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SF6 contaminated by SO2: Dielectric strength and influence on sealing materials

Conference Paper · June 2014

DOI: 10.1109/EIC.2014.6869434

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SF6 contaminated by SO2: Dielectric strength
and influence on sealing materials
M. Mattoso, F. Wypych, V. Cruz, L. H. Meyer, Senior Member, IEEE, N. A. Gomez, P. O. Fernandes,
Member, IEEE, and H. M. Wilhelm, Member, IEEE
 atom. This stability makes it a useful gas in electrical
Abstract-- This work investigates the influence of the presence
of SO2 in SF6 regarding its breakdown voltage. A test chamber
was built to accommodate a gas pressure of 2 bar, with a pair of
electrodes inside, separated by a variable distance. The SO2
concentration in SF6 was 0,5 and 500 ppm. Preliminary results
indicate that the influence of the presence of SO2 in SF6 regarding
the breakdown strength is minimal. The effect of SO2 was also
investigated on the switchgear sealing. For this purpose a metal
chamber was designed and built to test pure SF6 and mixtures of
SF6 and SO2 under 20 bar pressure, at 120 °C, for two months
with different sealing materials, in order to evaluate the relative
degradation of these materials. Preliminary results indicate that
these mixtures can affect the mechanical resistance of the sealing
material.
Index Terms - Accelerated aging, Contamination, Degradation,
Dielectric measurement, Gas insulation, Greenhouse gases, Power
system faults, Rubber, Sealants, Sulfur hexafluoride
I. INTRODUCTION
T HE Kyoto Protocol requires the gradual reduction of
atmospheric emissions of gases responsible for the
greenhouse effect, or global warming. In Brazil, the Kyoto
Protocol was internalized by means of Legislative Decree 144
of 2002, which gives legal status to the commitments made
under it.
Sulfur hexafluoride (SF6) is a greenhouse gas that is used
by electric utilities as an insulating medium and extinguishing
arc in circuit breakers [1], specifically in regions of high
population density, where small size of substations is
important.
It is a clear, odorless, non-flammable, non-toxic and
chemically stable gas and under normal conditions of
temperature and pressure it does not react with another
substance [2]. Its stability comes from the symmetrical
arrangement of the six fluorine atoms around the central sulfur
This work was supported by CTEEP.
M. Mattoso works for DIAGNO, Paraná, Brazil (e-mail:
mattoso@diagno.com.br).
F. Wypych is a professor in the Department of Chemistry, Federal
University of Parana (UFPR), Paraná, Brazil (e-mail: wypych@ufpr.br).
V. Cruz Mattoso works for CTEEP, São Paulo, Brazil (e-mail:
vcruz@cteep.com.br).
N. A. Gomez works for DIAGNO, Paraná, Brazil (e-mail:
neffer@diagno.com.br).
P. O. Fernandes works for DIAGNO, Paraná, Brazil (e-mail:
fernandes@diagno.com.br).
H. M. Wilhelm works for DIAGNO, Paraná, Brazil (e-mail:
helenaw@diagno.com.br).
1
equipment.
The handling and operation of gas-insulated equipment
always entails the possibility of leakage to the environment if
proper procedures are not followed by maintenance operators.
A study in 1999 by the United States Environmental Protection
Agency (USEPA) [3] found that 15.2% of SF6 installed in the
electrical system of the country was lost to the atmosphere.
Thus, it became clear that the focus of atmospheric
contamination by SF6 lies in the power sector and its use
should be given attention by environmental authorities. Since
then, both the European environmental agencies and the
USEPA have issued detailed regulations aimed at reducing
unintentional SF6 emissions. The results obtained by the
implementation of programs to regulate the use of SF6 in the
American electricity sector meant a reduction in losses of SF6
gas into the atmosphere of about 800 short tons within
approximately six years, which is equivalent, using the current
global warming factor (GWF), to release of about 18 million
tonnes of CO2.
As described in [4], the impact generated by the use of SF6
by a power company is about 43 times greater than that caused
by use of fossil fuels in internal combustion engines.
As SF6 gas is an inert material, it does not attack the
sealing material. However, SF6 degrades during use, causing
the main byproduct gas SO2 (sulfur dioxide). This is a very
reactive gas and readily reacts with oxygen and moisture to
form sulfuric acid, for example. It can attack the gasket
material, leading to leakage points. The seals of electrical
equipment such as gas/oil systems comprise the main barriers
preventing release of SF6 gas into the atmosphere.
The open use of systems with SF6 is banned in the
European Community and in Brazil as well, pursuant to
Legislative Decree 144 of 2002.
A standardized test of compatibility for the sealing
materials used in electrical equipment insulated with SF6 does
not exist. Here we propose a test for this purpose. We also
evaluate the effect of the SO2 byproduct on the dielectric
properties of SF6 gas.
II. EXPERIMENTAL
A. Characterization of new sealing materials
New sealing material samples were characterized by Fourier
transform infrared spectroscopy (FTIR), thermogravimetry
(TGA) and differential scanning calorimetry (DSC).
The FTIR analyses were performed in a Shimadzu IR
Prestige-21 spectrophotometer, using the ATR (attenuated
 2

total reflectance) accessory. The spectra were obtained in the Initially, the distances between electrodes were specified at
spectral region of 4000-650 cm-1 with resolution of 4 cm-1. 1, 2, 5 and 10 mm. In this work, the breakdown voltage for 1,
TGA analysis was performed on a Shimadzu TG-50 2, and 5 mm distances were measured.
analyzer under continuous flow of 50 and 100 mL. min-1 of
nitrogen (carrier gas).
DSC measurements were performed with a Shimadzu DSC-
50 calorimeter in nitrogen atmosphere with continuous flow of
50 to 100 mL. min-1.
The Shore A hardness was measured with a durometer. The
hardness value was determined by the penetration of the
durometer indenter foot into the sample according the ASTM
D2240 test method.

B. Accelerated aging tests of sealing materials in different

gaseous environments
An aging test apparatus to perform accelerated aging under
thermal stress (Fig. 1) of sealing materials (gaskets) with gases
was designed and built. Samples of sealing materials from four
Figure 2. Final version of the chamber, which have employed Teflon and
different suppliers (called S1, S2, S3 and S4) were inserted in Plexiglas, and electrodes shown externally.
six aging cells. Each of these six cells was pressurized to 40
bar with a different atmosphere: nitrogen (N2), pure SF6 and
mixtures of SF6/SO2 with 5, 12, 50 and 501 ppm of SO2. These
cells were placed in a preheated oven at 120 °C. After 1,529
and 2,321 h, the aged sealing material specimens were
removed. These materials were then analyzed for hardness and
submitted to FTIR and DSC analysis, using the same
equipment and conditions described in item A.

a) b)
Figure 3. a) Setup used for 60Hz and impulsive applied voltages. b) Detail of
the hemispherical electrodes.

III. RESULTS AND DISCUSSION

Figure 1. Cell used in accelerated aging tests of sealing materials from
different suplliers with N2, SF6 and mixtures of SF6/SO2.
C. Effect of the SO2 byproduct on the dielectric strength of SF6
A test chamber was built to evaluate the dielectric strength
of SF6 and mixtures of SF6 and SO2, at 60 Hz and impulsive
applied voltages, for various electrode distances. After testing,
the information was processed to obtain the breakdown
voltage for the gas medium under study. Fig. 2 shows the
chamber and electrodes used in the test.
To connect the SF6 gas cylinders to the test chamber, it was
necessary to install proper tubing, capable of supporting the
pressure in the gas cylinders. It was also necessary to use
pressure reducers and safety valves, as seen in Fig. 3. The tests
followed the IEC 60060-1 standard for 60 Hz (industrial
frequency) and impulsive applied voltage. A typical setup is
shown in Fig. 3, while Fig. 3b shows a detail of the
hemispherical electrodes.
A. Characterization of new sealing materials
Initially we determined the type of elastomer comprising
the sealing materials (S1, S2, S3 and S4). This analysis was
performed by FTIR. Ethylene-propylene rubber (EPDM) was
identified as the base polymer of the four sealing materials.
The major bands of this elastomer are shown in Table 1 [5].
TABLE 1
MAIN FTIR ABSORPTION BANDS OF THE NEW SEALING MATERIALS [5]
Assignments Wavenumber (cm-1)
C-H stretching 2925, 2850
CH2 deformation 1460, 712
CH3 deformation 1375
Thermogravimetric analyses were performed to evaluate
the thermal stability of the sealing materials. It was possible to
observe some differences in the thermogravimetric curves of
the materials, attributed to the addition of different types or
quantities of plasticizers or additives in the rubber production
process (Fig. 4). Up to about 235 °C no weight loss for any of
the sealing materials occurred. The greatest weight loss
occurred around 475 °C for all the materials. S2, S3 and S4
showed a second loss at about 560 °C, but this loss was not
 3

100 S1
observed for S1. Although the base polymer is the same
(EPDM) the thermogravimetric curves showed that the 90

formulations of the four gaskets are different. 80

Hardness (Shore A)
70
100
60
S1
S2 50

80 S3 40
S4
30

20
60
Mass (%)

10

0
40

SO2 501ppm, 2321 h

SO2 5ppm, 1529 h

SO2 5ppm, 2321 h

SO2 12ppm, 1529 h

SO2 12ppm, 2321 h

SO2 501ppm, 1529 h

SO2 50ppm, 1529 h

SO2 50ppm, 2321 h

N2 2321 h
Non-aged

SF6 1529 h
SF6 2321 h
N21508 h
20

0
100 200 300 400 500 600 700 800 100
S2
0 90
Temperature ( C)
80
Figure 4. TGA curves for the new sealing materials: S1, S2, S3 and S4.

Hardness (Shore A)
70

With the DSC analyses it was possible to evaluate the glass 60

transition temperature (Tg) of the new sealing materials. The 50

Tg values followed this order: S3>S4>S1>S2 (Fig. 5). 40

Different Tg values can be assigned to different processing 30

parameters and to the incorporation of different types and/or 20
amounts of plasticizers and additives. The amount of ethylene 10
in the EPDM elastomer, for example, will affect the 0
equipment's end-use characteristics. A high concentration of

SO2 501ppm, 2321 h

SO2 50ppm, 1529 h

SO2 50ppm, 2321 h

SO2 12ppm, 1529 h

SO2 501ppm, 1529 h

SO2 5ppm, 1529 h

SO2 5ppm, 2321 h

SO2 12ppm, 2321 h

SF6, 2321 h
N2, 1508 h

SF6, 1529 h
N2, 2321 h
Non-aged
ethylene imparts a more crystalline nature to the EPDM and
will increase its Tg and melting temperature.
S1
exo S2
S3
S4 Figure 6. Shore A hardness of non-aged and aged sealing materials: S1 and
S2.
Heat flow (mW/mg)

FTIR spectra of aged sealing materials were obtained in

-80 -60 -40 -20
0
Temperature ( C)
Figure 5. DSC curves for the new sealing materials: S1, S2, S3 and S4.
A. Accelerated aging tests of sealing materials in different
gaseous environments
The Shore A hardness measurements (Fig. 6 and 7) showed
some differences in the aged sealing materials in comparison
with non-aged samples. When aged under N2, an increase in
Shore A hardness was observed for S1, S2 and S3, indicating
stiffening of the gaskets by the effect of overheating at 120 0C
(Fig. 6 and 7). S4 had decreased stiffness after aging with N2
and SF6, indicating an increase in the flexibility of this material
(Fig. 7). Hardness remained practically constant for all the
sealing materials aged in the different mixtures of SF6/SO2.
order to identify any structural changes in the material in
comparison with non-aged samples (Fig. 8). Non-specific
interactions between all the EPDM gaskets and SF6 or SO2
were observed by the FTIR tests. This finding is based on the
absence of shifts or appearance of new bands that could
indicate interaction processes [6]. Changes in the intensity of
the main absorption bands of EPDM could be observed for all
0 20
aged sealing materials, including the specimens aged in N2
atmosphere (Fig. 8), showing that the temperature may have
contributed to these changes. Aging tests at different
temperatures are being conducted to better evaluate this effect.
The bands at 2357 and 2310 cm-1 in Fig. 8 are attributed to
carbon dioxide (CO2). After aging in N2, a decrease in the Tg
value of 3 °C for S1 and an increase of 4.6 °C for S2 (Table 2)
were observed. The Tg of S3 and S4 remained unchanged
(Table 2).
There are basically five factors that influence the Tg: free
volume, intermolecular forces, chain length, chain stiffness
and mobility of side groups. Double or triple bonds, for
example, tighten the chain and thereby increase the Tg. The
effect of these factors is still under evaluation based on the
analysis of specimens aged for longer times and at other
temperatures.
 4

100
S3
B. Effect of the SO2 byproduct on the dielectric strength of SF6
90
Table 3 shows the breakdown voltage as according to the
80
Hardness (Shore A)
IEC 60060 test standard for 60Hz. Table 4 shows the
70
impulsive voltage test results. Both tables are based on
60
intermediate spreadsheets as recommended by the IEC
50
standard.
40
The dielectric tests indicated higher breakdown strength of
30 SF6 than air as an insulating medium, for both 60Hz and
20 impulsive voltages. Also, the dielectric strength of the SF6 was
10 not affected by the presence of SO2. However, testing has to be
0 conducted with other electrode spacing distances.

SO2 12ppm, 2321 h

Non-aged

SO2 501ppm, 2321 h

SO2 50ppm, 1529 h

SO2 50ppm, 2321 h

SO2 5ppm, 2321 h

SO2 12ppm, 1529 h

SO2 5ppm, 1529 h

SO2 501ppm, 1529 h

N2, 1509 h

SF6, 1529 h
N2, 2321 h

SF6, 2321 h

TABLE 1
60 HZ BREACKDOWN VOLTAGE FOR AIR AND SF6, FOR ELECTRODE SPACING OF 1 mm,
2 mm AND 5 mm.

Breakdown Voltage at 60 Hz
Gas
100 S4 1 mm 2 mm 5 mm
90
Air at 1 atm 2.63 kV 6.23 kV 11.9 kV
80

70 SF6 + 5 ppm SO2 at 2 bar 17.83 kV 35.7 kV 62.9 kV

Hardness (Shore A)

60
SF6 + 500 ppm SO2 at 2 bar 19.86 kV 34.8 kV 61.6 kV
50

40
TABLE 2
30 IMPULSIVE BREAKDOWN VOLTAGE FOR AIR AND SF6, FOR ELECTRODE SPACING OF
1 mm, 2 mm AND 5 mm.
20

10 Impulsive Breakdown Voltage

Gas
0
1 mm 2 mm 5 mm
SO2 501ppm, 2321 h
SO2 12ppm, 1529 h
SO2 5ppm, 2321 h

SO2 501ppm, 1529 h

SO2 12ppm, 2321 h
N2, 2321 h

SO2 50ppm, 1529 h

SO2 5ppm, 1529 h
SF6, 1529 h
N2, 1509 h

SO2 50ppm, 2321 h

SF6, 2321 h
Non-aged

Air at 1 atm 9.2 kV 24.0 kV -

SF6 + 5 ppm SO2 at 2 bar 30.6 kV 59.0 kV 106.6 kV

SF6 + 500 ppm SO2 at 2 bar 30.8 kV 60.1 kV 97.5 kV

Figure 7. Shore A hardness of non-aged and aged sealing materials: S3 and
S4.
IV. CONCLUSION
TABLE 2
GLASS TRANSITION TEMPERATURE (Tg) OF NON-AGED AND AGED SEALING MATERIALS IN N2. Different properties were observed for the sealing materials
from different suppliers, especially as revealed by TGA, DSC
Sealing material Non-aged Aged
and Shore A hardness testing, indicating differences in the
S1 -42.3 -45.3 formulations. After accelerated aging at 120 °C, some of these
properties changed, being more pronounced in N2, SF6 or
S2 -46.5 -41.9
mixtures of SF6 and SO2, depending on the sealing material.
S3 -39.8 -40.9 Additional studies are being conducted to better understand
the influence of aging conditions and chemical composition
S4 -41.1 -41.1
change on these properties.
The variation of the dielectric strength of SF6 is little
affected by the presence of SO2, however, further tests are
ongoing, considering the additional distances presented.

Non-aged V. ACKNOWLEDGMENT
Absorbance (a.u.)

We acknowledge the financial support CTEEP, ANEEL the

Aged in N2 Diagno, FURB and Federal University of Paraná. We also
thank CTEEP and ANEEL for the approval of the project (no.
Aged in SF6 PD-0068-0024/2011), and Diagno, FURB and UFPR for
providing infrastructure and technical support.
Aged in S02, 500 ppm
VI. REFERENCES
3500 3250 3000 2750 2500 2250 2000 1750 1500 1250 1000 750
[1] J. Sihvenger, A. de Souza Machado, A. Martins, E. Marques, J. Leite, L.
-1
Wavelenght (cm ) Chanas. “Manuseio, segurança e manutenção de hexafluoreto de enxofre
Figure 8. FTIR spectra of non-aged and aged sealing material: S4. (SF6) em equipamentos elétricos”. Cigre-Brasil, 2012.
 5

[2] Task Force B3.02.01. “Guide for the preparation of customised 2
practical SF6 handling instructions". Cigre, 2005.
[3] United States Environmental protection Agency. “Publicação EPA 430-
R-11-005: Inventory of U.S. Greenhouse Gas Emissions and Sinks:
1990 – 2009”, pag 4-72, publicado em 15/04/2011.
[4] H. M. Wilhelm, Fernandes, P. O., V. Cruz, D. Gonçalves. “A
transmissão de energia elétrica e o aquecimento global: o papel da
manutenção de equipamentos isolados a SF6”. EletroEvolução No. 70,
pp. 16-22, 2013.
[5] R. Silverstein, F.Webster, and D. Kiemle. “Spectrometric identification
organic compounds”. New York: John Wiley & Sons, Inc. 2005.
[6] M. Umata. “Sistema para análise de subprodutos da degradação do gás
SF6 por espectroscopia no infravermelho com transformada de Fourier”.
Curitiba: Dissertação apresentada como requisito parcial à obtenção do
grau mestre. Programa Interdisciplinar de Pós-graduação em
Engenharia. Setor Tecnologia. Universidade Federal do Paraná. 2000.
VII. BIOGRAPHIES
R&D for quantifying emission of greenhouse gases in 2007 and is currently
manager of the project “Development of methodology for assessing and
minimizing the causes of leakage and deterioration of sealing materials in
equipment insulated with SF6” and an equipment specialist with CTEEP
(Paulista Electricity Transmission Company).
Luiz Henrique Meyer was born in Blumenau, SC,
Brazil in April 1968. He received his B.S. and M.S.
in Electrical Engineering from the Federal
University of Santa Catarina, Florianópolis, Brazil,
in 1991 and 1994, respectively. He received his
Ph.D. in Electrical Engineering from University of
Waterloo, Waterloo, Canada in 2003. He joined the
Electrical Engineering Dept. of the Regional
University of Blumenau, Blumenau, Brazil, in 1993
where he is involved with academic and research
activities. In 1999 he was director of the Technological Research Institute of
Regional University of Blumenau, Blumenau, Brazil.

Neffer Arvey Gómez was born in Cauca, Colombia

Helena Maria Wilhelm was born in Cerro Largo, in 1988. He received a B.Sc. in chemistry from Valle
Brazil in 1971. She received a B.Sc. in Chemistry University, Cali, Colombia in 2005 and a M.Sc. in
from the Federal University of Paraná, Curitiba, materials engineering from Federal University of
Brazil in 1993, a M.Sc .in Chemistry from Federal Paraná, Curitiba, Brazil in 2013.
University of Santa Catarina, Florianopolis, Brazil
in 1996 and a Ph.D. in Chemistry from State
University of Campinas, Brazil in 2000. Currently
she works on research and development projects
with the companies Diagno and Lactec, and is a
professor in the graduate course in technology
development of Lactec.

Fernando Wypych was born in São Mateus do Sul,
Paraná, Brazil, in 1959. He received a B.SC in
Chemistry from Federal University of Paraná
(UFPR) in 1984, a M.Sc. in Inorganic Analytical
Chemistry from Catholic University of Rio de
Janeiro in 1987, a Ph.D. in Inorganic Analytical
Chemistry from the same institution in 1992 and
post-doctoral degree from the Swiss Federal Institute
of Technology in 1997. Currently he is associate
professor at UFPR and performs research in the area
of intercalation compounds, chemical modification
of layered surfaces and applications of compounds in polymer
nanocomposites and catalysts. Currently he is a member of the editorial
boards of The Open Catalysis Journal and The Open Colloid Science Journal,
acts as a reviewer for 87 scientific journals and is editor of the book Clay
Surfaces - Fundamentals and applications (2004), published by Academic
Press.
Paulo de Oliveira Fernandes was born in Rio de
Janeiro, Brazil, in 1954. He has a B.Sc. in Chemical
Engineering from Rio de Janeiro State University in
1980 and a M.Sc. in Polymer Science and
Technology from Rio de Janeiro Federal University
in 1985. He worked at the Electrical Energy
Research Center – CEPEL as a researcher from 1981
to 1985; the Paraná State Power Company, as
Manager of the the Dielectrics Laboratory from
1985 to 1987; Westinghouse do Brasil Services
Division, as manager of the Dielectric Materials Laboratory and quality
manager and marketing manager for the Services Division from 1987 to
1993; and SDM do Brasil, as managing director from 1993 to 2008. He
currently is the managing director of the Diagno Research and Development
Laboratory. He has been a member of the Brazilian Standards Organization
since 1981 and is also a member of CIGRÉ Brasil.

Maurício Mattoso was born in Curitiba, Brazil, in

1978. He received a B.Sc. in Industrial Chemistry
from the Pontifical Catholic University of Paraná,
Curitiba, Brazil, an MBA in Environmental
Management Systems and a Master's in Materials
Engineering from Federal University of Paraná. He
has more than ten years of experience in SF6 gas
insulated systems, acting in monitoring and quality
control. Currently he is coordinator of the CE-03:
010.3 study group of the Brazilian Committee of
Electricity - COBEI, affiliated with the/ Brazilian Association of Technical
Standards - ABNT.

Vanderlei Ricardo Cruz was born in Itajubá,

Brazil in 1967. He has a technical certificate in
mechanics in Technical School from Itajubá, a
B.Sc. in Production Engineering from São
Francisco University, graduate specialization in
Project Management from the Jundiaí Polytechnic
University, and a M.Sc. in Materials Technology
from LACTEC. He worked as project manager of

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