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Power Technology and Engineering

Vol. 45, No. 1, 2011

CONTAMINATION OF THE TRANSFORMER OIL


OF POWER TRANSFORMERS AND SHUNTING REACTORS
BY METAL-CONTAINING COLLOIDAL PARTICLES
S. Yu. Lvov,1 V. B. Komarov,2 V. N. Bondareva,2 A. F. Seliverstov,2
E. O. Lyutko,3 Yu. N. Lvov,3 and B. G. Ershov2
Translated from lektricheskie Stantsii, No. 12, December 2010, pp. 35 41.

The results of a measurement of the contamination of the oil in 66 transformers by metal-containing colloidal
particles, formed as a result of the interaction of the oil with the structural materials (the copper of the windings, the iron of the tank and core etc.), and also the results of measurements of the optical turbidity of the oil
in 136 transformers when they were examined at the Power Engineering Research and Development Center
Company are presented. Methods of determining the concentration of copper and iron in transformer oil are
considered. The limiting values of the optical turbidity factors, the copper and iron content are determined.
These can serve as a basis for taking decisions on whether to replace the silica gel of the filters for continuously purifying the oil of power transformers and the shunting reactors in addition to the standardized oil contamination factors, namely, the dielectric loss tangent and the acidity number of the oil.
Keywords: transformer oil; metal-containing colloidal particles; optical turbidity; methods of determining the
concentrations of metals in transformer oil.

In this paper we present the results of measurements of


the optical turbidity and the content of copper and iron in oil
used in transformers and shunting reactors, and we also
choose methods for determining the metal content in the oil
for the purpose of estimating its contamination by metal-containing colloidal particles.
We inspected 136 transformers, and we measured the
optical turbidity of the transformer oil.
In Table 1 and Fig. 1 we show the frequence of the distribution of the values of the optical turbidity of transformer oil
in a sequence of n service transformers, which are defined as
the fractions of the transformers which have a specified
value of the turbidity and less than F = ni/n (ni is the number of transformers in which the values of the turbidity lie in
the ith turbidity interval). The accumulated frequences correspond to the upper limits of the turbidity intervals, and the
frequence equal to zero corresponds to the lower limit of the
first interval.
It is convenient to introduce as the integral criterion of
the contamination of transformer oil by colloidal particles
the factor of the limit value of the turbidity of the transformer
oil. This criterion enables us to distinguish transformers with
a high degree of development of colloidally dispersed processes in the oil and, as a consequence, having an increased
degree of contamination of the windings due to adsorption
by their insulation of products of oil contamination.

Transformer oil undergoes ageing during use, which is


the result not only of oxidation processes, but also due to the
formation and increase in the size of the colloidal particles
[1]. At the present time, quantitative information on the development of colloidally dispersed processes in oil-filled
transformer equipment can be obtained by measuring the optical turbidity of the transformer oil [2].
In [3] examples were given of the damage of 16 shunting
reactors due to the development of coil short circuits resulting from contamination of the winding insulation by metalcontaining colloidal particles (copper sulfide CuS2) when
using oil containing sulfur (Nitro 10 GBA or Nitro 10 GBN).
The deposition of metal-containing colloidal particles,
formed due to interaction of the oil with the structural materials (the copper of the windings, the iron of the tank, the
core etc.), on the insulation of the windings leads to the
occurrence of current-conducting bridges and, as a consequence, to a reduction in the electrical insulation sections,
an increase in the nonuniformity and an increase in the electric field strength, partial breakdown of the insulation, the
formation of gas microbubbles and, in the final analysis, to
breakdown of the dielectric and hence short circuits of the
windings.
1
2
3

LLC Presselektro, Russia.


A. N. Frumkin Institute of Physical Chemistry and Electrochemistry of
the Russian Academy of Sciences (IFCE of RAS), Russia.
JSC R&D Centre for Power Engineering, Russia.

76
1570-145X/11/4501-0076 2011 Springer Science + Business Media, Inc.

Contamination of the Transformer Oil of Power Transformers and Shunting Reactors

M + O2 [M ... O2].

(1)

The oxygen complex O2 possesses a greater reaction capability than oxygen in the free molecular state O2. Hence,
the fraction of the chain generation reaction
O2 + RH R + OOH

(2)

is less than the probability that a chain will form with the
participation of the metal
[M ... O2] + RH R + [HOO ... M],

(3)

where RH are the hydrocarbons of the transformer oil.


Free hydrocarbon radicals R easily react with oxygen,
giving peroxide radicals
R + O2 ROO.(4)
The free-radical particles formed interact further with the
components of the transformer oil and with the structural
materials of the transformer.
On heating, the oxidation process is intensified, leading
to an increase in oxygen-containing compounds, but their
concentration is then reduced due to the formation of poorly
soluble compounds with metals, so-called lacquer deposits.
As a whole, methods of determining the concentration of
metals in transformer oil can be divided into two groups: direct determination of the metal in the oil and the determination of the metal after procedures involving its separation
from the oil.

1.0

Accumulated frequency F

The limit value of the turbidity is defined by the following condition: the oil of 90% of the transformers has less and
equal turbidity. According to Fig. 1, this corresponds to a turbidity factor of 200 m1. This approach is used to determine
the limit concentrations of gases dissolved in the oil of the
transformers [4].
The dynamics of the formation of colloidal particles
when a transformer is being used are determined by the following main factors:
the type of protection of the oil from contact with the
surrounding air (from oxidation);
the transformer loading mode;
the presence and working capability of the filters for
continuously cleaning the oil;
the operating efficiency of the cooling system;
the group composition of the oil (aromatic hydrocarbons, unsaturated and saturated hydrocarbons of branched
and unbranched structure etc.);
the content of antioxidant additive ionol (agidol).
The main reactions by which transformer oil interacts
with the metal of structural materials are given in [1]. We
merely note that oxygen of the air O2, diffusing through the
oil film to the metal surface M, is absorbed by it, forming an
active complex in accordance with the reaction

77

0.8
0.6
0.4
0.2
0

50

100 150 200 250 300 350 400 450


Turbidity, m 1

Fig. 1. Distribution of the transformers as a function of the turbidity


of the transformer oil.

The first group includes methods based on the use of


atomic adsorption spectrometers or optical atomic emission
spectrometers, and also the use of x-ray fluorescence spectrometers. The main problem in using these technologies is
the need to calibrate the instruments with oil solutions or suspensions with the same metal salts of known concentration
as those being determined. Such a calibration requires considerable preliminary work to determine the forms in which
the metals exist in the oil and in producing appropriate imitators. Another drawback is the high cost of the measuring
equipment and the need to train highly qualified personnel. It
should also be noted that for instruments based on a measurement of x-ray fluorescence, a relatively low sensitivity to
copper is a characteristic feature: the lowest detection limit is
1 mg/liter. The concentration of copper in the oil of operational transformers is usually much lower.
Taking the above into account, for the purpose of choosing methods for the quantitative analysis of metals (copper
and iron) in transformer oil, we will consider methods in
TABLE 1. Distribution of the transformers with respect to the
value of the optical turbidity of the transformer oil
Interval
number i

Limits
of the interval
of optical
turbidity, m1

Number
of transformers
ni

1
2
3
4
5
6
7
8
9
10
11
12
13
14

0 10
10 20
20 30
30 40
40 50
50 100
100 150
150 200
200 250
250 300
300 350
350 400
400 450
450 500

12
31
38
2
13
11
10
6
5
6
0
0
0
2

Fraction
Accumulated
of the
frequence
transformers
F
Fi = ni/n
0.0886
0.2279
0.2794
0.0147
0.0955
0.0808
0.0735
0.0441
0.0367
0.0441
0
0
0
0.0147

Note. The total number of transformers n = 136.

0.0886
0.3165
0.5959
0.6106
0.7061
0.7869
0.8604
0.9045
0.9412
0.9853
0.9853
0.9853
0.9853
1.0000

78

which the metal ions are separated from the oil, and which
enable one to determine fairly low concentrations of metals
in oil.
Compounds of metals can be extracted from a sample of
the oil by one of the following methods:
extraction with nitric acid using a laboratory rocking
device;
extraction with nitric acid using an ultrasonic
generator;
the wet combustion process.
The first two methods are the simplest to use experimentally.
The essential feature of the method of extraction by using a laboratory rocking device is the extraction of metal ions
using an aqueous solution of nitric acid in an emulsion, obtained by shaking samples of mixtures of the oil and nitric
acid in a KM-30 or similar rocking device.
In the second method an emulsion is formed by the
action of ultrasound using a UZDN-A or similar ultrasonic
generator with a titanium sonic electrode (this method was
mainly employed in our investigation).
The most reliable method of extracting metals from a
sample of oil is the wet combustion of samples. This process involves complete oxidation of the sample of transformer oil to carbon dioxide and water by 100% nitric acid
in the presence of sulfur, and then hydrochloric acid [5].
The acidic solution obtained contains all the metals which
were present in the sample of oil employed in ionic form.
Further, for each of these methods one aims to analyze
the aqueous phase. The metal content is determined using
photometric or atomic-adsorption methods.
The basic principle of the photometric method of determining iron using 1,10-phenantrolene consists of reducing
the iron (III) in a weakly acidic aqueous solution of hydroxylamine hydrochloride. The divalent ions of iron form with
the 1,10-phenantrolene a crimson-colored complex, the optical density of which is measured at a wavelength of 512 nm
[6, 7].
The basic principle of the photometric method of determining copper consists of forming a violet-colored complex
of a compound of copper (II) with ditysonite, extracting it
with carbon tetrachloride and measuring the optical density
of the extract obtained at a wavelength of 550 nm.
The basic principle of the atomic-adsorption method of
determining the content of metals in transformer oil is a
quantitative comparison of the absorption of the resonance
radiation of the free metal atoms (iron and copper), formed in
an acetylene-air flame by introducing into it solutions of
samples of acidic aqueous extracts of transformer oils and
comparison solutions with known concentrations of copper
and iron [5]. It is this, essentially standard, method that was
used to obtain the experimental data presented in the present
paper.
Comparison experiments for these methods of extracting
the metal compounds from a sample of transformer oil and
their subsequent quantitative analysis, carried out at the

S. Yu. Lvov et al.

A. N. Frumkin Institute of Physical Chemistry and Electrochemistry, showed that in any case for two parallel determinations the relative error does not exceed 25% with a
confidence coefficient p = 0.95. Here the standards of internal operational control of convergence (a disagreement of
not more than 15% of the arithmetic mean for two results of
tests) and reproducibility (a divergence of not more than
35%) were well satisfied, i.e., the accuracy of the determination here corresponds to that obtained using similar standard
methods of determining the mass fraction of microelements
in other substances [5 7].
In Table 2 we show the results of measurements of the
optical turbidity and of the content of the metals of the main
structural materials (copper and iron) in the oil of 66 long
used and standby transformers. Of 65 chosen samples of oil,
six samples were taken from the tanks of RODGA-500 type
reactors, two samples were taken from TTs-300000/220 and
TTsG-275000/220 standard-type transformers, one sample
was taken from a standard-type standby transformer (type
OTsG-210000/500), 23 samples were taken from the tanks
of standby transformers of 110 kV substations, and 33 samples were taken from the tanks of operating transformers in
110 kV substations.
As follows from the data in Table 2, the content of
microquantities of iron in transformer oil varies from 2.308
to 11.580 mg/liter, the copper content varies from 0.167 to
1.710 mg/liter and the turbidity varies from 6 to 167 m1.
The maximum value of the turbidity of 167 m1 is less than
the limit value of 200 m1, which we recommend.
Owing to the operation of continuously acting oil cleaning filters, its additives and other operations, which lead to a
change in the concentration of metal-containing colloidal
particles in different modes of operation of the transformers,
it is difficult to analyze the kinetics of their formation in operating transformer equipment. Nevertheless, taking the
above into account, we can estimate the ratio of the copper
and iron rate of formation constants in operating transformers using the data in Table 2, by means of a kinetic equation
of the form
C = Kt + C0,

(5)

where C and C0 are the current (at the instant of measurement) and the initial concentrations of metals (iron or copper) in the transformer oil; t is the transformer oil operating
time; and K is the effective rate constant of the formation of
metal-containing compounds.
Relation (5) is a consequence of the well-known mechanism of the formation of metal-containing colloidal particles,
the kinetics of the formation of which is described by a
zero-order equation [8].
In fresh oils, copper and iron are present in only small
amounts, and their presence can only be detected by special
methods [9].

Contamination of the Transformer Oil of Power Transformers and Shunting Reactors

79

TABLE 2. Turbidity Factors and Iron and Copper Contents in Transformer Oil
Type of oil

No.

TK GOST 98256 + GK 38.101.1025-85

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65

TSp GOST 1012176 + GK TU 38.101.102585

TK GOST 98256
TSp GOST 1012162 + TSp GOST 1012176
TKP GOST 98268
TKp TU 38.101.89081
TSp GOST 1012176
TSp GOST 1012176 + import
75% TK GOST 98256 + 25% TSp GOST 1012176
GK TU 38.101-102585

TSp GOST 1012162


GK TU 38.101-89081 + TSp GOST 1012176 +
+ GK TU 38.101.83090 + GK TU 38.101.102585
T-1500 GOST 98280
TKp GOST 98268

Metal content, mg/liter

Year of introduction
into operational equipment

Turbidity
, m1

Fe

Cu

1965
1971
1966
1968
1974
1955
1979
1978
1977
1978
1968
1968
1968
1968
1958
1958
1958
1958
1962
1963
1986
1968
1968
1967
1954
1959
1968
1969
1977
1969
1969
1964
1985
1983
1979
1985
1987
1968

2005
1968
1968

1988

32
163
6
167
10
19
166
61
59
57
83
165
165
167
163
138
131
96
147
41
166
167
138
80
9
129
45
167
168
124
97
164
45
44
166
35
16
60
4
63
38
72
34
78
71
93
167

11.58
9.8
3.067
4.12
2.813
2.547
4.44
2.948
2.651
2.309
2.339
2.528
2.514
2.453
3.214
2.507
2.327
2.692
2.589
3.043
2.718
2.895
2.595
3.252
2.708
2.602
2.674
2.308
4.79
2.459
7.0
4.7
3.077
2.850
2.602
4.84
2.637
2.861
2.565
6.16
2.678
3.165
2.929
5.16
3.240
2.991
12.1

0.601
0.276
0.167
0.220
0.173
0.171
0.259
0.188
0.187
0.161
0.173
0.235
0.230
0.203
0.199
0.210
0.194
0.198
0.543
0.256
0.477
0.317
0.207
0.187
0.175
0.197
0.220
0.392
1.053
0.193
0.294
0.221
0.204
0.184
1.710
0.283
0.185
0.189
0.184
0.213
0.196
0.213
0.357
0.212
0.829
0.208
0.275

1960
1976

123
61
89
63
165
77
125
69
115
153
60
42
129
27
11
107
74
7

3.38
2.448
3.099
2.767
2.826
2.990
2.826
3.022
2.276
2.536
6.56
6.2
5.16
2.954
3.272
9.13
2.787
2.262

0.314
0.197
0.204
0.220
0.229
0.354
0.213
0.225
0.371
0.188
0.218
0.756
0.317
0.185
0.179
0.189
0.213
0.183

80

S. Yu. Lvov et al.

0.32

Since C > C0, we will estimate the possibility of the existence of the relation

0.30

CCu/CFe = KCu/KFe = const

[Cu], mg/liter

0.28
0.26
0.24
0.22
0.20
0.18
2.2
0.23

2.4

2.6

2.8

3.0

3.2[Fe], mg/liter

for different groups of transformers (CCu and CFe are the copper and iron concentrations).
The relation between the copper and iron content in the
oil of operating transformers is illustrated in Fig. 2.
A correlation analysis of the data in Table 2 revealed approximately three similar groups of transformers, in which
relation (6) is satisfied fairly well. The results of a correlation
analysis of the relation between the copper and iron concentrations in transformer oils for these groups of operating
transformers are presented in Table 3 in the form of constants
for the numerical relation

0.22

[ Cu] =

[Cu], mg/liter

0.21

K Cu
K Fe

[ Fe] + B.

(7)

0.20
0.19
0.18
0.17
0.16
2.2

2.4

2.6

3.0

3.5

2.8

3.0 [Fe], mg/liter

0.30

0.28
0.26

[Cu], mg/liter

(6)

0.24
0.22
0.20
0.18
0.16
2.5

4.0

4.5 [Fe], mg/liter

Fig. 2. Relation between the content of copper and iron ions in


the oil of working transformers: a, the ratio of the effective rate
constants of the formation of copper and iron compounds
0.10677 0.01264; b, for a ratio of 0.06774 0.00957; c, for
0.04674 0.00516.

As follows from the data in Table 3, the correlation coefficient for these groups of transformers is fairly high, which
indicates the deterministic nature of the formation of copper
and iron in oil during the operation of transformer equipment. However, the ratio of the current concentrations of
copper and iron for the different groups of transformers investigated may differ by more than a factor of 2.
We have not found, from the results of the analysis, any
strict correlation relationship between the concentrations of
the metals in the oil and the optical turbidity factor. This indicates that the turbidity factor is an integral function of the
state of the oil, which takes into account the formation not
only of metal-containing colloidal particles, but also of soluble sludge, and also of colloidal particles of oxidized compounds of oil hydrocarbons and water.
By analogy with the optical turbidity factor it is useful
to take the limiting values of the copper and iron content
in transformer oil, defined as follows: the oil in 90% of the
total number of operating transformers has lower or equal
values. According to our results, the limiting values in the
working oil of power transformers and shunting reactors are
as follows:
optical turbidity 200 m1;
copper concentration 0.26 mg/liter;
iron concentration 3.2 mg/liter.
Values greater than this may serve as a basis for taking a
decision on whether to replace the silica gel in the oil filters
of power transformers and shunting reactors or regenerate

TABLE 3. Correlation Analysis of the Relation Between the Concentrations of Copper and Iron in the Oil of Working Transformers
Group

Number of the analysis point in Table 2

KCu/KFe

Correlation
coefficient R

1
2
3

12, 13, 14, 16, 17, 20, 22, 23, 27, 30, 43, 48, 49, 51, 52, 65
6, 9, 10, 11, 18, 26, 37, 39, 41, 42, 46, 54, 55, 57, 64
2, 3, 5, 7, 8, 15, 24, 25, 33, 34, 36, 38, 50

0.10677 0.01264
0.06774 0.00957
0.04674 0.00516

0.05852 0.0354
0.01192 0.02584
0.04691 0.01751

0.931
0.900
0.940

Contamination of the Transformer Oil of Power Transformers and Shunting Reactors

the oil in addition to the oil contamination factors, standardized in [10] the dielectric loss tangent and the acid
number of the oil.
CONCLUSIONS
1. We have analyzed the dynamics of the change in the
turbidity factor and in the content of copper and iron in the
oil of power transformers and shunting reactors. We have
considered methods of determining the copper and iron concentration in transformer oil.
2. On the basis of our statistical investigations of the
contamination of transformer oil by colloidal particles, we
have determined the limiting values of the optical turbidity
factor and the copper and iron contents, any excess of which
may serve as a basis for taking a decision on whether to replace the silica gel of the oil purification filters of power
transformers and shunting reactors or to regenerate the oil
in addition to the standardized oil contamination factors.
REFERENCES
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hermetic leads of transformers, lektr. Stantsii, No. 4 (2000).

81

2. Systematic Indicators in Determining the Optical Turbidity of


the Transformer Oil of the Hermetic Leads of 110 kV and
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Approved JSC RAO EC Rossii VI/21/2007.
3. A. Vita, P. R. T. Patrocinio, S. A. Godinko, et al., The Effect
of Passivator Additive Used in Transformers and Reactors
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on Low Thermal Defect, CIGRE-2008, A2-215.
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in the Oil [in Russian], Moscow (2001).
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