Identification of DC corona generating SF6
decomposition gases adsorbed on CNT gas sensor
using FTIR Spectroscopy
Yul Martin, Zhenyu Li, Takuya Tsutsumi, Junya
Suehiro
Dept. of Electrical and Electronic Engineering
Kyushu University
Fukuoka, Japan
suehiro@ees.kyushu-u.ac.jp
Abstract—It is important to detect decomposition of insulating gas
SF6 caused by partial discharges for gas-insulated switchgear (GIS).
In the previous result, the author developed a novel partial discharges
sensing using carbon nanotube (CNT) gas sensor. In recently, an
application of high voltage DC for long distance electric power
transmission has been often used in various countries as the
interconnection system and overload demand. In this study we
applied the CNT gas sensor to detect partial discharges generated by
high voltage DC. There was polarity profile for DC compared AC
discharges. It was found, response of the sensor in the case of
negative discharges was much higher than positive discharges under
the same experimental condition. And the decomposed gases for each
case were identified by FT-IR spectroscopy. The result indicated
absorption peaks correspond to SF4 and SOF2 of positive discharges
was much higher than that of negative discharges.
Keywords-DC discharges;partial discharges;SF6decomposition
gases;gas insulated switchgear; carbon nanotube; gas sensor
I. INTRODUCTION
From1960, a high voltage direct current (HVDC) has been
recognized to be used for long distance electric power
transmission caused have had advantageous to support the
growth of renewable energy and integration into electricity
grids with the higher capacity and efficiency [1]. Gas insulated
Switchgear (GIS) for HVDC transmission filled with sulfur
hexafluoride (SF6) as insulation and arc-quenching medium,
are widely used because of high reliability and small size.
However, the partial discharges (PD) caused by small
protrusion, void, or impurities decompose SF6 resulting
deterioration of insulation. A sensitive PD measurement is
necessary for evaluation of the insulation condition. Early
detection of PD can provide a way to predict and avoid the
fatal failure.
For the PD measuring of physical effect as well as ultra
high frequency (UHF), acoustic emission (sound), optical
978-1-4244-6890-4/10$26.00 ©2010 IEEE
Kiminobu Imasaka
Dept. of Electrical Engineering
Kyushu Sangyo University
Fukuoka, Japan
Shinya Ohtsuka
Dept. of Electrical Eng. and Electronics
Kyushu Institute of Technology
Fukuoka, Japan
emission (light) had been developed [2]. Moreover, the gas
sampling method detecting decomposition gas products, has
been also regarded as effective technique. Up to now,
decomposition products were successfully detecting using a
detection tube, a gas chromatography, a mass spectrometer
and an ion mobility spectrometer [6]. The detection tube is
handy and can detect main decomposition products such as
sulfur dioxide (SO2) or hydrogen fluoride (HF) at ppm-levels.
However, the detection tube suffers from poor accuracy and is
not suitable for automated remote monitoring. On the other
hand, the gas chromatography and the spectrometers with high
sensitivity are costly and suitable for laboratory-based analysis
rather than on-line monitoring. It is essential to develop a new
type of gas sensor, which is easy to use on-site and sensitive
enough to detect slight PD in SF6.
It is well known that SF6 decomposition gases under
electrical discharge and overheating are consists of SF4, F2,
SOF2, SO2F2, SOF4, SO2, and HF as a result produced of SF6
decomposition and the reactions with water vapor and oxygen
under discharges condition [3]. To date, several kinds of gas
sensor has been proposed to detect SF6 decomposition gases
[3-4]. For example, ion-conductive solid electrolyte, which
could cause an electrochemical reaction with HF to generate
ion current, has been successfully used as a SF6 decomposition
gas sensor [3]. However, it is be used to detect only arc
discharge and local overheating in GIS.
In the previous study [6], the authors proposed a new
detection method of PD generated in SF6 gas using a gas
sensor composed of carbon nanotubes (CNTs). Recently,
interest in CNTs has been rapidly growing in various scientific
and engineering fields. Especially, CNT-based gas sensors [6]
have received considerable attention because of their
outstanding properties such as faster response,higher
sensitivity, lower operating temperature and a wider variety of
1
663 TENCON 2010
detectable gas. The authors have proposed a new fabrication
method of a gas sensor composed of multi-wall carbon
nanotubes (MWCNTs) using dielectrophoresis (DEP) [7].
In this study, it was investigated that the sensor response to
decomposition gas SF6 generated HVDC PD and component
of the gas by FT-IR spectroscopy. The FT-IR spectra of SF6
decomposition gas were taken from a KBr card comprising
CNT. The card was exposed by the positive and the negative
partial discharges. At that time, several components of the
decomposed gas were adsorbed on CNT in Kbr card. We
considered the adsorbed gas causes the sensor response. FT-IR
absorbance peaks were observed around 735 cm-1 and 480
cm—1. Based on this result, SF4 and SOF2, which were
attributed responding the sensor after PD generated. In our
case, absorbance peaks of positive were larger than that of
negative. Additionally, it was discussed the sensor response of
negative partial discharges was higher than that of positive..
II. EXPERIMENTAL METHOD
The objective of the experiment was to investigate
adsorbed components of the SF6 decomposition gases using
FT-IR spectroscopy and comparing with the measurement by
passive detector tubes. The schematic diagram of experimental
setup for PD detection is shown in Fig.1 [9]. The experimental
setup fundamentally consisted of an high voltage DC power
source, a model stainless steel cylinder tank (50 cm inner
diameter, 90 cm long), an electrode system (point-to-plane
electrode system made of stainless steel with 50 µm point
radius and 10 mm gap length), CNT sensors, and an
impedance measuring system (a lock-in amplifier controlled
by a PC). The electrode system was vertically placed in the
tank, which was filled with fresh SF6 gas at atmospheric
pressure before each test run. The CNT sensors were placed in
the stainless steel cylinder tank and in the same plane as the
plane electrode. The fabrication method of CNT gas sensor
has been described in detail in the previous paper [8]. The
distance x of the sensor from electrode was 10 cm along the
horizontal axis of the stainless steel cylinder tank.The
impedance change of the sensor response was continuously
measured at room temperature and 100 kHz. DC high voltage
at +15 kV and -15 kV was applied to the point electrode to
generate corona discharge (simulated PD). The PD signals
were detected using a shunt resistance of 50Ω inserted
between the plane electrodes to ground.
Fig.1 Experimental setup of PD exposure of CNT gas sensor
664
In order to analyze SF6 decomposed products generated
HVDC partial discharges adsorbed on CNT of the gas sensor
and KBr card comprising CNT was placed same position of
the CNT gas sensor in tank. HVDC was applied to needle to
generated PD for 4,8 or 18 hours. After the PD exposure, the
Kbr card was used for taking FT-IR spectra. Within 30
minutes after the PD exposure. FT-IR analysis was done using
FTIR-620 (Jasco Corporation, Japan) within 30 minutes after
the PD exposure. All our experimental were carried out at
atmosphere pressure (0.1 MPa SF6) and ambient temperature.
The decomposition of SF6 by positive and negative corona
discharges has been investigated using FT-IR spectroscopy.
Before the FT-IR analysis of PD decomposition, the FT-IR
spectra measured using sample placed in ambient air or SF6
gas for hours in order to obtain background sognal.
III. EXPERIMENTAL RESULT
Figure 2 shows FTIR spectra at various measurement with
KBr card only and Kbr Card including CNT gas sensor at
negative and positive polarity applied voltage U = + 15 kV or
-15 kV for 4 hours. This result suggests that KBr card only did
not detection by FT-IR, which that needed uses CNT as
adsorbed gas molecules. Remarkable absorbed peak were
appeared around of 735 cm-1and 480 cm-1. The absorbance at
735 cm-1 and 480 cm-1 was not observed without the PD and
increased with PD duration (Fig.4 and 5). Comparing the
absorbance peaks between negative and positive PD polarities,
the peaks of absorbance of the positive PD much larger were
than that negative.
0.2
Negative PD
0.15
Positive PD
Absorbance
0.1
KBr card with CNT
0.05
KBr card only
0
KBr card
KBr CNT
Positive
Negative
-0.05
1600 1200 800 400
Wavenumber (cm-1)
Fig.2 FTIR spectra of SWCNT with the KBr card without
CNT and with CNT gas sensor.
2
 Figure 3 summarizes previously reported FT-IR spectra of
SF6 and typical SF6 decomposition gas species, which can be
adsorbed on CNT gas sensor [7]. These data were used as
reference for identifying the FT-IR spectra obtained in this
study. Figure 4 depict that the FT-IR spectra obtained under
negative PD generated in SF6 for 4,8 and 18 hour,
respectively. Remarkable absorbed peaks were appeared
around of 735 cm-1 and 480 cm-1. The absorbance at 735 cm-1
and 480 cm-1 was not observed without the PD duration.
Figure 3 Summary of adsorption bands of main SF6
decomposition by product and interference gas.
0.6
NDC 18h
NDC 8h
0.5 NDC 4h
No PD
0.4
Absorbance
0.3
0.2
0.1
0 IV.
900 800 700 600 500 400
Wavenumber (cm-1)
Figure 4 FT-IR spectra of CNT gas sensor exposed to PD
generated by HVDC under negative voltage polarity.
In this result, absorbance peak after occurred the SF6
decomposition gases increased with the PD application time. It
means amounts of decomposition product tend to increase with
increasing time of exposure. Figure 5 shows the FT-IR spectra
obtained under PD generated in SF6 for the duration time with
positive voltage polarities. The absorbance peaks tends
665
appeared at 735 cm-1 and 480 cm-1. According to some
literatures, this absorbance peaks correspond to SF4 or SOF2
that of decomposition by product as shows at Fig.3 [11] This
result also the same with our previous study using high voltage
AC [10].
Comparing the absorbance peaks between the negative and
the positive PD polarities. The peaks of positive were higher
than that of the negative The absorbance peaks values of the
negative were smaller as about 0.15 and 0.1 and 480 cm-1
rather than that of the positive. Both of the value of absorbance
peaks increasing as gas molecule can adsorbed the
decomposition gases on CNT gas sensor surface depend on
discharges energy at duration time PD exposure. In this case
positive DC polarity faster reaches peak compared with the
negative DC polarity. However, we compare with the result of
response of CNT gas sensor [8], which the author had been
research for detecting SF6 decomposition generated by HVDC.
As long as that the data of negative DC polarity much higher
than positive in the same experimental condition.
PDC-18h
PDC-8h
2.5 PDC-4h
No PD
2
Absorbance
1.5
1
0.5
0
900 800 700 600 500 400
Wavenumber (cm-1)
Fig.5 FTIR spectra of CNT gas sensor exposed to PD
generated by HVDC under positive voltage polarity.
DISCUSSION
A. Identification and determines of SF6 decomposition product
by FTIR.
When SF6 is in environment of electrical discharges,
including arc or glow, spark, and partial discharges (corona
discharges) will dissociate into lower order sulphur fluorides,
sulphur and fluorine. It is known that major primary
decomposition products such as SF5,SF4, and SF2 are produced
in corona discharges by electron impact as follows [5] :
SFx + e-  SFx-1 + F + e-1 (6≥x≥1) (1)
The stain less steel chamber of high voltage system equipment
is usually not a contamination-free environment. Some of the
3
dissociation of SF6 will react with contaminant such as water
vapour (H2O) or oxygen (O2) and with the metal surfaces and
electrodes of the discharges chamber to form stable gaseous
molecular species including gaseous sulfur oxyfluoride, SOF2,
SO2F2, and SOF4; sulfur oxide, SO2; and hydrofluoric acid,HF;
as well as solid product such as metal fluoride [10]. For
example, SF4 react with H2O and undergo hydrolysis as :
SF4 + H2O  SOF2 + 2 HF (2)
SOF2 + H2O  SO2 + 2 HF (3)
The final decomposition products, SO2 and HF, have been
widely employed as consequence, a reduction in SF6
concentration takes place and the insulating efficiency of the
system is degraded. Eventually, the SF6 must be renewed, if
failure of insulation is to be prevented.
In this study, however, we did not observe absorption of
spectra SO2 and HF due to background absorption of H2O,
shown in the Fig.3. But it did not mean that SO2 and HF
molecules were not adsorbed on CNT. On the other hand,
adsorption of SF4 or SOF2 (or both) was highly expected from
Fig.4 and 5. The reason of why difficult to detect SF4 or SOF2
separately is that hydrolysis of SF4 into SOF2 is so fast.
Therefore, it has been considered and quantified together as
(SF4+ SOF2) in the past [10]. Although theirs separation are
impossible at this point, the FTIR spectroscopy revealed that
SF4 or SOF2 (or both of them) were adsorbed on CNT.
B. Response of CNT gas sensor to HF and SO2
Although adsorption of SF4 or SOF2 on surface of CNTs
was realized, it has not been clarified yet if they were
responsible for PD response of CNT gas sensor [11]. In order
to discuss this point, the CNT gas sensor responses to HF and
SO2 at ppm level were investigated. The experimental set up
and procedure were almost similar to experimental before but
there were a little different. In this experiment we applied
voltage 20 kV for generating PD in SF6 (0.1 Mpa) and setting
gap length at 10 mm, PD exposure time about 18 to 20 hours.
After the PD stopped, a part of SF6 decomposition gases (25
mL) was taken gas –tight syringe and the gas inject ed into a
small chamber (200µL in volume) for four times during each
10 minutes. Before injected SF6 decomposition gases within
small chamber, we must flowing N2 gas as carrier for 5
minutes. After that we injected SF6 decomposition gases within
chamber for four times during each 10 minutes. The last step of
this experiment that flowing of N2 gases again during 30
minutes. The result was found conductance change under
positive and negative DC polarity.
In this case, an application of CNT gas sensor for off-line
diagnosis (detection was carried out 18 hours later after PD
stopped) using syringe and gas detector tube was realized. It
was found that the CNT gas sensor higher response to the
negative polarity than that positive. The series of experiment to
detect HF and SO2 using detector tube (pump type) at ppm
level with indicate the color change for both of negative and
positive DC polarity. Target of this experiment to detect
decomposition of gases: HF and SO2 in the decomposition gas.
Passive detector tube was detected HF at 1 to 2 ppm level and
SO2 at over 40 ppm for both polarities. This result suggested it
was necessary long period of discharges time to detect HF to
666
higher level as well as 11 ppm level but SO2 more reactive
gases.
Considering the both result, the FTIR spectroscopy and
passive detector tube test, it was suggested that SF4 and SOF2
were possible decomposition component to respond for CNT
gas sensor response. However, it is necessary to investigate
deeply for describing adsorption of molecule gas on CNT gas
sensor for the positive higher than the negative one. It was
identified that SF4 and SOF2 were adsorbed on CNT by FT-IR
spectroscopy.
V. CONCLUSION
We have performed a series of experiment to explore SF6
decomposition gases in HVDC partial discharges. FT-IR
spectra showed that SF4 and SOF2 gas molecules were
adsorbed on CNT gas sensor under exposing the PD in SF6.
ACKNOWLEDGMENT
This result was partially supported by TEPCO Research
Foundation.
REFERENCES
[1] W.Breuer,D.Povl, D.Retzman, and E. Teltsch,” Trends for future HVDC
application,” CEPSI conference 2006. The 16th Conference of the
Electric Power Supply Industry
[2] S.Tominaga, H.Kuwahara, K.Hiroka, T. Yoshioka, SF6 gas- analysis
technique and its application for evaluation of internal condition in SF6
gas equipment, IEEE Trans.Power Appar.Syst PAS-100 (1981) 4196-
4206
[3] B.Belmany,J.Casanova,AM Casanova, “ SF6 decomposition under
power arc-chemical aspect”,IEEE Tran.Elect.Insul., vol.26,pp.1177-
1182, 1991..
[4] T.Minagawa,M.Kawada,S.Yamauchi, MKamei,Nishida, “Development
of SF6 gas sensor,” Surf. Coat Technol., vol. 169/170, pp. 643–645.
1991
[5] R.Irawan,G.B.Scelsi and G.A.Woolsey “Optical fiber sensing of SF6
degradation in high voltage switchgear,” J.Nonlin. Opt Phys., vol
10,pp.181-195,2001..
[6] J.Suehiro,G.Zhou, and M.Hara, “Detection of partial discharges in SF6
gas using a carbon nanotube based gas sensor,” J. Sensors and Actuators
B,105, 2005, pp. 164-169.
[7] H.M.Heise, R.Kurte, P.Fisher,D.Klockow, and P.R.Janissek, “Gas
analysis by infrared spectroscopy as a tool for electrical fault diagnostics
in SF6 insulated equipment ”, Fressenius J.Anal.Chem, vol.358,pp.793-
799,1997.
[8] J.Suehiro,G.Zhou, and M.Hara,” Fabrication of a carbon nanotubes-
based gas sensor using dielectrophoresis and its application for ammonia
detection by impedancy spectroscopy”,J.Phys.D:
Appl.Phys.,vol.36,pp.L109-L114,2003.
[9] Z Li,Y Martin,T.Tsutsumi,K.Imasaka,J.Suehiro,S.Ohtsuka,” Responses
of carbon nanotube gas sensor to partial discharges generated by DCHV
of different polarities in SF6,” Proc. of National Convention of IEEJ
(2010).
[10] W.ding,R.Hayashi,K.Ochi,J.Suehiro,K.Imasaka,M.Hara,N.Sano,E.Naga
o,and T.Minagawa,” Analysis of PD-generated SF6 decomposition gases
adsorbed on carbon nanotubes. IEEE Transac. On DEI, vol
13,No.6,2006.
[11] Y.Martin, Z.Li,T.Tsutsumi,K.Imasaka,J.Suehiro,S.Ohtsuka,” Analysis of
SF6 decomposition gases absorbed on carbon nanotubes under DCHV
partial discharges”, Proc. of National Convention of IEEJ (2010).
4