33 (1986) 234.
Fig. 11. Comparison between tan 6 of 10% styrene varnish 6 Badran, B. M., El-Awar, I. M., Ibrahim, M. S. & Ghanem, N. A,, J .
Oil Col. Chem. Assoc., 63 (1980) 399,427.
film ( 0 ) and 3% maleic anhydride varnish film (0) at 7 Instruction Manual for Decameter DK05. Wissenschaftlich-
0.1 kHz. Technische Werkstatten, Weil hem/obb., Germany, 1966.
8 Glasstone, S., Laidler, K.J. & Eyring, H., Theory of Rate Processes.
McGraw Hill, New York, 1941.
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duction mechanism which is temperature-activated. At rnical Kiads, Budapest, 1977, p. 289.

POLYMER INTERNATIONAL VOL. 36, NO. 4. 1995